Effect of reprocessing cycles on mechanical properties and antibacterial

performance of in situ compatibilized PBS/PLA blends doped with HPQM

Panupong Srimalanon1*, Benjaphorn Prapagdee2, Ignacio Martín-Fabiani3,
Narongrit Sombatsompop1
1
Polymer PROcessing and Flow (P-PROF) Research Group,
Division of Materials Technology, School of Energy, Environment and Materials,
King Mongkut’s University of Technology Thonburi (KMUTT), Bangkok 10140, Thailand
2
Laboratory of Environmental Biotechnology, Faculty of Environment and Resource Studies,
Mahidol University, Nakhon Pathom 73170, Thailand
3
Department of Materials, Loughborough University, Leicestershire LE11 3TU, United Kingdom
*E-mail: [email protected]

Hygienic in situ compatibilized polybutylene succinate/polylactic acid (PBS/PLA)

reactive blends (at content ratios of 20/80 and 40/60 wt%) were prepared by adding optimum
dosages of dicumyl peroxide (DCP) as a radical initiator and 2-hydroxypropyl-3-piperazinyl-
quinoline carboxylic acid methacrylate (HPQM) as antibacterial agent via melt blending
process. The effect of reprocessing on mechanical and physical properties, and antibacterial
performance against Escherichia coli of PBS/PLA blends were investigated. The results
showed that varying processing cycles affected the fracture behaviour of PBS/PLA blends. The
toughness of the PBS/PLA blends increased with increasing number of cycles. Three
processing cycles exhibited the highest elongation at break and tensile toughness, while the
number of processing cycles did not significantly affect the tensile modulus and strength. For
the effect of the number of processing on antibacterial performance against E. coli of PBS/PLA
blends doped with HPQM, the percentages of bacterial reduction tended to increase with
contact time, but decreased with increasing number of cycles. The study suggests that
PBS/PLA blends could be reprocessed up to 3 times to retain optimal properties.

1. Introduction thermoplastic that has high tensile modulus

Recently, plastic pollution is and strength.2 However, the brittleness and
considered one of major global issues in the low toughness of PLA is a major drawback
environment. The problem is getting worse for packaging applications. Polybutylene
when the size of plastic decreases to became succinate (PBS) is a flexible biodegradable
“microplastic”. It can be potentially taken up polymer with good toughness and high
and ingested by living organisms, in elongation at break. Many studies have
particular animals.1 The consumption of demonstrated that PLA can be blended with
contaminated animals poses a route for PBS,3-4 resulting in a ductility improvement.
human exposure to microplastic. To prevent Nevertheless, PLA is immiscible with PBS,
the problem of microplastic contamination in resulting in poor mechanical properties due
the environment and food chains, to low miscibility and interfacial adhesion
biodegradable plastics produced from between the two polymers.
renewable resources or bio-based plastics are An effective method for improving
an interesting alternative to replace the miscibility between PBS and PLA is in
petroleum-based synthetic plastic. Polylactic situ reactive compatibilization. In our
acid (PLA) is biodegradable and compostable previous work,5 we found that the addition of PC1

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
dicumyl peroxide (DCP) as a free radical compatibilized PBS/PLA blends doped with
initiator notably increased tensile toughness HPQM.
of in situ compatibilized PBS/PLA blends at Thus, this proposed work of studies
the recommended loading of 0.2 pph. This on the recycling for life extension of in situ
was attributed to the formation of branching compatibilized PBS/PLA blends. The
and/or crosslinking networks which prevent changes in mechanical properties and
coalescence and improve toughness antibacterial performances of recycled
properties of the blends. In addition, in situ hygienic in situ compatibilized PBS/PLA
compatibilized PBS/PLA blends have been blends were characterized and analyzed for
developed for hygienic food packaging different numbers of processing cycles.
products to inhibit and control the bacterial
growth by adding 2-Hydroxypropyl-3- 2. Materials and Methods
piperazinyl-quinoline carboxylic acid 2.1 Materials and chemicals
methacrylate (HPQM) as an antibacterial PLA (Ingeo™ biopolymer, grade
agent. HPQM is claimed to be an 2003D) was purchased from NatureWorks,
environmental friendly organic biocide and is USA. PBS (BioPBS™, grade FZ91PM) was
allowed for use in the food industry.6 purchased from PTT MCC Biochem Co.,
Since PBS/PLA blend packaging Ltd., Thailand. DCP (grade Percumyl D GP),
products have low contamination, recycling purchased from Kij Paiboon Chemical Ltd.
or reprocessing is a feasible method to Thailand, was used as a crosslinker. HPQM
recover the disposed PBS/PLA blend (BioCleanAct™, grade 101A0), obtained by
materials. It does not only extend the life of Koventure Co., Ltd., Thailand, was used as
the blend products but also helps the an antibacterial agent.
biopolymer market financially by 2.2 Specimen preparation and reprocessing
contributing to the circular economy of The PBS/PLA blends were prepared
thermoplastics.7 PLA can be recycled by by adding DCP and HPQM in dry-blended
either mechanical or chemical processes8. PBS/PLA at the content of 20/80 and 40/60
Mechanical recycling presents lower wt% using a high-speed mixer (LMXS;
environmental impacts than chemical Labtech Engineering, Thailand) at 1000 rpm
recycling through a life cycle assessment for 5 min. The optimum contents of DCP and
study. It yields better results than chemical HPQM were 0.2 pph and 2000 ppm,
recycling, in human health, ecosystem respectively. The PBS/PLA blends doped
quality and resources categories.9 with HPQM were melt-blended using a
Żenkiewicz et al. 10 characterized multi- counter rotating twin-screw extruder
extruded PLA properties and found that PLA (HAAKE™ Rheomex CTW 100 QC;
tensile strength, elongation at break and Thermo Fisher Scientific, USA). The
impact strength decreased with rising number temperature profiles of feed to die zone were
of extrusion cycles, while melt flow rate, adjusted at 165, 170, 175 and 180 °C with a
water vapor and oxygen permeability screw speed of 60 rpm. The pellets
increased. To the best of our knowledge, compounds were processed for different
there have been no reports regarding the number of cycles (1, 2, 3, 4 and 5). The
mechanical properties and antibacterial specimens were prepared by a compression
performance of multi-reprocessed in situ molding machine (LP-20M; Labtech
PC2

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Engineering, Thailand) at 190 °C under in peptone water and then shaken in an orbital
pressure of 150 kg/cm2 for 6 min and then shaker at 150 rpm at 37 °C. The bacterial
with a cool press at 25 °C under the same suspension was collected at 1, 2, 3 and 4 h,
pressure for 3 min. respectively and then diluted in 0.85%
2.3 Tensile properties testing procedures normal saline solution. A 10 µL dilutions
Tensile properties of specimens were were dropped on PCA plates and incubated at
investigated following the standard test 37 °C overnight. The bacterial colonies on
method ASTM D638 (2010), using a the agar plates were counted and calculated
universal testing machine (Lloyd LR50K as percentage of bacterial reduction
Plus; Lloyd Instruments, USA) with a
crosshead speed of 10 mm/min. The tensile 3. Results & Discussion
test results were averaged from at least five 3.1 Mechanical properties
independent measurements. Figure 1a and b demonstrate stress and strain
2.4 Molecular weight curves for in situ compatibilized PBS/PLA
The molecular weight of specimens blends at content of 20/80 and 40/60 wt%,
was measured using a gel permeation respectively. The ductility of the blends
chromatography (GPC, 1260 Infinity II increased with the increasing number of
GPC/SEC system; Agilent, USA) at a flow processing iterations up to 3 cycles and then
rate of 1 mL/min with refractive index dramatically decreased when number of
detector (RID). The average molecular processing cycles was higher than 3.
weight of specimens was calculated using a
calibration curve from polystyrene standards.
2.5 Surface contact angle measurement
The surface contact angle value of
specimens was measured following the
standard test method ASTM D7334 (2008),
using a drop shape analyser (DSA100;
KRÜSS, Germany) by dropping 5 µL
droplets of deionized water. The surface
contact angle results were an average of at
least five measurements at different locations
on the sample.
2.6 Antibacterial performance evaluation
Antibacterial performance of
specimens was evaluated using standard plate
count agar (PCA) technique in accordance
with the standard test method ASTM E2149
(2013). The E. coli (ATCC 25922) inoculum
was put into peptone water to obtain cell
turbidity of OD600 ~ 0.1. Two pieces of
specimens (25 × 50 mm2) were individually Figure 1. Stress–strain curves of in situ
placed into a 250 mL Erlenmeyer flask compatibilized PBS/PLA blends with
containing 50 mL of the bacterial suspension
PC3

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
different number of processing cycles: (a) elongation at break (Figure 2c) and tensile
20/80 wt% and (b) 40/60 wt%. toughness (Figure 2d) of the blend at 40/60
wt% was higher than those of 20/80 wt% due
Figure 2 illustrates the tensile
to the larger flexibility of PBS. The number
properties of in situ compatibilized PBS/PLA
of processing cycles did not significantly
blends with the different number of
affect the tensile modulus and strength, this
processing cycles. It was found that the
observation being in line with Yarahmadi et
tensile modulus (Figure 2a) and strength
al.11 It was interesting to note that in this
(Figure 2b) of PBS/PLA blend at 20/80 wt%
study the number of processing cycles
was higher than those of 40/60 wt% due to
affected significantly the elongation at break
the higher stiffness of PLA. In contrast, the
and tensile toughness.

Figure 2. Tensile properties of in situ compatibilized PBS/PLA blends for different number
of processing cycles: (a) tensile modulus, (b) tensile strength, (c) elongation at break and (d)
tensile toughness.

At the 3rd cycle of processing, the with peroxide radicals. Thus, PBS is
blends had the highest elongation at break expected to generate branching and/or
and tensile toughness. This was because more crosslinking structures more easily than
branching and/or crosslinking networks were PLA.5 However, the toughness properties of
formed by residual radicals. The formation of the blend decreased when number of
branching and/or crosslinking networks processing cycles was greater than 3 due to
could be presented in PBS phase as a result chain scission, especially in the PBS phase.
of more secondary hydrogen atoms in PBS
and stronger interaction of hydrogen atoms PC4

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.2 Reaction mechanism and molecular
weight
Predicted reaction mechanisms are
shown in Figure 3. In the initiation step, DCP
generates free radicals under thermal
activation and high shear conditions. In the
propagation step, the secondary hydrogen of
the α-carbon atoms on PBS or PLA chains
interacts with the free radicals, leading to free
radical creation on PBS or PLA main chains.
In the termination step, the free radicals on
PBS or main PLA chains possibly
recombined to form branched and/or
crosslinked networks. However, residual free
radicals in the system can be recombined
during reprocessing of the blends, resulting in
the generation of more branched and/or
crosslinked networks. This is in agreement
with the results of molecular weight given in
Table 1, which suggests that the Mw for Figure 3. Predicted reaction mechanisms for
PBS/PLA at both blending ratios increased in situ compatibilized PBS/PLA blends when
with increasing number of processing cycles passed reprocessing.
up to 3. This confirms the branched/
Table 1. Molecular weight of in situ
crosslinked networks in the in situ
compatibilized PBS/PLA blends with
compatibilized PBS/PLA blends. If this is the
different numbers of processing cycles.
case, it would be the reason why the in situ
compatibilized PBS/PLA blends showed PBS/PLA Number of Mw
optimum mechanical properties after 3 (wt%) processing cycles (g/mol)
20/80 1 203762
processing cycles. However, the blends 3 212661
processed for more than 4 cycles show a 5 194558
reduced molecular weight due to hydrolysis 40/60 1 243329
and oxidative chain scission of PBS and PLA 3 262608
5 258887
chains during multiple processing.
3.3 Antibacterial activity
The percentage reduction of bacteria
with various number of processing for in situ
compatibilized PBS/PLA blends are shown
in Figure 4. It was found that the percentage
of bacterial reduction tended to increase with
contact time because of the releasing of
HPQM in time. However, the percentage of
bacterial reduction for the PBS/PLA blends
at the content of 20/80 (Figure 4a) and 40/60
wt% (Figure 4b) decreased with increasing PC5

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
number of processing cycles. This might be decrease with increasing the number of
due to a loss of HPQM during processing. processing cycles.
The loss of HPQM could be generated by
moisture and water during the reprocessing
process, as it can be dissolved in water.12 This
implies that the remaining HPQM inside the
blends during antibacterial testing would be
low and insufficient to achieve a 99.9%
reduction of bacteria. Moreover, branched
and/or crosslinked networks in the blends
may retard the migration of HPQM to the
surface, as reflected by progressive decreases
in the percentage of bacterial reduction.
HPQM diffusion from the in situ
compatibilized PBS/PLA blends could be
explained by the change in the chemistry of
its surface, as indicated by contact angle
results is shown in Table 2. It was found that
the surface contact angle value of both blends
tended to decrease with the addition of
HPQM due to its high polarity and
hydrophilicity when HPQM was added, this
implies that HPQM could diffuse to the blend
surface. In addition, the surface contact angle
of the PBS/PLA blends with HPQM tended
to increase with the increasing number of
processing. This suggested that HPQM
migrated out of the specimen during the
reprocessing, which is related to the changes
in the antibacterial performance.

4. Conclusion
The number of processing affected
the toughness properties of hygienic in situ
compatibilized PBS/PLA blends, the
elongation at break and tensile toughness
increased with increasing number of
processing up to 3 cycles. The number of
processing did not significantly affect the
tensile modulus and strength. The
antibacterial performance against E. coli of
the blends doped with HPQM was found to
PC6

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 4. Percentage of E. coli reduction with number of processing cycles at different contact
times for in situ compatibilized PBS/PLA blends doped with HPQM: (a) 20/80 and (b) 40/60 wt%.
Table 2. Contact angle of in situ compatibilized PBS/PLA blends doped with HPQM with
different number of processing cycles.
Contact angle (o)
PBS/PLA
Number of processing cycles
(wt%)
1 2 3 4 5
20/80/HPQM 62.13 (±0.33) 68.13 (±0.40) 69.79 (±0.75) 70.69 (±0.62) 72.78 (±0.74)
40/60/HPQM 60.16 (±0.18) 65.32 (±0.53) 67.95 (±0.46) 70.03 (±0.41) 71.25 (±0.87)

Acknowledgements Kositchaiyong, A.; Sombatsompop, N.

J. Macromol. Sci. B. 2009, 48, 755-765.
The authors would like to thank the Thailand 7. Shojaeiarani, J.; Bajwa, D.S.;
Science Research and Innovation (TSRI) under Rehovsky, C.; Bajwa, S.G.; Vahidi, G.
a Directed Basic Research Grant Polymers 2019, 11, 58.
(DBG6280004), and the Royal Golden Jubilee 8. Castro-Aguirre, E.; Iñiguez-Franco, F.;
PhD Program (PHD/0053/2558). Appreciation Samsudin, H.; Fang, X.; Auras, R. Adv.
is also expressed to Koventure Co., Ltd. Drug. Deliv. Rev. 2016, 107, 333-366.
(Thailand) for supply of chemicals. 9. Piemonte, V.; Sabatini, S.; Gironi, F. J.
References Polym. Environ. 2013, 21, 640-647.
1. Lo, H-S.; Xu, X.; Wong, C-Y, Cheung, 10. Żenkiewicz, M.; Richert, J.; Rytlewski,
S.G. Environ. Pollut. 2018, 236, 208- P.; Moraczewski, K.; Stepczyńska, M.;
217. Karasiewicz, T. Polym. Test. 2009, 28,
2. Karamanlioglu, M.; Preziosi, R.; Robson, 412-418.
G.D. Polym. Stab. 2017, 137,122-130. 11. Yarahmadi, N.; Jakubowicz, I.; Enebro,
3. Fortunati, E.; Armentano, I.; Iannoni, J. J. Appl. Polym. Sci. 2016, 133, 439.
A.; Barbale, M.; Zaccheo, S.; Scavone, 12. Eksirinimitr, A.; Wimolmala, E.;
M.; Visai, L.; Kenny, J.M. J. Appl. Taptim, K.; Sombatsompop, N. Polym.
Polym. Sci. 2012, 124, 87-98. Test. 2016, 55, 123-134.
4. Hassan, E.AM.; Elarabi, S.E.; Wei, Y.;
Yu, M. Text. Res. J. 2018, 88, 1735-1744.
5. Srimalanon, P.; Prapagdee, B.;
Markpin, T.; Sombatsompop, N. Polym.
Test. 2018, 67, 331-341.
6. Chammanee, P.; Sombatsompop, K.; PC7

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
A polymeric hydrogel modified cotton thread-based colorimetric device for
hydrogen peroxide detection
Pornchanok Punnoy1, Nipapan Ruecha2, Pranut Potiyaraj2, 3*
1
Multidisciplinary Program in Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn
University, Bangkok 10330, Thailand
2
Metallurgy and Materials Science Research Institute (MMRI), Chulalongkorn University, Bangkok 10330,
Thailand
3
Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
*E-mail: [email protected]

In this research, the cotton thread was successfully modified and applied for distance-
based colorimetric detection of hydrogen peroxide (H2O2). The detection was based on the
oxidation of potassium iodide (KI), preloaded on the thread with H2O2, which was wicked
along the thread at the distance relating to its concentration. The cotton thread was initially
treated with the starch so that the colorimetric change from light yellow to dark blue, caused
by the oxidized KI, can be readily observed with the naked eye. To adjust the analytical
performance of the detection, the thread was also treated with poly(vinyl alcohol) (PVA). After
the systematic optimization, it was found that the length of the dark blue band increased as the
concentration of H2O2 increased. A linear range of 1.0-6.0 mM and a low detection limit of
0.25 mM were achieved for H2O2. We further propose that the same approach can be applied
to measure glucose concentration via tracing of H2O2 product produced by an enzymatic
reaction of glucose in the presence of glucose oxidase (GOx).

1. Introduction observing the change of color intensity.

The sensing device based on cotton However, the optical instruments ( e. g.
thread has gained tremendous attention due camera or scanner) and software are still
to its straightforward use and economical required for quantitative analysis. 6 To
aspect. 1- 3 Cotton thread consisting of overcome this limitation, the combination
twisting strands of cellulosic fiber can be between thread- based device and distance-
used as the substrate as the tiny gaps based colorimetric detection is an
between strands and vacancies of each fiber alternative approach for quantitative
automatically create the capillary effect and analysis, which is a main investigation of
are responsible for the liquid wicking and this work.7
flowing along the thread length. Based on Distance- based colorimetric
this principle, the sample consumption detection is a length measurement of color
decreases and the use of auxiliary pumps change on a device without the use of
can essentially be avoided. 4 Therefore, this external instrument. For this purpose, the
device is one of the ideal candidates used device substrate must be modified so that
for point- of- care diagnosis, such as early the distance, which an analyte can travel
stage screening of diseases in developing along the thread, directly relates to its
countries. 5 Recently, Li et al. developed concentration. Among the polymers used
thread- based glucose detection device by for modification of the cotton thread PC8

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
surface, starch is preferable owing to its Sigma–Aldrich (St. Louis, MO, USA). 30%
vast availability, biodegradability, and v/v H2O2 was purchased from Merck
biocompatibility. However, starch lacks the (Schuchardt OHG 85662, Hohenbrunn,
required strength and processability.8 Thus, Germany). Phosphate buffered saline
it was often blended with other polymers (PBS) was prepared by dissolving 0.28 g of
such as poly( vinyl alcohol) ( PVA) to sodium hydrogen orthophosphate
improve both optical and physical (Na2HPO4), 0.27 g of potassium
properties. Furthermore, the use of PVA dihydrogen phosphate (KH2PO4) and 0.12 g
can improve the immobilization stability of of sodium chloride (NaCl) in 100 mL of
the chemical reagents and biomolecules high purity water. All solutions were
(e.g. enzymes). 9 prepared in high purified water (Millipore,
The development of hydrogen USA, R ≥ 18.2 MΩ cm-1) and used for all
peroxide ( H2O2) sensor is an important the experiments.
device for clinical diagnosis since H2O2 is a 2.2 Modification of cotton threads with
key product generated from the oxidase PVA/starch
based enzymatic reaction. For example, the 10 mL of aqueous dispersion
colorimetric detection of glucose, which containing 0.2 g of starch and 0.1 g of PVA
H2O2 produced from glucose oxidase were heated at 150 °C in a water bath and
(GOx) catalysis of glucose is detected.10, 11 stirred by a magnetic stirrer to obtain well-
Herein, the distance- based dispersed mixture. Then, the mixture was
colorimetric detection on the modified degassed in a sonicator (Branson
cotton thread was created for quantitative CPX5800H, Danbury, CT, USA) for 15
determination of H2O2. PVA/ starch was min at room temperature. Cotton thread was
used to modify cotton thread for enhanced soaked in the PVA/starch mixture for 5
sensitivity of colorimetric change. The min. Finally, the thread was air-dried at
systematic optimization and detection of room temperature and kept in the
the developed methods are presented in the desiccator, as a ready-to-use modified
following sections. thread.
2.3 Characterization of PVA/starch
2. Materials and Methods modified cotton thread
2.1 Materials The morphology of unmodified and
100% cotton thread was purchased modified threads was characterized by a
from a local thread store (Bangkok, scanning electron microscopy (SEM)
Thailand). PVA (MW = 13,000), rice (JSM-6400; Japan Electron Optics
starch, horseradish peroxidase (HRP) and Laboratory Co., Ltd., Tokyo, Japan).
potassium iodide (KI) were purchased from

PC9

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 1. Design and principle of distance-based colorimetric detection of H2O2 proposed in
this study.

2. 4 Design of a thread- based device for intense colored iodine– starch complex,
H2O2 detection resulting in the increase of dark blue–black
The device consists of a sample length on the detection zone. Eventually,
loading zone (Ø = 6 mm of a filter paper) the length of dark blue- black color can be
and a detection zone (40 mm length of the measured in centimeter (cm) for
modified thread) for color development and quantitative determination.
measurement, respectively, as shown in 3.2 Modification and characterization of
Figure 1. A mixture of 0.5 M KI and HRP cotton thread
1 mg/mL was spotted on the detection zone, To improve the color intensity and
and allowed to dry. The thread was then length on cotton thread, unmodified, starch
ready to use for H2O2 detection. During modified, PVA modified and PVA/ starch
H2O2 detection, different H2O2 modified cotton threads were studied. In
concentrations (10 μL) were dropped onto Figure 2A, PVA/ starch modified thread
the sample loading zone. After completed displayed the longest length of color and the
reaction, the color change band was highest intense dark blue- black color,
observed and measured. indicating that PVA/starch can significantly
improve the color change signal because
3. Results & Discussion PVA can promote the ability of the enzyme
3.1 Detection principle for distance- immobilization and indicator reagent
based colorimetric detection of glucose entrapment on the cotton thread, allowing
As illustrated in Figure 1, the for better color length differentiation. In
successful detection of H2O2 was addition, the starch which modified on the
implemented. Based on the colorimetric cotton thread can improve the color
distance, H2O2 immediately oxidized intensity due to the formation of the iodine
potassium iodide ( colorless) to iodine starch complex, leading a simple and rapid
( yellow brown) using HRP as catalytic assay by direct readout with naked eye.11
agent. Then, iodine reacted with the starch
on the modified thread and formed the PC10

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Furthermore, the surface morphology of
PVA/ starch modified thread was
characterized by SEM (Figure 2C).

Figure 2. (A) Color change of the cotton thread with different modifications using 5 mM H2O2,
SEM images of (B) unmodified thread, (C) PVA/starch modified thread with a magnification
of 500×.
compared with the unmodified one ( Figure shown in Figure 3A. The optimal volume of
2B) . SEM image of the unmodified thread sample was evaluated by comparing capillary
presented the smooth surface, whereas the wicking length. The color length increased
modified thread revealed thin film. These along with the increasing of aqueous solution
results confirmed the successful modification volume until 10 μL of sample. After that, the
of PVA/starch on the cotton thread surface and solution was found to exceed the volume
possible hydrogen bond formation between capacity of the modified thread ( 40 mm) .
PVA/starch and cellulose because both PVA Hence, 10 μL was selected as an optimal
and starch are polymer containing hydroxyl volume for H2O2 detection.
groups (–OH) in their chemical structure. these PVA/starch ratio was varied at 2:1, 1:1,
hydroxyl groups tend to form hydrogen bonds 1: 2, 1: 3 and 1: 5 ( PVA: Starch) as shown in
between PVA/starch and cellulose.12 Figure 3B. At the ratio of 2: 1 and 1: 1, color
3.3 Optimization of experimental conditions length was difficult to determine due to pale
To enhance the efficiency and color change. At the ratio of 1:3 and 1:5, color
performance of the created device, several signal was too low because of high starch
parameters were systematically investigated, viscosity. In this work, PVA/starch at the ratio
such as volume of sample, ratio of PVA and of 1:2 was selected as an optimal value because
starch, volume of KI and volume of HRP. The results can be vividly observed by naked eyes.
influence of such parameters on the color
An effect of KI volume was varied
development was investigated by measuring
between 4 and 10 µL (Figure 3C). The highest
intense dark blue–black color length.
color length was observed at 8 µL, and the
The effect of sample volume ranging color length was directly related with H2O2
from 5- 30 μL was studied using a food concentration. Thus, 8 µL was selected as
coloring additive as an example of sample as an optimal KI volume. PC11

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
The different volumes of HRP ranging to 10 mM. The calibration curve between color
between 2 and 10 µL were studied (Figure 3D). length (cm) and H2O2 concentration (mM) was
6 µL and 8 µL of HRP displayed the longest shown in Figure 4B. Thread based device
color length, and 8 µL of HRP provided wider developed in this work displayed a linear range
linearity than 6 µL. Therefore, an optimal HRP of 16 mM (R2 = 0.9987, n = 5) and a detection
volume was 8 µL as same as the optimal limit of 0.25 mM for H2O2.
volume of KI.

Figure 4. ( A) Photograph image of thread-

based device upon analyzing different
concentrations of H2O2 and ( B) A calibration
curve between color length ( cm) and H2O2
concentration ranging from 1 to 6 mM (n = 5).

4. Conclusion
Figure 3. (A) Distance of solution at different Herein, the cotton thread-based device for
applied sample volume and Optimization of H2O2 detection was successfully developed
parameter ( B) ratio of PVA and starch, ( C) using PVA/starch modified cotton thread
volume of KI and (D) volume of HRP. coupled with the visual distance-based
Hence, the ratio of KI and HRP at 1: 1 was colorimetric readout. Under the optimal
optimum for this work. conditions, this created device exhibited a
linear range of 1 -6 mM with a detection limit
3.4 H2O2 detection of 0.25 mM for H2O2. The promising results of
The dark blue– black length on the this system towards H2O2 detection allow for
detection zone was produced by the reaction the future application of thread- based device
between H2O2 and KI in the presence of HRP for glucose and other enzymatic product
as shown in Figure 4A. The different analytes in the real samples.
concentrations of H2O2 were varied from 0. 25 PC12

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Acknowledgements
One of the authors ( Ms. Pornchanok
Punnoy) would like to thank Science
achievement Scholarship of Thailand ( SAST)
for scholarship support.

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Lab on a Chip 2013, 13(12), 2397-2404.
7. Tian, T.; Li, J.; Song, Y.; Zhou, L.;
Zhu, Z.; Yang, C. J. Lab on a Chip 2 0 1 6 , 1 6
(7), 1139-1151.
8. Tang, X.; Alavi, S. Carbohydr. Polym.
2011, 85(1), 7-16.
9. Nery, E. W.; Kubota, L. T. J. Pharm.
Biomed. Anal. 2016, 117, 551-559.
10. Wei, X.; Tian, T.; Jia, S.; Zhu, Z.;
Ma, Y.; Sun, J.; Lin, Z.; Yang, C. J. Anal.
Chem. 2016, 88(4), 2345-2352.
11. Liu, Y.; Lei, L.; Zhang, Z. Sens.
Actuators B Chem. 2017, 248, 195-200.
12. Avérous, L.; Fringant, C.; Moro, L.
Polymer 2001, 42(15), 6565-6572.

PC13

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Microencapsulation of essential oils and synthetic mosquito repellents
by the complex coacervation method
Worn Donchai1, Arunee Kongdee Aldred2*, Anuluck Junkum3, Arpaporn Chansang3
1
Applied Chemistry Program, Faculty of Science, Maejo University, Chiang Mai 50290, Thailand
2
Program in Industrial Chemistry and Textile Technology, Faculty of Science, Maejo University,
Chiang Mai 50290, Thailand
3
Center of Insect Vector Study, Department of Parasitology, Faculty of Medicine, Chiang Mai University,
Chiang Mai 50200, Thailand
*E-mail: [email protected], [email protected]

Plant essential oils can be used as effective mosquito repellents. However, they are unstable
due to rapid evaporation and susceptibility to degradation when exposed to environmental stresses such
as oxygen, high temperature, and light, causing loss of efficacy and shortening of the time of the
repellent effect. Therefore, encapsulation technology was implemented to ensure the encapsulated
material, which could be protected from immediate contact with the environment and to allow for
controlled release. In this study, The EOs were extracted from 6 plants (Cymbopogon nardus Linn.,
Litsea cubeba, Chrysopogon zizanioides (L.) Roberty, Amomum biflorum Jack., Eucalyptus globulus
Labill., and Zanthoxylum limonella Alston) by the hydrodistillation method. Microencapsulated plant
essential oils (EOs) and synthetic repellents (DEET, Picaridin) microcapsules were synthesized by
complex coacervation using gum Arabic and chitosan as the wall material utilizing sodium
tripolyphosphate (NaTPP) as the crosslinking agent. Both natural and synthetic repellent microcapsules
obtained in this study were examined by light-microscopy and found to be mononuclear with the
spherical shape. The average diameter of the microcapsules ranged from 1.55 µm to 9.12 µm. The
synthetic microcapsules could be dried into powder using the Freeze-drying method.
Thermogravimetric analysis (TGA) found that microcapsules decomposed at 260 °C and released 58%
of the encapsulating substance.

1. Introduction encapsulation technology has been

Mosquito-borne diseases have a long implemented to ensure the encapsulated
history, such as those spread by the bite of an material is being protected from immediate
infected mosquito such as yellow fever, Zika contact with the environment and offers the
fever, chikungunya, dengue, and malaria, etc. potential for controlled release of the active
The mosquito inhibitors used for the ingredients.
management of mosquito-borne diseases are Microencapsulation technology has
mostly synthetic chemicals that may have to been used in a variety of industries, such as
affect people's health and environmental chemicals, cosmetics, food, textile, and
concern.1 medicine.3 The capsule can enclose and release
Plant essential oils (EOs) can be used the chemical payloads as needed, dependent on
as an effective mosquito repellent.2 However, the properties required. The size and shape of
due to its nature, which was unstable, rapidly the encapsulation agent vary depending on the
evaporate and susceptible to degradation when materials and methods used in the preparation.4
exposed to oxygen, temperature, and light, Coacervation or phase separation is a method
causing loss of efficacy and shorten the for preparing microcapsules consisting of
repellent effect. Therefore, in the present work, two phases, and being the phase of the core PC14

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
and the other being the phase of the wall, Eucalyptus globulus Labill. (leaf), and
causing the substance to encapsulate and coat Zanthoxylum limonella Alston)(fruit)
the core. In complex coacervation, the purchased from N&B Organizer, Thailand.
technique uses two polymers that have an Litsea cubeba (Aromahub Group Co., Ltd.,
opposite charge to form a wall wrapped around Thailand) and Chrysopogon zizanioides (L.)
the core.5 Generally, Gelatin and gum Arabic Roberty (The Royal Project Foundation,
are used as wall materials. Natural complex Thailand). The synthetic repellents were
polymers such as chitosan have been used to obtained from N, N-Diethyl-3-methyl benza
encapsulate active ingredients due to its low mide (DEET) (Alfa Aesar, Thermo Fisher
toxicity and the ability to mold mucous Scientific Inc.), and Picaridin/Saltidin (PS
membrane films in high tensile strength.6 Grand Chemical, USA).
Mostly crosslinking chemicals used are 2.2 Preparation of microcapsules
formaldehyde, glutaraldehyde, glyoxal, Microencapsulated EOs and synthetic
diisocyanate, and epichlorohydrin had repellents (DEET, Picaridin) microcapsule
limitations due to their biological toxicity. were synthesized by complex coacervation
Butstraen and Salaün have studied the techniques7 using gum Arabic and chitosan as
development of chitosan-gum Arabic wall materials and NaTPP as a crosslinking
microcapsules by using sodium agent at room temperature.
tripolyphosphate (NaTPP), a non-toxic 2.2.1 Solutions preparation
crosslinking agent.7 Acidic chitosan solutions (1.25% v/v)
This study focuses on the preparation were prepared by dissolving Chi powder (1.25
of microcapsule of EOs mosquito-repellent g) in a 100 ml acetic acid (2% v/v) under
extracts from plants and synthetic repellents magnetic stirring condition (1000 rpm) at 45
(DEET, Picaridin) by complex coacervation °C. Gum Arabic solutions (5% w/v) was
technology using gum Arabic and Chitosan as prepared by dispersing 5.0 g of gum Arabic
wall material and sodium tripolyphosphate powder in 100 ml of water. NaTPP solution
(NaTPP) as the crosslinking agent. The was prepared by dissolution of 2.0 g of NaTPP
operating process for encapsulation was in 100 ml of water, and the pH value of
conducted under room temperature conditions. solutions was adjusted from pH ~8 to pH ~4
The EOs microcapsules obtained in this study using acetic acid (2% v/v).
were characterized by light-microscopy, FTIR 2.2.2 Microencapsulation of essential oils
spectroscopy, and Thermogravimetric analysis and synthetic mosquito repellents
(TGA). The EOs or synthetic repellents of 5 ml
were mixed with 100 ml of an aqueous solution
2. Materials and Methods of gum Arabic and formed an emulsion. The
2.1 Materials mixture was homogenized using
Chitosan (Chi) (deacetylation degree = Homogenizer/high-speed blender (T25 digital
85%) and gum Arabic (GA) (Ajax FineChem, ULTRA-TURRAX, IKA, Germany) at 11,000
Australia) were selected as wall materials. rpm, followed by room temperature for 15 min.
Sodium tripolyphosphate (NaTPP) (Sigma, Then the dropwise addition of acidic Chi
Aldrich, USA) and acetic acid (99.8 %, RCI solution of 100 ml was added to create GA-Chi
Labscan, Thailand) were of the analytical coacervation. After that, the crosslinking agent
grade used. The core materials, the EOs were (NaTPP solution) was added to form a
extracted from 6 plants by the hydrodistillation microcapsule. The mixture was stirred at 1000
method, including Cymbopogon nardus Linn. rpm for 2 hr. Finally, the microcapsule was
(leaf), Amomum biflorum Jack. (all parts), PC15

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
separated by decantation, filtered, and washed carboxylic groups (–COO-) of gum Arabic and
with water. the amino groups (–NH3+) of chitosan(Figure
The synthetic microcapsules were 1a). Finally, the crosslinking agent solution
dried into powder using the Freeze-drying (NaTPP) was added to form the particle. The
method (Freeze Dryer, Laboratory Freeze mixture was stirred at 1000 rpm for 2 hr.
Dryer -58 °C, FD 5-4, Gold Sim, Czech Finally, the obtained white paste
Republic). microcapsules were separated by decantation
2.3 Characterization of microcapsules (Figure 1b), filtered under vacuum, and lastly,
To obtain the size and morphology, washed with distilled water to get rid of acids
both natural and synthetic mosquitoes repellent and other residues. It was observed that the
microcapsules were examined using the optical final product is stable, white powder. The
microscopy (light-microscope CX43 standard, resulting microcapsules were divided into two
Olympus, Japan) with Canon DS126571 portions; the first part was dried in a hot air
camera (Canon Inc., Japan), Fourier-transform oven at 45 °C, 12 hr and the second part was
infrared spectroscopy, FTIR (Spectrum Two, freezed at -80°C for 3 hr, and dried by Freeze
FTIR Spectrometer, PerkinElmer Inc., USA) Dryer at -58 °C, 4 mTorr, 20 hr. The
was used to identify the chemical structure of microcapsules that were dried with a hot oven
microcapsules. The samples were mixed with turned a yellow/brown solid film (Figure 1c).
KBr in the pellet form using high-pressure There was some oil on the outside, which was
compression. The test samples were the wall caused by the surface being evaporated quickly
materials (Chitosan, gum Arabic), at high temperatures. Therefore, there were a
microcapsule of mosquito repellent, and part of the oil evaporated from the capsule, and
microcapsule without mosquito repellent. the capsules are flat, tight, not stable in the
The wall materials, mosquitoes same sphere. For the freeze-dried
repellent, microcapsule of repellent, and microcapsules, it was a solid, yellowish-white
microcapsule without mosquitoes repellent powder (Figure 1d).
were analyzed using thermogravimetric
analysis (TGA, TG8120, Rigaku, Japan) at a
heating rate of 10 °C/min from 30-600 °C in a
nitrogen atmosphere.

3. Results & Discussion

3.1 Preparation of microcapsules
Microencapsulation of EOs and
synthetic mosquitoes repellents were
successfully synthesized by complex
coacervation using gum Arabic and Chitosan
as the wall material. Firstly, the oils (EOs or
synthetic mosquitoes repellents) were mixed
with gum Arabic solution to form emulsion by
using a homogenizer. The mixture is a colloid
of oil spread in water (oil-in-water emulsion).
Then to form the polymeric wall around the Figure 1. Microcapsule preparation (a),
core, the dropwise of chitosan solution was decantation (b) microcapsules dried by the hot
added to create the GA-Chi coacervation oven (c) and freeze dryer (d)
complex by the interactions between PC16

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 1 shows the microcapsule
preparation and illustrates the separation by
decantation and the white powder
microcapsule product after dried using the
Freeze-drying method.
3.2 Characterization of microcapsules
Morphology of resulting
microcapsules was investigated by optical
microscopy. The capturing optical
micrographs of MCs obtained in this study
(Figure 2) show that the microencapsulated
EOs and synthetic mosquitoes repellent
fabricated in the same type of mononuclear
with a spherical shape and their apparent
diameter which varied from 1.55 to 9.12 µm.
Table 1 shows the mean diameters of
the produced microcapsules; Litsea cubeba (Ø
1.55 µm), DEET (Ø 2.79 µm), Amomum
biflorum Jack. (Ø 2.93 µm), Eucalyptus
globulus Labill. (Ø 3.35 µm), Cymbopogon
nardus Linn. (Ø 3.82 µm), Chrysopogon
zizanioides (L.) Roberty (Ø 3.95 µm),
Picaridin (Ø 5.13 µm) and Zanthoxylum
limonella Alston (Ø 9.12 µm) respectively. Figure 2. Optical microscope images of
microcapsules of EOs and synthetic repellents
(100x).

Table 1 Mean diameter and morphology of the

microcapsules.
Mean
No. Core materials diameter Morphology
(µm)
1 Picaridin 5.13 mononuclear
2 DEET 2.79 mononuclear
3 Litsea cubeba oils 1.55 mononuclear
4 Cymbopogon nardus 3.82 mononuclear
Linn. oils
5 Chrysopogon 3.95 mononuclear
zizanioides (L.)
Roberty oils
6 Eucalyptus globulus 3.35 mononuclear
Labill. oils
7 Amomum biflorum 2.93 mononuclear
Jack. oils
8 Zanthoxylum 9.12 mononuclear
limonella Alston oils

PC17

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 FTIR spectra of gum Arabic, chitosan, respectively. At 1635 cm-1 characteristic amide
and MCs without core substance (Figure 3) I band attributed to C=O vibration of the
were analyzed in their solid-state in order for acetylated units (–CONH2 groups. An
the characteristic of their structure. The FTIR absorption band at 1580 cm-1 corresponds to
spectrum of Chi showed the strong absorption the N–H bending of the primary amine. The
band in the region 3290-2350cm-1 corresponds absorption band at 1150 cm-1 corresponds to
to N–H and O–H stretching, a typical band at the symmetric stretching of C–O–C; the
3350 cm-1 stretching band of hydroxyl groups absorption bands at 1065 cm-1 and 1025 cm-1
(–OH). This band is broad due to inter and are associated with the C–O stretching
intramolecular hydrogen bonding. The vibration8. GA showed typical bands of the
absorption bands at approximately 2910 and –OH bond stretching at 3330 cm-1. The band at
2870 cm-1 can be attributed to C–H symmetric 2925 cm-1 is characteristic of the carboxylic
and asymmetric stretching vibration of >CH2,
group. The strong bands at 1590 cm-1 and 1400
cm-1 are due to the asymmetric and symmetric
stretching vibration of the carboxylic acid salt
–COO- and the absorption bands at 1275 cm-1
and 1050 cm-1 is the stretching of the C–O
bond. GA–Chi microcapsule showed a band at
3265 cm-1 of -NH2 and -OH groups stretching
vibration. The FTIR of the GA–Chi coacervate
changed significantly in the carbonyl-amide
region. The –NH3+ groups (band at 1530 cm-1) Figure 4. TGA diagram of Picaridin, Chitosan
and asymmetric and symmetric –COO- (Chi), Gum Arabic (GA), MCs without
stretching vibration at 1615 cm-1 and 1410 cm- Picaridin (GA-Chi) and MCs containing
1
, respectively. The FTIR spectra show Picaridin(Picaridin-GA-Chi).
characteristic bands at 1200 cm−1 assigned to
P–O stretching, 1155 cm−1 for the stretching of Percent encapsulation of microcapsule
the PO2 groups, 1055 and 885 cm−1 attributed was examined by Thermogravimetric analysis.
to the stretching vibration of the PO3 groups Figure 4 shows TGA diagrams of Picaridin,
and P–O–P asymmetric stretching, Chitosan, Gum Arabic, MCs without Picaridin,
respectively. 7 and MCs containing Picaridin. TGA analysis
of the MCs without Picaridin shows the mass
loss between 25 ºC and 200 ºC, corresponded
to the evaporation of the water adsorbed in the
capsules. The mass loss between 260 ºC and
650 ºC corresponds to the decomposition of the
wall. The mass loss of around 58% shows the
release of the encapsulating substance.
Confirmation by a thermogram of materials
used in the preparation, solely thermogram of
the Picaridin, starts to decompose at the
beginning until completely decompose quickly
Figure 3. FTIR spectra of chitosan ( a) , gum before 200 °C. However, the wall materials
Arabic ( b) and MCs without core substance (Chitosan, Gum Arabic) and MCs without
(c). Picaridin decompose at almost 300 °C, as PC18

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
compared with the microcapsule of Picaridin, Chemistry, Faculty of Science, Maejo
which slowly decomposes. University.

4. Conclusion References
The microencapsulation of EOs 1. Raja, A.; Kawlekar, S.; Saxena, S.;
(Cymbopogon nardus Linn., Litsea cubeba, Arputharaj, A.; Patil, P. Int. J. Mosq. Res.
Chrysopogon zizanioides (L.) Roberty, 2015, 2 (4), 49-53.
Amomum biflorum Jack., Eucalyptus globulus 2. Tisgratog, R.; Sanguanpong, U.;
Labill., and Zanthoxylum limonella Alston), Grieco, J. P.; Ngoen-Kluan, R.;
DEET and Picaridin were undertaken by Chareonviriyaphap, T. Acta Tropica 2016,
complex coacervation using gum Arabic and 157, 136-144.
chitosan as the wall material, utilizing sodium 3. Kausadikar, S.; Gadhave, A. D.;
tripolyphosphate (NaTPP), a non-toxic cross- Wanghmare, J. Adv. Appl. Sci. Res. 2015, 6
linking agent. An optical microscope (4), 69-78.
examined the resulting microcapsules obtained 4. Munmaya, K. M., Overview of
in this study; the morphology of MCs was Encapsulation and Controlled Release. In
mononuclear with a spherical shape. The Handbook of Encapsulation and Controlled
average diameter of the microcapsules ranged Release, CRC Press: London, 2015.
from 1.55 µm to 9.12 µm. The synthetic 5. Asbahani, A. E.; Miladi, K.; Badri, W.;
microcapsules could be dried into powder Sala, M.; Addi, E. H. A.; Casabianca, H.;
using the Freeze-drying method. FTIR was Mousadik, A. E.; Hartmann, D.; Jilale, A.;
employed for the composition of MCs. Renaud, F. N. R.; Elaissari, A. Int. J. Pharm.
Moreover, the spectra confirmed the 2015, 483 (1), 220-243.
encapsulation of materials. The 6. Alonso, D.; Gimeno, M.; Sepúlveda-
thermogravimetric analysis found that Sánchez, J. D.; Shirai, K. Carbohydr. Res.
microcapsules decomposed at 260 °C and 2010, 345 (6), 854-859.
released 58% of the encapsulating substance. 7. Butstraen, C.; Salaün, F., Carbohydr.
In the present work, it was found that the Polym. 2014, 99, 608-616.
encapsulation of the EOs and synthetic 8. Espinosa-Andrews, H.; Ofelia, S.-C.;
mosquito repellent by complex coacervation Vázquez, H.; Vernon-Carter, E. J.; Lobato-
was a success. In a further study, MCs will be Calleros, C. Carbohydr. Polym. 2010, 79, 541-
applied to textile materials as the mosquito 546.
repellent agent continues to understand the
additional properties of MCs.

Acknowledgments
The authors sincerely thank the
Industrial Research and Technology Capacity
Development Program: IRTC, Northern
Science Park Thailand, for financially
supported. The instruments for this work were
supported by the Program in Applied

PC19

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Study of ground tire rubber / natural rubber composites prepared from
NR latex
Varittha Mitsaichon1, Sombat Thanawan1,2*, Krisda Suchiva1,2, Taweechai Amornsakchai1,3,4
1
Program in Polymer Science and Technology, Faculty of Science, Mahidol University, Phuttamonthon 4 Road,
Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
2
Rubber Technology Research Centre, Faculty of Science, Mahidol University. 25/25 Phuttamonthon 4 Road,
Salaya, Nakhon Pathom 73170, Thailand.
3
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol
University, Phuttamonthon 4 Road, Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
4
Center of Sustainable Energy and Green Materials, Faculty of Science, Mahidol University, Phuttamonthon 4
Road, Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
*E-mail: [email protected], [email protected]

The recycling of used tires to become ground tire rubber (GTR) has considerable
significance in term of environmental and economic aspects. This work aims to apply natural
rubber latex (NRL) as binder for GTR for rubber flooring applications. Various GTR sizes of
7, 20, 30 and 40 mesh were mixed with different concentration of NRL by immersion
technique. Effects of mesh size of GTR, concentration of NRL and immersion time on
mechanical properties of the composites were studied. Amount of dried NRL coated on GTR
increased with immersion time and NRL concentration. The composites were cured by sulfur
vulcanization system and shaped by compression moulding. The evolution of tensile strength,
compressive strength, and compression set improved with increasing of GTR mesh size. As
mesh size of GTR increased from 7 mesh to 40 mesh, tensile strength and compressive strength
increased 169 % and 105 %, respectively but compression set decreased 29 % approximately,
while rebound resilience property showed no significant change.

1. Introduction from the rubber during waste tire recycling

.1 Generally, there are three ways to recycle
The worldwide growth of the
and reuse waste tire rubber: retreading,
automobile industry grows rapidly every
grinding and reclaiming.2 One of the major
year. This is generated massive stockpiles
method of sustainable management of used
of used tires. The lack of recycling
tires is grinding and extracting a powder
programs of used tires rubber has become
called ground tire rubber (GTR). GTR has
an environment, social and economic
been usually used as a reinforcement filler
problem. The main difficult of recycling of
for composites materials as a feasible way
used tires is due to the very complex
to reduce the number of waste tires in added
structure and composition of used tires
value application.3 Many technologies have
material. The basic component of waste tire
been developed for a further usage of GTR
rubber, which makes up about 70-80% of
as a toughening agent for thermoset,
the total mass of the tires is vulcanized
thermo-plastic, asphalt modifier and others
rubber by sulfur, filled by carbon black,
.4 However, one of the main drawbacks for
silica and many kinds of chemical
using GTR as a filler is its low compatibility
compounds. Moreover, tires contain also
because of the high molecular weight and
steel and fibers made from nylon, polyester
crosslinking bonds.5 Several attempts have
and cellulose, which have to be separated PC20

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
been made to utilize the GTR by either stabilized. GTR/NRL composites were
chemical or physical methods.6 Most of vulcanized at 120˚C at 20 MPa of pressure
these methods have succeeded, up to a in compression molding with optimum cure
certain limit to incorporate the GTR with time (T90) derived from the moving die
different matrix materials with acceptable rheometer (MDR).
performance and mechanical properties. Table 1. Formulation of NRL solution
One of the most important recycling fields
Ingredients phr
for GTR is the polymer matrix. The
interface between the GTR particles and the DRC 100
polymer matrix is the main issue, which Sulphur 1.2
governs the final properties of the material.7
ZDEC 1.5
This study has been interesting to
use the natural rubber latex (NRL) as binder ZnO 0.5
with GTR for making rubber composites.
2.3 Characterization
Different particle mesh sizes of GTR have
Compressive strength
been incorporated in various concentrations
The compressive strength was
of NRL. The properties of composite
performed by using the tensile testing
vulcanizates have been investigated and
machine. The compression velocity of
discussed.
10 mm/min and stress force at 25 %
compression were set. The samples were
2. Materials and Methods
prepared by compression-molding for the
2.1 Materials
specimens 25 mm width and 50 mm
High ammonia natural rubber latex
thickness according to ASTM.
(NRL) at 60 % dried rubber content (DRC)
Compression set
was obtained from Thai rubber latex group
Compression set test was performed
public company limited, used as master
on ASTM D-395 method B type A under
NRL ( mNRL) . Lower concentrations of
constant deflection in air. The specimens
NRL were prepared by dilution from
were pressed 25 % of their thickness at 70
mNRL to be 40 % and 20 % DRC. GTR at
˚C for 22 hours.
7, 20, 30, 40 mesh size were supplied from
Tensile strength
Union Commercial Development Co., Ltd.
Tensile strength at break and
All ingredients for curing of NRL were
elongation at break were determined by a
purchased from Thanodom trading Co.,
tensile testing machine. The tests were
Ltd.
performed according to ASTM D-412.The
2.2 Preparation of GTR/NRL composites
specimens of dumbbell shape with 2 mm
GTR was mixed with NRL (60, 40
thickness were prepared. The across head
and 20 % DRC) – followed by Table 1.
speed used was 500 mm/min.
Next step, GTR 100 g was immersed into
Rebound resilience properties
100 g of NRL for 5 minutes, before being
The tests were carried using
sieved out of GTR and placed into plastic
rebound pendulum, following the ASTM
square mold. After that, GTR/NRL
D1051-91.
composites were left to dry at room
3. Results & Discussion
temperature for 24 hrs. Drying step was
3.1 The amount of NRL binder
monitored until the total weight was
PC21

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Ground tire rubber produced from 80

The amount of dried NR (%)

the whole tire was subjected to sieving 70
analysis and categories into 4 particle mesh 60
sizes (7, 20, 30 and 40 mesh). Each mesh 50
size was immersed in NRL, according to 40
the recipe as mentioned in Table 1. 30 7
20 m
All compositions had the same es
10
mixing and curing procedures. The h
0
concentration of NRL was varied at 60 %, 0 10 20 30 40 50 60 70
Time (min)
40 % and 20 % DRC.
Table 2. Particle size of GTR Figure 1. The amount of dried NR binder
Sieve size Sieve size Specific with GTR at 60 DRC.
(mesh) surface area
(µm) (mm2/g) 70

The amount of dried NR

60
7 2000 -
50
20 742.38 0.00895 40
(%)

30
30 416.54 0.018
20 7
40 299.82 0.0243 m
10
e…
0
To study the effect of immersion 10 30 50 70
time on amount of dried NR coated onto Concentration of NRL (DRC)

GTR surface, it found that when immersion Figure 2. The amount of dried NR binder
time increased, most of the dried NR with GTR at different particle mesh sizes of
increased until the immersion time GTR and concentration of NRL.
increased in 5 minutes then leveled off 3.2 Mechanical properties
afterwards. The higher mesh size ( smaller The influence of particle size of
particle size) , the greater amount of dried GTR and concentration of NRL on the
NR coated on GTR. This was similar for all compressive strength were investigated and
concentrations of NRL, as presented in shown in Figure 3. The results show that the
Figure 1. Therefore, the immersion time at stress at 25 % of compression increased
5 minutes was selected for further steps in with decreased the concentration of NRL
this work. because NRL is soft as compared to hard
Figure 2 shows the effects of segments of GTR, whereas the
concentration of NRL and particle mesh concentration at 20 DRC provided too low
sizes of GTR on the amount of dried NR of dried rubber content therefore the stress
coated with GTR. It was found that the at 25 % of compression also decreased. It
amount of dried NR increased with DRC seems that big particle size (7mesh) the
concentration. On the other hand, the compressive strength was low and slightly
amount of dried NR increased with changed as function of DRC of NRL, due to
increasing the mesh size of GTR because less amount of dried NR coated on GTR
smaller particle size gives higher surface surface. The results for 20, 30 and 40 mesh
area, hence high ability to combine with size exhibited close compressive strength
NR. values and similar trend. They may get PC22

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
good packing to resist the compressive 80
force as compared to big size of 7 mesh. 70 20

Compression set (%)

D…
2.0 60
Stress at 25% compression

20 50
1.5 D… 40
30
(MPa)

1.0 20
10
0.5 0
7 mesh 20 mesh 30 mesh 40 mesh
Particle size of GTR
0.0
7 mesh 20 mesh 30 mesh 40 mesh
Particle size of GTR
Figure 4. Compression set of GTR/NR
composites.
Figure 3. Stress at 25 % of compression of
GTR/NR composites. 6
Figure 4 shows the relationship 20

Tensile strength (MPa)

5 DR
between compression set of GTR/ NR C
4
composites and the permanent deformation
3
of GTR/ NR composites. It can be seen that
the percentage of compression set increased 2

with the concentration of NRL. These 1

results indicated that high concentration of 0
NRL provided high dry rubber content, that 7 mesh 20 mesh 30 mesh 40 mesh
Particle size of GTR
exhibits the good elasticity and good
resistance to the permanent deformation
Figure 5. Tensile strength of GTR/NR
under given deflection and temperature. In
composites
addition, all cases of particle size of GTR
attributed the same trend in compression set Figure 5 presents the tensile
value. When compared the percentage of strength of GTR/NR composites with
compression set of GTR/ NR composites at respect to DRC concentration of NRL. The
different particle size of GTR. It found that tensile strength increased gradually with
the percentage of compression set value is GTR mesh size for 40 % and 60 % DRC of
close among the particle sizes of GTR at 60 NRL, but slightly changed for 20 % DRC.
% DRC of NRL. On the other hand, in case At 40 % DRC, this increase is clearly
of 40 and 20 % DRC of NRL, large particle significant. For 7 mesh size at 20 % DRC,
size of GTR presents the high percentage of the specimen for testing could not be
compression set and small particle size prepared due to least amount of dried NR
presents the low percentage of compression on GTR, too much voids and roughness on
set. This effect could be considered on composite surface. Figure 6 shows a
amount of dried NR coated on different comparison between elongation at break
GTR size. Smaller mesh size contained with different particle size of GTR and
higher amount of dried NR which respond concentration of NRL. It is clear that
to elasticity of the composites. elongation at break increased with the GTR
particle size. The results expressed that
elongation at break was proportional to
PC23

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
amount of dried NR on GTR that exhibited 4. Conclusion
more elongation of the composites.
In this work, the use of NRL as new
350 binder for GTR is possible. Compressive
strength, compression set, tensile strength,
Elongation at break (%)

300
250 elongation at break as well as rebound
200 resilience depend strongly on the amount of
150 dried NR coated onto GTR surface.
100
20
Concentration at 40% DRC of NRL seems
50 D… to be the most appropriate conditions for
0 making GTR/NR composites with 20, 30
0 20 40 60
Particle size of GTR (mesh)
and 40 mesh size of GTR.

Figure 6. Elongation at break of GTR/NR Acknowledgements

composites. The researchers are grateful to the
Union Commercial Development (UCD)
Figure 7 provides an information on
CO., Ltd. for providing of all ground tire
the effect of particle size and concentration
rubbers grades, Polymer Science and
of NRL on rebound resilience property.
Technology Programs for supporting the
This data indicates clearly that the
instruments facilitation to this research.
concentration of NRL affect the percentage
of rebound resilience. The percentage of
References
rebound resilience slightly increased with
1. Sienkiewicz, M.; Janik, H.;
increasing the concentration of NRL
Borzędowska-Labuda, K.; Kucińska-
because of dry rubber content. Higher DRC Lipka, J. J. Clean. Prod. 2017, 147,
content correlated to higher percentage of 560-571.
rebound resilience. This could also be 2. Adhikari, B.; De, D.; Maiti, S.,
attributed to amount of dried NR coated on Reclama-tion and recycling of waste
GTR surface that give the difference among rubber. Prog. Polym. Sci. 2000, 25 (7),
GTR mesh size. 909-948.
3. Amari, T.; Themelis, N. J.; Wernick, I.
K., Resource recovery from used rubber
tires. Resour. Policy 1999, 25 (3), 179-
70
20 188.
Rebound resilience (%)

60 DR
C
4. Luo, T.; Isayev, A. I., Rubber/Plastic
50 Blends Based on Devulcanized Ground
40 Tire Rubber. J. Elastom. Plast. 1998, 30
30 (2), 133-160.
20 5. Yehia, A.; Mull, M. A.; Ismail, M.;
10 Assem, Y.; Abdel Bary, E. J. Appl.
0 Polym. Sci. 2004, 93, 30-36.
7 mesh 20 mesh 30 mesh 40 mesh 6. Colom, X.; Cañavate, J.; Carrillo, F.;
Particle size of GTR
Suñol, J. J. Appl. Polym. Sci. 2009, 112,
Figure 7. Rebound resilience of GTR/NR 1882-1890.
composites. 7. A. Alshukri, A.; Abdul Aziz, F.;
Sapuan, S.; Aziz, N.; H. Al-Maamori,
M.; Zageer, D., Effect of Crumb Rubber PC24

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Content and Particle Size on the
Mechanical and Rheological Properties
of Passenger Tyre Tread Composite.
2017; Vol. 12, pp232-238.

PC25

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Effect of organic filler on properties of natural rubber vulcanizates
Tanarat Suphadit1*, Sombat Thanawan1,2, Krisda Suchiva1,2, Taweechai Amornsakchai1,3,4
1
Program in Polymer Science and Technology, Faculty of Science, Mahidol University, Phuttamonthon 4 Road,
Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
2
Center for Rubber Research and Technology, Faculty of Science, Mahidol University. 25/25 Phuttamonthon 4
Road, Salaya, Nakhon Pathom 73170, Thailand
3
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol
University, Phuttamonthon 4 Road, Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
4
Center of Sustainable Energy and Green Materials, Faculty of Science, Mahidol University, Phuttamonthon 4
Road, Salaya, Phuttamonthon, Nakhon Pathom 73170, Thailand.
*E-mail: [email protected]

Utilization of Waste Rubber Powder (WRP) is still trend for industries to reduce cost of rubber
products. This work studies systematically the effect of particle mesh size of WRP in rubber composite
on mixing energy (ME), mechanical properties, and abrasion resistance. WRP used at particle mesh
size 7, 20, 30 and 40 were mixed with NR at 10, 30, 50 and 70 phr. ME, abrasion resistance and
hardness increased with mesh size and concentration of WRP, meanwhile elongation at break decreased
with concentration and mesh size. Tensile strength increased with mesh size but decreased with
concentration of WRP. This study pointed out that ME reduced from 346 kNm to 312 kNm for 40 to 7
mesh size, which could be claimed and related to cost of process for industrial production.

1. Introduction to get a micro particle size and separated

particle size to the commercial particle size
In recent decades, the enlargement of
with sieve filter. Application of WRP has
the automobile industry and the increasing
been studied by Li. S, et al by incorporating
use of cars as the main means of transport
in NR compounds. Tensile strength, hardness
have significantly increased tire production.
and abrasion resistance of NR/WRP
This has generated massive stockpiles of
composites tended to become poorer and
used tires. Due to tire has a lifetime of
more brittle with the increase in WRP
approximate 5 years. After that, it was worn
loading, due to less compatibility between
down and became to waste tire. The waste
NR and WRP.2
tire can’t be reused for its intended purpose,
regrooving or retread. The management of This work studied the influence of
waste tire was various methods include WRP particle size and loading in NR/WRP
landfill disposal, use tires as fuel, pyrolysis, composite on mixing energy during com-
reclaimed rubber, but the WRP method was pounding, cure characteristic, mechanical
popularly trended in the industry. properties, abrasion resistance and hardness
properties. The results will be shown and
WRP can be obtained generally from
discussed.
ambient or high temperature grinding
process. Most of WRP was derived from used
2. Materials and Methods
tires. Steel was removed by magnetic
2.1 Materials
separation and textile fiber was removed by
Natural rubber (NR, grade STR5L)
density.1 Then WRP was repeatedly grinded PC26
was supplied by MBJ enterprise Co., Ltd.,

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Thailand (Mooney viscosity, ML (1+4)
100°C 60). WRP (commercial-grade) (7, 20,
30 and 40 mesh) were supplied by Union
Table 1. The rubber compounds.3
Ingredients phr

Natural rubber (STR 5L) 100

WRP 7, 20, 30, 40 mesh 10 30 50 70

Zinc oxide 3

Stearic acid 1

N-tert-butyl-2-benzothiazole
1.5
sulphenamide

Sulfur 1.5

Commercial Development (UCD) Co., Ltd 2.4 Characterization of properties

(Thailand). Zinc oxide and stearic acid were The tensile properties of the
supplied by Thal-Lysaght Co., Ltd., Thailand vulcanized rubber were measured by using an
and Acidchem international Sdm. Bhd., Instron Universal Tester Model 5566
Malaysia respectively. For curatives: N-tert- according to ASTM D412 at cross head speed
butyl-2-benzothiazole sulphenamide and 500 mm/ min and with force of 1 kN. The
sulfur were obtained from Siam chemical specimens were cut into dumbbell-shape with
public Co., Ltd., Thailand. 2 mm thickness type C die.
2.2 Compounding and mixing energy The abrasion resistance following
(ME) DIN 53516 was used to determine the volume
Compounding (Table 1.) was loss of the vulcanized rubber, which was
prepared by using an internal mixer at 40 °C, calculated the average volume loss by using
rotor speed 50 rpm for 10 min. ME was 3 specimens.
evaluated by internal mixer equipped with Hardness property was measured
torque sensor. It was the energy used per using Wallace H17A hardness tester ( shore
mass unit of NR/WRP compound, which A) according to ASTM D2240. The thickness
calculated from mixing torque. of specimens was 8 mm. Specimens were
2.3 Cure characteristics measured at 6 positions for average hardness
Cure characteristics (T90 and T2) of value.
the rubber compound was determined
following ASTM D5289 using a moving die
rheometer (MDR) at 155 °C.

PC27

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 1. ME curves of NR compounds with WRP 40 mesh at various loadings.

Figure 2. ME curves of NR compounds with WRP 10 phr with various mesh sizes.
3. Results & Discussion accelerator TBBS and vulcanizing agent
3.1 Mixing energy analysis sulphur for 3 min. Figure 1 shows ME
The diagram of ME curves was increased while loading of WRP increased.
divided into three phases. The first phase, The comparison of WRP mesh size, Figure 2
mastication NR and mixed activators ZnO exhibits the energy of mixing increased with
and stearic acid in 3 min. The second phase WRP mesh size.
added WRP for 4 min. This phase exhibited
difference energy with WRP various size and
loading. Then, the last phase added

PC28

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 380
and WRP were similar polarities. However,
Total energy (kNm)

360 the comparison of WRP loading, the higher

loading of WRP, the smaller tensile
340
strength. The result shows the same
320 tendency for all WRP mesh sizes. This
40 mesh
30 mesh indicates the less compatibility of surface
300
20 mesh adhesion between NR and WRP due to
7 mesh
280 WRP was already crosslinked. It couldn’t
10 phr 30 phr 50 phr 70 phr replace than virgin rubber.
WRP loading 600
Figure 3. Total mixing energy of NR/WRP 40 mesh
500 30 mesh

Volume loss(mm3)
composite. 20 mesh
However, the total ME used to 400 7 mesh
incorporate WRP with NR compound 300
(Figure 3) varied with WRP loading and 200
particle mesh size. In a comparison of WRP
100
particle mesh size, the total ME of 7, 20, 30
and 40 mesh size found being 312, 335, 340 0
10 30 50 70
and 346 kNm respectively. It is explained
WRP loading (phr)
that ME of compound is related directly to
WRP both loading and mesh size. Figure 5. Abrasion resistance of NR/WRP
composite.
18
16 40 mesh 3.3 Abrasion resistance
30 mesh
14 20 mesh
The Figure 5 shows the result of
Stress (MPa)

12 7 mesh volume loss that decreased with WRP

10 loading. It seems that WRP mesh size did
8 not give significant difference in abrasion
6
test presenting with volume loss. The
4
2
higher amount of WRP loading shows
0 greater volume loss indicating the poor
10 30 50 70 interaction between NR and WRP.
WRP loading (phr)
50
Figure 4. Tensile strength of NR/ WRP
composite at various WRP mesh sized and 48
Hardness (Shore A)

loadings. 46
3.2 Mechanical properties 44
The effect of WRP loading and 42
particle mesh size on tensile strength is 40 40 mesh
30 mesh
shown in Figure 4. The tensile strength of 38 20 mesh
NR/WRP was found to increase from 5.5 7 mesh
36
MPa for 7 mesh to 16.5 MPa for 40 mesh. 10 30 50 70
This could be contributed to the surface WRP loading (phr)
area of WRP due to WRP 40 mesh was the Figure 6. Hardness of NR/WRP composite.
smallest particle size and highest surface
area. It was adhesion with NR because NR 3.4 Hardness properties PC29

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 6 shows the result of 2. Li, S.; Lamminmäki, J.; Hanhi, K.,
hardness testing that increased with WRP Macromol. Symp. 2004, 216(1), 209-
loading and particle mesh size. This reflects 216.
that the hardness of WRP was higher than 3. Radabutra, S.; Thanawan, S.;
NR. WRP acts as rigid filler in NR Amornsak-chai, T. Eur. Polym. J. 2009,
compound, which could be used as 45, 2017-2022.
hardness modifier of NR compound.

4. Conclusion
WRP could be used for preparation
of NR/WRP composite. Smaller WRP
mesh size consumes more energy in mixing
as monitored using internal mixer. When
particle mesh size of WRP increases:
mixing energy, tensile strength and
hardness increase. When WRP loading
increases: mixing energy increases, but
tensile strength and volume loss decrease.
WRP is derived from used tires that the
molecules of rubber are already crosslinked
that is difficult to form co-crosslinking with
NR during curing process. So that their
interfacial interaction between NR and
WRP is poor which could be responsible of
the decrease in tensile strength. By the way,
high loading of WRP gives less volume loss
that is preferable for rubber product.

Acknowledgements
The author would like to thank the
Union Commercial Development ( UCD)
Co., Ltd (Thailand) for providing all grades
of WRP, and Rubber Technology Research
Centre (RTEC) Faculty of Science Mahidol
University, for help and suggestion on
properties characterization.

References
1. Bekhiti, M.; Trouzine, H.; Aissa, A.
Eng. Technol. Appl. Sci. Res. 2014, 4,
669-672.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Physical properties and crystal violet adsorption of biosorbent prepared
from lemon grass fiber coated with polylactic acid/cellulose acetate blend
Khoiria Nur Atika Putri, Watchanida Chinpa*
Department of Materials Science and Technology, Faculty of Science, Prince of Songkla University, Hat Yai,
90110, Thailand
*E-mail: [email protected]

Lemon grass leaves (LG) as lignocellulosic waste material had been utilized as
biosorbent for crystal violet (CV) removal. Prior treatment using sodium hydroxide was done
to produce lignocellulosic fibers (LGF). LGF were coated with polylactic acid (PLA) and
cellulose acetate (CA) blend solution to form biosorbent sheet (LGF-PLA/CA). The effect of
PLA and CA ratios on the mechanical properties, swelling capacity, stability in acidic medium
and CV adsorption capacity of LGF-PLA/CA sheet was studied. LGF-PLA/CA tensile strength
value decreased with increased CA content, while all biosorbents prepared using various ratio
of PLA and CA was observed relatively stable in acidic medium. The highest %swelling and
CV adsorption capacity was possessed by biosorbent prepared using PLA:CA ratio of 30:70.

1. Introduction of 17.39-27.38%) are possible to have various

Agricultural crops such as rice, corn, application ranging from materials for
sugarcane, fruits and herbs were cultivated as papermaking,9 composite reinforcement,10
a food source for human. Yet only some parts and adsorbent for wastewater treatment.11
of the crops are consumable while some Previous studies had proven that LG,
others are not. The non-consumable parts are as an adsorbent, had good adsorption capacity
prone to be waste. Several attempt starting towards metal and dye compounds.11–13
from utilizing the agricultural crops waste as However, aforementioned works only studied
an animal feed stuff1–3 to the attempt of the use of LG in powder and flake forms
turning it into high-added value material for which had vulnerability in after-use
particular purpose such as biofuel, pollutant separation process. The use of polymer as a
detector, and material for treating coating material may be the best solution to
wastewater4–6 has been widely practiced to make adsorbent derived from LG more
reduce the number of waste. convenient to use. Natural polymers such as
Lemon grass (LG) is indigenous crop polylactic acid (PLA) and cellulose acetate
growing in tropical and subtropical area that (CA) that possess great mechanical
widely used as herb and flavor enhancer in properties, biodegradability and naturally
curries, stews and soups across Asia.7 LG abundant14,15 may be a prominent option for
parts can be bifurcated into consumable parts coating material. PLA film had been reported
and non-consumable parts. LG stems and as an emerging biodegradable material having
stalk were commonly used as herb while the special properties of high stiffness and high
upper leaves were often trimmed and ended strength16 but it has a drawback of brittleness
up as waste.8 LG leaves having high content that lead it into limited applications.17
of lignocellulosic compound (holocellulose of Meanwhile, CA was known as a
68.51%, α-cellulose of 35-44.6% and lignin thermoplastic material that is easy to process, PC31

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
tough, but easy to cut and tear18. Other than were prepared using the polymer solutions of
that, PLA and CA structures have plenty of 5 wt% PLA and PLA/CA blend with the mass
hydroxyl and carboxylic side groups that are ratio of 90:10, 70:30, 50:50 and 30:70 were
expected having good interaction with labeled as LGF-PLA, LGF-P9C1, LGF-
pollutant molecules thus favoring the P7C3, LGF-P5C5, LGF-P3C7, respectively.
adsorption process. 2.3 Mechanical properties
Therefore, this study aimed to In order to study the mechanical
fabricate a novel lignocellulose fiber properties including tensile strength and
biosorbents derived from LG leaf wastes elongation at break of biosorbents. The LGF-
combined with coating materials consisted of based sheets were cut in 1x4 cm2 rectangular
PLA and PLA/CA blend. The effect of shapes and were introduced to universal
PLA/CA ratios in the blend on its mechanical testing machine (Instron 3365) to conduct the
properties, swelling and stability in acidic desired test. Tests were carried out using
medium had been investigated. Their 100N load cell with speed of 5 mm/min.
adsorption capacities towards crystal violet 2.4 Swelling
(CV) as model pollutant were also The biosorbents ability to absorb
investigated. The prepared biosorbents are water was investigated by swelling method.
prospected to be applied as adsorbent in The sheets were cut in rectangular shape and
wastewater treatment process. weighed. The sheets were immersed in 30 mL
distillated water for 24h in ambient
2. Materials and Methods temperature. Swelling percentage was
2.1 Materials calculated based on the weight change
Lemon grass (LG) leaves were following Eq (1).
trimmed off from LG that is cultivated in 𝑊𝑓 − 𝑊𝑖 (1)
%Swelling = ×100
southern Thailand. CA in a powder form was 𝑊𝑖
obtained from Eastman Chemical USA while Where Wf is a final weight and Wi is the initial
PLA pellets was supplied by Natureworks. N- weight of the sheets
methyl-2-pyrrolidone (NMP) as a solvent was 2.5 Stability in acidic medium
supplied by Sigma-Aldrich. Acetic acid The stability of biosorbents in acidic
(CH3COOH) and sodium hydroxide (NaOH) medium was investigated by immersing the
were supplied by Labscan. CV powder was 0.01 g of uniformly shaped sheets into 20 mL
purchased from Lobachemie (India). of 1 M CH3COOH solution. The sheets were
2.2 LGF-PLA/CA preparation immersed for 24h in ambient temperature.
LG leaves were trimmed in the size of The change on the weight was used to
12 cm and oven-dried at 40oC for 48h. LG calculate %weight loss.
leaves were pretreated using 10wt% 2.6 Crystal violet batch adsorption study
NaOH(aq) using ratio of LG:NaOH 1g:25 mL
Study of adsorption capacity of LGF-
(w/v) for 2h at 85oC to turned them into LG
based biosorbents towards CV was
fibers (LGF). After washing until pH was
investigated in batch adsorption process LGF-
neutral, the obtained LGF were molded into
based biosorbents were contacted with CV
LGF sheet using aluminum mesh. LGF sheet
having concentration of 10 mg L-1 and volume
was immersed into the polymer solution for 1
of 20 mL for 3 h at 25oC. The adsorption
min followed by immersion in water and
capacity and %Removal was calculated based
drying at 60oC in oven. The biosorbent sheets
on Eq (2) and Eq (3). PC32
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 ( C0  Ct )  V (2) to biosorbents having higher CA ratio. This
qt 
m can be correlated to the more hydrophobic
( C0  Ce ) nature of PLA20 as compared to CA which
% Re moval   100 (3)
C0 hinders water penetration through the
where C0, Ct and Ce (mg/L) are the liquid- biosorbents.
phase concentrations of dye at initial, at time 700
t and at equilibrium respectively. V (mL) is 600
the volume of the solution and m is the weight 500

%Swelling
of adsorbent (g). 400
300
3. Results and Discussions
200
3.1 Mechanical properties
100
Mechanical properties including
0
tensile strength and elongation at break were
investigated to provide information about
LGF-based biosorbents durability under
given force. The values of tensile strength and
elongation at break for each sample was Figure 1. %Swelling of LGF-based biosorbents.
summarized in Table 1. 3.3 Stability in acidic medium
Table 1. Mechanical properties of LGF-based The stability of biosorbent sheets in
biosorbents. the acidic medium was observed to study the
Tensile strength Elongation adsorbent endurance in the extreme pH
Sample
(MPa) at break (%)
condition as a common condition in
LGF-PLA 1.9118 ± 0.5203 4.5841 ± 1.9040 wastewater. Acetic acid was reported as
LGF-P9C1 2.1951 ± 0.7719 2.4878 ±0.6749
efficient desorbing agent for various
21–23
materials thus LGF-based biosorbents
LGF-P7C3 1.9019 ± 0.4277 4.1947 ± 0.3783 stability investigation in acetic acid solution
LGF-P5C5 1.5174 ± 0.2998 3.2934 ± 1.0678
will be an useful information for future
regeneration of used biosorbents. The weight
LGF-P3C7 0.7986 ± 0.1687 2.2657 ± 0.2097 change and visual observation of LGF-based
The results showed that the tensile biosorbents after overnight immersion in
strength decreased as the content of CA acidic medium were presented in Figure 2. As
increased. The lowering value was attributed investigated based on the samples weight
to the incompatible nature of PLA/CA blend change after immersed into acetic acid
as reported by Claro et al19. The solution, it was observed that the weight
incompatibility resulted in inability to change decreased with increased CA content.
withstand the force causing the brittleness of It could be inferred that CA could stabilize
the material. LGF and PLA to retain its shape under acidic
3.2 Swelling capacity condition. At CA content above 50 wt%, the
Swelling capacity values calculated biosorbent (LGF-P3C7) had the largest
based on weight difference after overnight weight lost (Figure 2a). These phenomena
immersion are summarized in Figure 1. LGF could be attributed to the reduction of
biosorbents having higher ratio of PLA was interfacial adhesion between LGF and
possessed lower swelling capacity compared polymers due to the excess amount of CA
PC33
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 leading to the easier degradation of CA due to The results in Figure 3 shows that the
the cleavage of the glycosidic bond on its adsorption capacity and %removal of
structure.24 biosorbents increased along with increased

10
9
8
%Weight change

7
6
5
4
3 LGF-PLA LGF-P9C1 LGF-P7C3
2
1
0

LGF-P5C5 LGF-P3C7
(a) (b)

Figure 2. %Weight change (a) and visual appearance (b) of LGF-based biosorbents after
overnight immersion in 1M CH3COOH solution.

portion of CA content in the blend. This

The visual observation of the finding was related to the swelling behavior
biosorbents in Figure 2b showed that the which showed similar trend. The
samples were stable and able to retain its hydrophilicity of CA made the minimum
original shape in acidic conditions. Thus, the hindrance of solvent penetration facilitating
sample will not be having shape and better interaction between CV and biosorbent
functional deterioration when being used in active sites.
extreme acidic condition and indicating the 80
use of acetic acid as desorbing agent will be a 70
%Removal (%)
great prospect. q (mg/g)
60
3.4 CV adsorption study
Adsorption

CV is a synthetic dye widely used in 50

textiles industries. The direct discharge of CV 40
to the water system without prior treatment 30
could threatened aquatic ecosystem.25 The
20
adsorption capacity of LGF-based
biosorbents towards CV was investigated and 10

summarized in Figure 3 to study its 0

possibilities to be used as biosorbent for CV
removal.
PC34
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 3. LGF-based biosorbents adsorption Li, X.; Hou, H.; Zhou, M. J. Mol. Liq
capacity towards CV. .2019, 285, 62–74.
7. Kanatt, S. R.; Chawla, S. P.; Sharma,
4. Conclusions A. 2014, 6, 24–30.
The effect of PLA/CA ratio in 8. Albert, S. Lemon Grass: Kitchen
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observed having poor mechanical properties Gautam, A. J. Sci. Technol. 2012, 1 (8),
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compound. Duns, G. J.; Yu, C.; Jin, L.; Li, X.; Jia,
All biosorbents were observed Q.; Chen, J. BioResources. 2017, 12
having excellent stability in acidic medium. (3), 5564–5681.
LGF-P3C7 was observed having good CV 11. Singh, H.; Dawa, T. B. Carbon Lett.
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%swelling contributed by the hydrophilic 12. Zuo, X.; Balasubramanian, R.; Fu, D.;
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13. Lee, L. Y.; Lee, X. J.; Chia, P. C.; Tan,
Acknowledgements K. W.; Gan, S. J. Taiwan Inst. Chem.
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Department of Materials Science, Prince of 14. Sattar, M.; Hayeeye, F.; Chinpa, W.;
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T. M.; Le Minh Tri, N.; Kim, H. H.; 2019, 7, 1–16.
Cho, K. H.; Lee, C. J. Water Process 21. Badruddoza, A. Z. M.; Hazel, G. S. S.;
Eng .2020, 33, 101037. Hidajat, K.; Uddin, M. S. Colloids
6. Chen, S.; Qin, C.; Wang, T.; Chen, F.; Surfaces A Physicochem. Eng. Asp.
PC35
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 2010, 367 (1–3), 85–95. (28), 28500–28509.
22. Paulraj, A.; Elizabeth, A. T. Chem. Sci. 24. Yamashita, Y.; Endo, T. J. Appl.
Trans. 2016, 5 (1), 87–96. Polym. Sci .2004, 91 (5), 3354–3361.
23. Maeda, C. H.; Araki, C. A.; Moretti, A. 25. Wathukarage, A.; Herath, I.; Iqbal, M.
L.; de Barros, M. A. S. D.; Arroyo, P. C. M.; Vithanage. Environ. Geochem.
A. Environ. Sci. Pollut. Res. 2019, 26 Health 2017, 1–15.

PC36
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Smart carboxymethyl cellulose food package derived from durian rind
Gittipong Jitprawat, Inthira Markjaroenpol, Supranee Kaewpirom*
Department of Chemistry, Faculty of Science, Burapha University, Chonburi, 20131, Thailand.
*E-mail: [email protected]

This research focuses on the synthesis and characterization of carboxymethyl cellulose

derived from durian rind by carboxymethylation reaction. The synthesis of carboxymethyl
cellulose showed the percentage of carboxymethyl cellulose product of 130±4 %, with respect
to dry weight of cellulose. Chemical structure of carboxymethyl cellulose was confirmed by
ATR-FTIR. Biofilm was then prepared from the resulting carboxymethyl cellulose product
using solvent casting technique. The resulting biofilm showed smooth surface and yellowish-
white color with a thickness 0.1 mm. With no additives, tensile strength, Young’s modulus,
and elongation at break of carboxymethyl cellulose film were 3.7±0.9 MPa, 390±19 MPa and
2.8±0.3 %, respectively. pH-sensitive property of the film was then improved by the addition
of purple-cabbage extract. The biofilm showed the change in its color when immersed in buffer
solutions. The film displayed red, blue and yellowish-green when submerged in acidic, neutral,
and basic buffer solutions, respectively.

1. Introduction carboxymethylation. One of the important

With an increasing demand for fresh sources of cellulose is agricultural waste
and safe food, smart packaging technology including durian rind that contain roughly
has been introduced into food industry. Smart 30% cellulose. In order to increase its value,
packages integrated sensors or indicators durian rind was used as cellulose source for
provide supportive information about the producing CMC.6
quality and safety of the packed food.1,2 In this present study, cellulose was
Moreover, smart packages could replace extracted from durian rind using aqueous alkaline
“use-by” date to cut food waste that is one of solution. Carboxymethyl cellulose was then
synthesized from durian rind by
the major global environmental problems.
carboxymethylation and its film properties were
Carboxymethyl cellulose (CMC) is
evaluated. Finally, purple-cabbage extract was
known as a water-soluble cellulose incorporated into the film as a pH-sensitive
derivative. This biodegradable polymer has sensor providing useful information about the
been widely used in many applications such food freshness.
as food and beverages, pharmaceutical and
cosmetic industries.3 In food packaging 2. Materials and Methods
industry, the application of CMC can be 2.1 Materials
enlarged by its modification such as blending Montong durian rind was obtained
with other polymers and self-crosslinking or from Rayong province, Thailand.
crosslinking with other crosslinking agents.4,5 Monochloroacetic acid and sodium
With the incorporation of sensors or hydroxide were purchased from Loba
indicators, CMC has a potential application Chemie. Hydrogen peroxide, isopropanol,
in smart packaging. methanol, ethanol, and glycerol are from
CMC was synthesized from the most QRëC. All chemicals are AR grade and used
abundant biopolymer called cellulose via as received without any further purification. PC37
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.2 Cellulose extraction respect to the dry weight of CMC) was mixed
Durian rind was cleaned, chopped with water prior to dissolving CMC in the
into small pieces before being grounded mixed solvent.
using food processor. The grounded product In order to prepare the pH-sensitive
was dried at 60°C in a hot air oven for 72 h CMC films, a dried CMC film was immerged
and subsequently refluxed in a 10%w/v into purple-cabbage extract for 15 min. The
NaOH aqueous solution at 100°C for 3 h. The soaked film was then dried at 50℃ for 24 h
resulting black slurry was filtered, washed until constant weight was obtained.
with water several times (until neutral pH 2.4 Characterization
was obtained) and dried. Then, it was The chemical structures of both
bleached with 35%w/v H2O2 and grounded cellulose and CMC was confirmed by ATR-
into fine powder and sieved with 60 mesh FTIR (Perkin Elmer, System 2000) from
sieve. 400–4000 cm-1 wavenumbers with 2 cm-1
2.2 Synthesis of carboxymethylcellulose resolution and 4 scans per sample.
Cellulose powder of 15 g was Mechanical properties of CMC film
dispersed in the mixed solution of 30%w/v were evaluated according to ASTM D882-
NaOH (50 mL) and 450 mL isopropanol and 80a (Tensile testing of thin plastic sheeting
stirred for 30 min at room temperature. Then (film) using Tensometric Micro 350
18 g of monochloroacetic acid was added universal tensile testing machine. The film
while the mixture was continuously stirred at was cut into 0.50 cm × 5.00 cm rectangular
55°C for 3 h. After the reaction was strips and preconditioned at 23±2℃,
completed, the mixture was filtered, 70±5%RH prior to testing. Load cell, grip
suspended in methanol, and neutralized. separation and cross-head speed were 500N,
Finally, the carboxymethylcellulose (CMC) 30 mm and 30 mm/min, respectively.
product was washed several times using Young’s modulus, tensile strength and
ethanol before drying at 55°C for 24 h. The elongation at break were recorded from the
yield of CMC product was measured on dry averaged values of at least 6 tests.
weight basis using the following equation7: Thickness of the films was measured
using a digital Vernier caliper. The average
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑀𝐶 (𝑔) thickness of the prepared film was
𝑌𝑖𝑒𝑙𝑑 𝑜𝑓 𝐶𝑀𝐶 (%) = × 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒 (𝑔)
approximately 100 m.
2.3 CMC film preparation
CMC solution was prepared by 3. Results & Discussion
dissolving 3.0 g of CMC in 100 ml of distilled 3.1 Chemical structure
water and constantly stirring at 80 °C for 10 The yield of the extracted cellulose
min. The solution (45 mL) was then casted on was 21.20±0.88 % with respect to dry weight
to a Petri-disk (with a diameter of 10 cm) and of durian rind. This result is in good
left to dry at room temperature overnight accordance with the results reported in
before further drying in a hot air oven at 50°C literatures.6-7 Photos of freshly-chopped
for 24 h. The resulting CMC film with the durian rind, extracted cellulose and CMC
thickness ⁓ 100 m was obtained. For CMC film are shown in Figure 1.
that plasticized with glycerol, 30%w/w (with PC38
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 1. Freshly-chopped durian rind (a),
resulting cellulose product (b) and CMC film
(c).
After carboxymethylation was
completed, the CMC product was obtained
with 130±4 % yield. It was known that the
reaction is divided into 2 steps: alkalization
and etherification. In the first step, hydroxyl Figure 2. FTIR spectra of cellulose and CMC
groups of cellulose reacted with NaOH via obtained from durian rind.
substitution reaction.7 This was evidenced by It was proposed by Kamthai and
the shift of carbonyl absorption band from Magaraphan8 that alkalization technique can
1635 cm-1 (in cellulose) to 1587 cm-1 (in defibrillate cellulose molecules before
CMC). The carbonyl group found in cellulose etherification or carboxymethylation leading
was due to the trace amount of to an improvement on degree of substitution
hemicelluloses, pectin and waxes residues.8-9 of CMC.
Moreover, the hydroxyl absorption (–OH
stretching) of CMC at 3337 cm-1 also showed 3.2 Mechanical properties
broader peak, compared with cellulose, after Typically, stiffness and brittle
the alkalization reaction was completed. In characters of CMC film limit some of its
etherification, the alkaline-pretreated applications. Therefore, in this study CMC
cellulose reacted with sodium- was plasticized by glycerol in order to
monochloroacetate. Two significant improve its flexibility. Tensile properties of
absorption bands found at 1587 cm-1 CMC film with the incorporation of glycerol
(conjugated carbonyl) and 1412 cm-1 (C–H in (CMC-G30) and without glycerol (CMC) are
plane blending) illustrated the efficiency of shown in Figure 3
etherification. Other important functional
groups of CMC found in Figure 2 are –CH
stretching (2922 cm-1), –OH bending (1323
cm-1), and C–O symmetric stretching (1048
cm-1).8

PC39
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 3. Tensile properties of the neat CMC
film and the CMC film plasticized with
30%w/w of glycerol (CMC-G30).

Without glycerol, tensile strength, Young’s

modulus, and elongation at break of CMC
film were 3.7±0.9 MPa, 390±19 MPa and
2.8±0.3 %, respectively. With 30%w/w of
glycerol, tensile strength, Young’s modulus,
and elongation at break of CMC film were
3.4±0.4 MPa, 30.5±8 MPa and 25.0±1 %,
respectively. The sudden drop of Young’s
modulus and sharp rise of elongation at break
were mainly due to the plasticization effect of Figure 4. Color change of CMC film
glycerol. It is well known that glycerol is the incorporated with purple-cabbage extract
most widely used plasticizer for while soaking in buffer solutions with
10
biopolymer. Due to its small size with 3 different pH values.
hydroxyl groups, glycerol can penetrate It can be clearly seen in Figure 4 that
through CMC chains, resulting in the the film showed the change in its color when
breakage of inter-chain hydrogen bonds. The being immersed in buffer solutions. The film
hydrogen bonds between hydroxyl groups of displayed red, blue and yellowish-green in
glycerol and CMC are formed. The CMC acidic, neutral, and basic buffer solutions,
chain separation helps to improve the film respectively. The color change was easily
flexibility. detected by the naked eye. Hence, if the rate
3.3 pH-sensitive property of color change of the film correlated well
Purple-cabbage extract is one of the with the rate of deterioration of the food in
promising natural indicators that can be used respect to temperature variation and time
as a food freshness sensor. According to during transportation, distribution, and
Kuswandi,11 the market needs for freshness storage, this will drive the need for freshness
sensors in the food packaging systems are sensors in future food packaging.10
predicted to have a promising future. In this
present study, purple-cabbage extract was 4. Conclusion
incorporated into CMC film. The pH- CMC derived from durian rind was
sensitive property of such CMC film was successfully synthesized via carboxymethyl-
tested against buffer solutions with the pH lation with the yield of 130±4%. CMC film
range of 1 to12. The preliminary test results incorporated with purple-cabbage extract
are shown in Figure 4. was prepared using solvent casting
technique. In different pH environments, the
color change of the film can be clearly
evidenced by naked eyes. Therefore, CMC
film incorporated with purple-cabbage PC40
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
extract has confirmed its potential application
in smart packaging.
Acknowledgements
This work was financially supported
by the Research Grant of Burapha University
through National Research Council of
Thailand (Grant no. 51.1/2562).

References
1. Ahvenainen, R. Active and Intelligent
packaging: an Introduction. In Novel
Food Packaging Techniques,
Ahvenainen, R., Ed.; Woodhead
Publishing Ltd., Cambridge, 2003; pp 5–
21.
2. Kerry, J. P.; O′Grady, M. N.; Hogan, S.
A. Meat Sci. 2006, 74, 113–130.
3. Gregorova, A.; Saha, N.; Kitano, T.;
Saha, P. Carbohydr. Polym. 2015, 117,
559–568.
4. Anbergen, U.; Oppermann, W. Polym.
1990, 31(10), 1854–1858.
5. Wach, R. A.; Mitomo, H.; Nagasawa, N.;
Yoshii, F. Radiat. Phys. Chem. 2003, 68,
771–779.
6. Khemkaew, S.; Kaewpirom, S. J. Indust.
Technol., 2016, 12, 11-21.
7. Rachtanapun, P.; Luangkamin, S.;
Tanprasert, K.; Suriyatem, R. LWT-Food
Sci. Technol., 2012, 48(1), 52–58.
8. Kamthai, S.; Magaraphan, R. Ind. Crops.
Prod., 2017, 109, 753–761.
9. Bolio-López1, G.I.; Cadenas-Madrigal,
G.; Veleva, L.; Falconi, R.; Cruz-Burelo,
P.; Hernández-Villegas, M.M.; Pelayo-
Muñoz, L. Inter. J. Innovat. Sci. Eng. &
Technol. 2015, 2(4), 977–981.
10. Shojaee, M.; Sofla, K.; Mortazavi, S.;
Seyfi, J. Carbohyd. Polym. 2020, 232,
115784.
11. Kuswandi, B. Freshness Sensors for Food
Packaging. In Reference Module in Food
Science, Smithers, G. W., Ed.;
Amsterdam; Elsevier, 2015; pp. 1-11.
PC41
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Effect of carboxymethyl cellulose on physical and mechanical properties of
LLDPE/TPS film
Pakpoom Boonphan1, Anchasa Kamjaikittikul2, SupraneeKaewpirom1*
1
Department of Chemistry, Faculty of Science, Burapha University, Chonburi 20131, Thailand
2
Research and Development Division, Multibax Public Company Limited, Chonburi 20230, Thailand
*E-mail: [email protected]

This research focuses on the effect of carboxymethyl cellulose (CMC) on physical and
mechanical properties of linear low density polyethylene (LLDPE)/thermoplastic starch (TPS)
film. The preparation of such bio-based film began with the preparation of 3.3%, 6.6%, 9.9%,
and 13.3 %w/v of CMC solution, using a mixture of water and glycerol (1:9) as a solvent. CMC
solution was then mixed with starch in the ration 30:70. The CMC/TPS blend was further
mixed with LLDPE and processing-aid additives, using a twin-screw extruder. The resulting
bio-based thermoplastic pellets were dried at 105 ℃ for 3 h before being blow-molded into
plastic films. Physical and mechanical properties of both the pellets and the blown films such
as density, melt flow index, tensile properties, dart impact, and morphology were investigated
in related with CMC content. The density of the pellets was about 1.00 g/mL, whereas melt
flow index increased (from 1.3 g/10min to 1.6 g/10min) with increasing CMC content. In
contrast, tensile strength, elongation at break, Young’s modulus and dart impact of the films
reduced accordingly with increasing CMC content. The lessening in such mechanical
properties were caused by the gel formation of CMC, as also confirmed by SEM micrographs.
.

1. Introduction ratio of starch are vary with botanical

Environmental pollution caused by origin. Differences of starch
non-degradable plastic waste has become physicochemical characteristics have
one of the biggest global problems. As long impact on their functional properties,
as this situation has been concerned, the affecting their suitability for specific and
polymer technologists have developed targeted use. For example, high amylose
several kinds of plastic packages from starch is use for fried food coating batter
biodegradable materials. Among them, due to its excellent film forming properties3
natural-derived polymers such as cellulose that provides crispy texture.
and starch are commonly used. This was Carboxymethyl cellulose (CMC) is
due to they are biodegradable and a water soluble cellulose derivative that has
renewable with low cost and ease to be no harmful effects on human health. CMC
processed using conventional processing is widely used in food industry as highly
devices.1 effective additive to improve texture quality
Starch can be obtained from of food product. Moreover, CMC is used to
different botanical sources that affect the increase viscosity, act as a binder in food
physicochemical properties of starch-based contact materials4 and can be applied in
films and the interaction with other various fields such as cosmetics,
materials for polymer blends production.2 pharmaceuticals, ceramic and textile
Starch consists of amylose and industries.5
amylopectin. The size, shape and the In film processing industry, CMC
composition of amylose to amylopectin was used to improve the barrier and PC42
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
mechanical properties of corn starch-based powder in the solution of water/glycerol
edible films.6 With the addition of CMC (1:9) and constantly stirred at 90 °C for 3 h.
(0%-20%), the ultimate tensile strength of 2.3 Preparation CMC/TPS/LLDPE film
the starch film increased with increasing The CMC/TPS blend was prepared
CMC content. Furthermore, there was no by mixing CMC solution with starch
significant depressing effect on flexibility (30:70). The CMC/TPS blend was further
of starch film. mixed with LLDPE and processing-aid
The addition of CMC for enhancing additives (PA) (CMC/TPS: LLDPE: PA
the mechanical and hydrophobic properties was 30:62:8) using a twin-screw extruder.
of corn and cassava starch film was also The resulting bio-based thermoplastic
investigated.7 The film with the addition of pellets were dried at 105 ℃ for 3 h before
CMC presented a smoother surface with being blow-molded into plastic films at 180
few small bubbles. Besides, the maximum ℃. The film with a thickness of
tensile stress of the film increased without approximately 25 m was obtained.
affecting its elastic modulus.
In this present study, the effects of 3. Characterization
CMC) on physical and mechanical Melt flow index (MFI)
properties of linear low density measurement of LLDPE/CMC/TPS pellets
polyethylene (LLDPE)/thermoplastic was performed according to ASTM 1238.
starch (TPS) film. The CMC/TPS blends at The test temperature and introduced weight
various concentrations of CMC was were 190 ℃ and 2.16 Kg, respectively. MFI
prepared and further mixed with LLDPE was expressed in grams of polymer per 10
and other processing-aid additives using a min of duration of the test.
twin-screw extruder. Physical and Density of LLDPE/CMC/TPS
mechanical properties of the blown films pellets was tested by gravimetric method
such as density, melt flow index, tensile according to ASTM D792. Approximately
properties, dart impact, and morphology 0.5 g of the pellets was weighed both in air
were evaluated. and in water or isopropanol.
Tensile testing of LLDPE/
2. Materials and Methods CMC/TPS film was carried out following
2.1 Materials ASTM D882. The film was cut into a 2.0
Food grade carboxymethylcellulose cm × 25.0 cm rectangular strip and
(CMC), was purchased from Chemipan preconditioned at 23±2℃, 70±5%RH prior
Co., Ltd. Thailand. to testing. Load cell and cross-head speed
Linear-low density polyethylene were 500N and 30 mm/min, respectively.
(LLDPE) was supplied by PTT Global The grip separation were set at 100 and 50
Chemical Public Company Ltd. Thailand. mm for MD and TD test, respectively.
Cassava starch was from Young’s modulus, tensile strength and
Kijroongruang Tapioca Factory Co. Ltd. elongation at break were recorded.
Thailand. Drop dart Impact test was carried
2.2 Preparation of CMC solution out following ASTM D1709. The film was
CMC solution with the cut into a 22.0 cm × 25.0 cm rectangular
concentration of 3.3, 6.6, 9.9 and 13.3 strip. The weight of the dart was varied
%w/v were prepared by dissolving CMC PC43
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
from 20-390 g and the drop height was set for pellets made from LLDPE and TPS.8
at 66 cm. With the incorporation of CMC into
Surface morphology of films was LLDPE/TPS, MFI values significantly
analyzed using scanning electron increased. This result suggests the
microscopy (SEM, LEO 1450 VP). increased flow behavior of the pellets at
high temperature of 190℃. With increasing
4. Results & Discussion CMC content, MFI of LLDPE/CMC/TPS
4.1 Physical properties pellets was found to increase accordingly.
The effect of the CMC content on This was because of the gel formation of
MFI and density of LLDPE/CMC/TPS CMC molecules owning to their physical
pellets are shown in Figure 1. crosslink that lessens hydrogen bonding
between starch and CMC. Therefore, both
starch and CMC molecules can freely flow.
This result is in good accordance with the
result proposed by Garg and Jana9 that MFI
of LDPE increased with cross-linked
starch. Furthermore, CMC gel formation
was apparently evidenced by SEM analysis
and the result was displayed in Figure 2.
The addition of CMC in starch matrix,
therefore caused a rugged surface with
dispersed gel. According to Porsch and
Wittgren 10, hydrogel network formation of
CMC was a result of physical cross-linking
through intermolecular H-bonding in CMC
molecules. The hydrogen bonds act as
cross-linked points, inducing a decrease of
CMC solubility in water and bring about the
formation of an elastic hydrogel. As the 3D-
network of CMC formed, the mechanical
properties e.g. tensile strength and Young’s
modulus as well as hydrophobicity of
LLDPE/TPS incorporated with CMC
hydrogel are expected to increase.
Figure 1b shows the decrease in
Figure 5. Effect of CMC content in melt density of LLDPE/TPS from 1.065 g/cm3 to
flow idex (a) and density (b) of 0.968 g/cm3 when 3.3%w/w CMC solution
LLDPE/CMC/TPS pellets. was introduced to LLDPE/TPS blend. This
may be due to the hydrogen bonding
MFI indicates the flow properties of
between starch and CMC molecules
pellets to determine shearing and heating
lessened the interactions between starch
parameters in plastic processing. It was
molecules themselves. With an increase in
found that MFI of all film formula are in the
CMC content, the density was slightly
range 1.3 to 1.6 g/10 min, which are typical PC44
increased. The gel formation of CMC is
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
believed to be responsible for this result. The gel formation of CMC brought about
Like gelatinization in starch,11 when non-homogeneous structures, thus leading
gelatinized, intermolecular interactions to the lessening in such mechanical
between CMC molecules were broken properties. The effect of non-homogeneity
down, and the molecules faced a hardship of the LLDPE/TPS film on the deterioration
to from crystal structure. Therefore, density of its mechanical properties was also noted
decreased. by Nguyen et al.12
The effect of CMC concentration on
4.2 Mechanical properties drop dart impact of the LLDPE/CMC/TPS
Tensile properties e.g. tensile film is also shown in Figure 4.
strength, Young’s modulus and elongation
at break of LLDPE/CMC/TPS films were
evaluated and the results are displayed in
Figure 3.

Figure 2. SEM micrographs of

LLDPE/TPS (a) and LLDPE/CMC/TPS
(13.3 %w/v of CMC) (b) at a magnification
of 100X.
In Figure 3, it was found that with
the addition of 3.3 %w/v CMC, tensile
strength, elongation at break and Young’s
modulus of the LLDPE/CMC/TPS film
were equivalent to those of LLDPE/TPS
film. However, those three values reduced Figure 3. Effect of CMC content on tensile
accordingly with increasing CMC content. strength (a), Young’s Modulus (b) and PC45
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
elongation at break (c) of CMC, tensile strength, Young’ modulus,
LLDPE/CMC/TPS films in both machine elongation at break and drop dart impact
direction (MD) and transverse machine were almost unaffected. However,
direction (TD). excessive amount of CMC worsened
mechanical properties of
LLDPE/CMC/TPS films because of the
increased heterogeneity of the system due
to CMC gel formation.

Acknowledgements
This work was financially
supported by the Research Grant of
Burapha University through National
Research Council of Thailand (Grant no.
51.2/2562). The authors would like to thank
Multibax Public Company Limited for
courtesy of bio-plastic processing and
analysis.
Figure 4. Effect of CMC content on drop
dart impact of LLDPE/CMC/TPS films. References
Like the effect of CMC content on 1. Cao, X.; Chen, Y.; Chang, P. R.;
the tensile strength, elongation at break and Stumborg, M.; Huneault, M. A. J.
Young’s modulus, when 3.3 %w/v CMC Appl. Polym. Sci. 2008, 1(109),
was introduced into LLDPE/TPS film, drop 3804-3810.
dart impact of the film was almost 2. Joshi, M.; Aldred, P.; Mcknight, S.;
unchanged. However, an increase in CMC Panozzo, J. F.; Kasapis, S.; Adhikari,
concentration created the decline in dart R.; Adhikari, B. Carbohydr. Polym.
impact of the films, due to their non- 2013, 92 (2), 1484–1496.
homogeneous structure. 3. Fu, Z.; Wang, L.; Li, D.; Wei, Q.;
Adhikari, B. Carbohydr. Polym.
5. Conclusion 2011, 86 (1), 202–207.
In film processing industry, a 4. Young, W.; Dejager, L. Food Addit.
suitable amount of CMC can be used to Contam. Part A 2018, 35(12), 2309-
improve the flow property as well as the 2314.
density of starch-based films without 5. Ma, X.; Chang, P. R.; Yu, J.
deterioration of their mechanical properties. Carbohydr. Polym. 2008, 72(3),
For LLDPE/TPS system, the addition of 369–375.
3.3% w/v of CMC into TPS before blending 6. Ghanbarzadeh, B.; Almasi, H.;
with LLDPE resulted in LLDPE/CMC/TPS Entezami, A. A. Ind. Crops Prod.
pellets with increased MFI and reduced 2011, 33 (1), 229–235.
density. The increased MFI helps to 7. Tavares, K. M.; de Campos, A.;
facilitate film-blowing and the reduced Mitsuyuki, M. C.; Luchesi, B. R.;
density is beneficial for transportation. Marconcini, J. M. Carbohydr.
Moreover, with this suitable amount of Polym. 2019, 223, 115055. PC46
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8. Panronga, T.; Karbowiak, T.; 27–35.
Harnkarnsujarita, N. Food. Packag. 11. Morris, V.J. Trends Food Sci.
Shelf Life. 2019, 21, 100331. Technol. 1990, 1, 2–6.
9. Grag, S.; Jana, A. K. Euro. Polym. J. 12. Nguyena, D.M.; Vua, T.T.; Grillet,
2007, 43(9), 3976–3987. A.C.; Ha Thuc, H.; Ha Thuc, C.N.
10. Porsch, B.; Wittgren, B. Carbohydr. Polym. 2016, 136, 163–
Carbohydrate Polymers. 2005, 59, 170.

PC47
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Prediction lifetime of membrane (PEBAX) for separation of co2/ch4
mixture
Araya Chonnikorn1, Kajornsak Faungnawakij2, Chalida Klaysom1*
1
Department of Chemical Engineering and Center of Excellence in Particle and Material processing
Technology, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
2
Nanomaterials for Energy and Catalysis Laboratory (NEC), National Nanotechnology Center (NANOTEC),
National Science and Technology Development Agency (NSTDA), Pathumthani, 12120, Thailand
*E-mail: [email protected]

Membranes are widely used as separation systems in many industries due to its many
benefits such as small size of system space, high reliability, and durability. In terms of the
durability of the membranes, their lifetime should be considered. Lifetime of the membrane is
a crucial factor determining performance, stability and operating cost for membrane
replacement of the system. The membrane lifetime is dependent on many effects such as
material manufacture, operating, condition and maintenance. Physical aging is a phenomenon
that causes a change in the molecular chains of polymer, thus affecting free volume and
separation performance of membrane. In this study, we choose PEBAX as a membrane for the
study because it has superior mechanical and dynamic properties (flexibility, impact resistance,
energy return, fatigue resistance). A mathematical model for predicting lifetime of membrane
for separation of CO2/CH4 mixture in biogas upgrading application was successfully
developed. This model was developed by using a time-temperature superposition concept in
which membrane separation experiment was conducted under different operating temperature.

1. Introduction The lifetime of membranes depends

Membrane technology is widely used on many factors, such as the material used to
as a separation unit in many industries make the membranes, operating system,
including it is mainly due to the membrane operating conditions, and the maintenance
technology has many benefits such as space cycle, etc.
saving, system optimization reliability, Polyether block amide or PEBA is a
durability, cost reduction, etc. In order to thermoplastic elastomer (TPE) and it is
implement a gas separation system using widely used for making a gas separation
membrane technology, efficiency and cost membrane. PEBA is known under the
must be considered. Another important factor tradename of PEBAX® (Arkema). It is a
is the lifetime of membranes, which block copolymer obtained by polyconden-
determines the operating costs of system. sation of a carboxylic acid polyamide (PA6,
The performance of gas separation PA11, PA12) with an alcohol termination
membranes will degenerate by service period polyether.2
because of their natural physical aging In this study, the model will be
behavior. Physical aging is the molecular created to predict the lifetime of the PEBAX
realignment of polymer chains that were membrane for separating carbon dioxide and
frozen in place during processing prior to methane in biogas. The model was developed
reaching thermodynamic equilibrium. by using time-temperature superposition
Therefore, it is useful to predict the lifetime concept and will be used to find the lifetime
of membrane for designing a system.1 of the selected membranes. PC48
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2. Materials and Methods cylinder. After that, the prepared hollow fiber
2.1 Materials support was dipped into the coating solution
Polysulfone (PSF, MW~22,000 for 15 min. Finally, thin coated composite
g/mol) were bought from SigmaAldrich. hollow fiber membranes were dried
Polyether-block-amide (Pebax 1657) was overnight in an oven at 60 °C
purchased from Arkema Inc. N-Methyl-2- 2.3 Characterization method
Pyrrolidone (NMP, 99%) was obtained from Scanning electron microscope (SEM,
Acros Organics. Ethyl alcohol (EtOH) was Hitachi S-3400N) was used to observe
bought from Carlo Erba. morphology and structure of the prepared
2.2 Membrane preparation membranes. The membrane sample was
2.2.1 Support layer fractured in liquid nitrogen and gold (Au)
The support layer of hollow fiber was coated on the sample by an ion sputter
membrane was prepared by a dry-jet/wet coater (Hitachi E-1010).
quench spinning process. The solution Hollow fiber membranes were
prepared by mixing PSF in NMP at 400 rpm, packed in a stainless-steel module with 40
65°C. The concentration of solution is 20 mm inside diameter by using an epoxy glue.
wt%. After that, left the PSF solution at room The membrane module was then attached to
temperature for 20 min and 10 min of the gas permeation apparatus illustrated in
sonicated for degas the air trapped in the dope Figure 1 20 cm3/min of CO2, CH4, CO2/CH4
solution. Solution was added into the dope (50:50 mol ratio) gas mixture was fed from
solution and distillated water into the bore the shell side of membrane module, while
fluid cylinder of extruder. The extrusion helium was fed from the tube side of the
parameters were controlled as follows: membrane module to carry permeate gas to
- Air gap between spinneret and the gas chromatography (GC, Shimadzu GC-
coagulation bath = 10 cm 14B) and film flow meter (Horiba Stec VP-2)
- Extruder temperature = 30°C at 30 °C. All prepared composite membranes
-The mass flowrate of dope solution were tested at the steady state and isothermal
and bore fluid = 1 . 1 g/min and 0 . 2 8 g/min, conditions. The range of temperature,
respectively. pressure and time are 30-70 °C, 2 bar and 0-
The obtain support layer of hollow 120 min, respectively.
fiber was kept in distillated water for 2 days
and dried overnight in a vacuum oven at 5 0
°C.
2.2.2 Coating Pebax1657 of the selective
layer on the PSF support
Solution of Pebax1657 was prepared
by mixing 5 wt% of Pebax1657 with a mixed
solution of water and ethanol. Then, 20 min
of sonication was applied for degassing the
air trapped in the solution Flow meter
The prepared coating solution
containing PEBAX was added into a glass Figure 1. Gas permeation apparatus diagram. PC49
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.4 Permeability method  Preparing the master curve by
The Eq.1 was used to determine the shifting data At temperature lower
permeability of CO2 and CH4 in gas mixture than the reference temperature, the
in Barrers unit, where 1 barrers = 10-10 cm3 data were shift to the left. At
(STP).cm/cm2.s.cmHg. temperature higher than the
reference temperature, the data were
shift to the right. Such that, all curve
(1) collapses into a single curve by
means of horizontal shift factor).
Where Pi = component, i = gas Master curve was created for
permeability, Ji = component i gas flux, p0, prediction of the lifetime of
i - pℓ, i = transmembrane pressure of membrane.
component I, ℓ = membrane thickness
2.5 Model method 3. Results & Discussion
Time-temperature superposition is 3.1 Membrane characterization
a tool to determine the material properties The cross-section morphology of
over broad range of times and temperature the hollow fiber membrane was
by shift factor. The principle typically investigated by a scanning electron
involves the following steps: microscopy (SEM) and shown in Figure 2.
 Experimental determination of The structure of hollow fiber membrane
frequency-dependent curves of showed a porous structure with a dense
mechanical properties at several selective layer on the outer surface. The
temperatures and for a range of outsize diameter and the thickness of PSF
time. support layer hollow fiber were about
 Finding a shift factor from 600±30 μm and 100±30 μm, respectively.
Williams-Landel-Ferry or WLF The thickness of polyether-block-amide
model3,4 by:
(Pebax) was around 2.12±0.22 μm.

(2)
Where at is shift factor, C1 and C2 are
constants, T is temperature in Kelvin, T0 is
reference temperature in Kelvin. (WLF
equation is applicable for system having
glass transition temperature, Tg. If To ≈ Tg
then C1 ≈17.44 and C2 ≈ 51.6 K.)

PC50
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Pebax

PSF

Figure 2. The cross-section of PSF/Pebax composite membrane (left) and it close-up at the
outer fiber diameter of the composite membrane (right).
3.2 Membrane Performance from one place to another place if there is
3.2.1 The effect of temperature and time sufficient empty space or free volume.6
on gas separation properties of Pebax Therefore, the free volume of the
membranes membrane increases, the permeability also
The permeability of carbon dioxide increases.
and methane tested at different The permeability gradually
temperatures (30-70 ˚C) is shown in Figure decreased with time, implying the physical
3. In addition, at higher operating aging of the membranes. Physical aging is
temperature the permeability tended to thermodynamic in nature that influenced
increase. In the rubbery state the polymer the transport of small molecules in glassy
segments can rotate freely along the main polymer.6 Polymer chain packing is the
chain bonds, implying a high degree of driven toward the lowest free energy state
chain mobility.5 For this reason, it increases that causes the molecules to seek the
free volume and thus the gas can permeate minimum free volume condition.1 The free
through the membrane easily. The basic volume is decreased, the permeability also
concept is that a molecule can be diffusive decreases.

Figure 3. (left) Permeability of carbon dioxide with different temperature and time (right)
Permeability of methane with different temperature and time. PC51
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.3 Lifetime Prediction superposition was applied to form a master
Figure 4. Show the permeability curve in Figure 5. The master curve shown
fraction of CO2 and CH4 versus time with the continually decreased and stable at 70
different temperature. The permeability % at 8E+13 min on CO2 and CH4.
increased with increasing operating
temperature. The time-temperature

Figure 4. (left) The permeability fraction of carbon dioxide with different temperature (right)
The permeability fraction of methane with different temperature.

Figure 5. (left) The master curve of Pebax membrane (Carbon dioxide) (right) The master
curve of Pebax membrane (Methane).

4. Conclusion work, Time-temperature superposition

concept was applied to create the master
There are two factors that affect the
curve that can be used to predict the lifetime
membrane performance: temperature and
of membrane. The lifetime prediction from
operating time. In term of temperature, at
the developed model in this work showed
higher operating temperature the
that the performance of prepared PEBAX PC52
permeability tended to increase. In this
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
membrane are quite stable. After being
used for several years, the performance will
only drop for 30%.

Acknowledgements
The authors acknowledge support
from Center of excellence in Particle and
Material Processing Technology,
Department of Engineering and Center of
Excellence in Particle and Material
processing Technology, Faculty of
Engineering, Chulalongkorn University also
acknowledge instrumental analysis support
from Nanomaterials for Energy and Catalysis
Laboratory (NEC), National Nanotechnology
Center (NANOTEC), National Science and
Technology Development Agency (NSTDA)

References
12. Ywu,J.F.;Sheng,W.H.;Kueir,R.L.;Juin,Y
.L.Prediction of long-term physical
aging of poly(methyl methacrylate)
membranes for gas separation
Elsevier.B.V.,2007,08,0011-9164.
13. Polyether block amide.
http://en.wikipedia.org/wiki/
Polyether_block_amide (accessed
Sep 14, 2018)

14. Time-temperature superposition.

http://en.wikipedia.org/wiki/Time- temperature_superposition (accessed

July 20, 2019)
15. Time-temperature superposition.
http://www.powershow.com/viewht/8265ec-MDdjZ/Time-
temperature_superposition_powerpoint_ppt_presentation(accessed Dec 10, 2017)
16. Basic Principless of Membrane Technology.Kluwer Academic Publishers, 2nd ed.; Marcel
Mulder; Netherlands, 1997;Vol.2 , pp 31-33

PC53
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Nanoencapsulation of Andrographis paniculata extract by cellulose
derivatives
Titapa Singchuwong1, Theerachart Leeprasert1 and Thitinun Karpkird 1*
1
Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand
*E-mail: [email protected]

In this project, acetone crude extract of Andrographis paniculata (AP) was

encapsulated by using hydroxyethylcellulose (HEC), biocompatible polymer, to increase the
releasing time and improve the biological activities. The major components of crude extract
were determined using HPLC-MS and found that andrographolide (61%), 14-
deoxyandrographolide (15%), neoandrographolide (10%) were three major components. The
crude extract was encapsulated by HEC with the 1:1 ratio of polymer: crude extract, and
provided 41% loading efficiency. The morphology of HEC nanoparticles was studied by SEM
and showed sphere nanoparticles. The size of nanoparticles was 270.0±115.13 nm investigated
by DLS. The controlled release of andrographolide from nanoparticles was done in PBS pH
5.5, and showed that the andrographolide encapsulated in nanoparticles released slower than
pure andrographolide. This study can develop the nanoparticles that retard the release rate of
active ingredients in the biological systems.

1. Introduction
Andrographis paniculata (AP) is one
of the most popular medicinal plants used
traditionally for the treatment of array of
diseases.1 The major components found in
Andrographis paniculata leaves are andro-
grapholide, neoandrographolide, 14-
deoxyandrographolide and 14-deoxy-11,12-
didehydroandrographolide (Figure 1). But Andrographolide Neoandrographolide
the most biological activities extracted from
herb have been degraded short time. The
encapsulation by polymers can be reported to
improve the biological activities and retard
the releasing time. Cellulose and cellulose
derivatives are most used in industrial such as
food, medicine, cosmetics, detergents, paper,
textiles, etc.2 In this work, hydroxylethyl-
cellulose (HEC) was used for Andrographis
14-deoxy-11,12-
paniculata crude extract encapsulation.
14-deoxyandro- didehydroandro-
HEC-AP nanoparticles (HEC-AP-NPs) can grapholide grapholide
be developed to improve the biological
activities that retard the release rate of active Figure 1. Chemical structures of
ingredients in the biological systems. andrographolide, neoandrographolide, 14- PC54
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
deoxyandrographolide and 14-deoxy-11,12- weight and loading efficiency was calculated
didehydroandrographolide. follow the equation below.
2. Materials and Methods weight of extract
%Loading = ( ) × 100
Andrographis paniculata extraction. weight of nanoparticle
Andrographis paniculata leaves Study of control release andrographolide
powder 200 g was soaked in acetone 500 mL. encapsulated in nanoparticles.
After 2 days, the solution was filtered and HEC-AP-NPs 5mg (equivalent to
solvent was evaporated by rotary evaporator. andrographolide 2 mg) dispersed in 2mL
Determination of the components from PBS pH 5.5. Andrographolide 2 mg
Andrographis paniculata crude extract. dissolved in 2mL PBS pH 5.5 was also
AP crude extract 125 ppm was prepared. The studied solution was added
prepared in 1 mL methanol. The HPLC-MS into dialysis bag (cut-off 3500) and soaked in
condition was: injection volume 10 µL, 50 mL PBS pH 5.5. The 1 mL of PBS
temperature column 25 ๐C, flow rate 0.5 solution was collected after 1, 2, 3, 6 and 24h
to determine the amount of andrographolide
mL/min, mobile phase 35% ACN (0-6 min),
released by HPLC with condition : injection
35-45% ACN (6-12 min), 45-35% ACN (12-
volume 1 0 µL, temperature column 2 5 ๐ C,
13 min), 35% ACN (13-15 min), ESI,
negative mode, capillary voltages 3000 V, flow rate 0 . 5 mL/min, mobile phase 3 5 %
nebulizer pressure 20 psi, gas temperature : ACN (0-6 min), 35-45% ACN (6-12 min),
220 ๐C, gas flow : 12 L/min.3 45-35% ACN (12-13 min), 35% ACN (13-
1 5 min),3 detector : UV-Vis 229 nm.
Encapsulation of Andrographis paniculata
Andrographolide was used as standard.
extract by HEC.
Hydroxyethylcellulose (HEC) 100
3. Results & Discussion
mg dissolved in 20 mL D.I. water and heat at
Determination of the components from
70 ๐C. AP crude extract 100 mg dissolved in
Andrographis paniculata crude extract.
5 mL ethanol then added into HEC solution The major components from AP
drop by drop with rate 2 mL/min, stir crude extract was studied by HPLC-MS.
overnight. The suspension was appeared and HPLC-MS Chromatogram of AP crude
centrifuged. The remained AP crude extract extract are shown in Figure 2. As the results,
solid was removed. The suspension solution andrographolide (61%), neoandrographolide
of nanoparticles was freezed dry. The size (10%), 14-deoxyandrographolide (15%) and
and shape of nanoparticles were determined un-identified compounds (14%) were found
by DLS and SEM. in AP crude extract as peak 1, 2 and 3,
Determination of loading efficiency of respectively (Figure 2a).
nanoparticles.
HEC-AP-NPs 30 mg dispersed in 2
mL acetone in test tube. The solution was
sonicated for 15 min and the remained solid
was removed by syringe-filter. The acetone
was evaporated the remained solid was
PC55
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 3. SEM images of blank NP (HEC-
NPs) (a) and loaded NP (HEC-AP-NPs) (b).
Control release study.
The control release of
andrographolide in nanoparticles was done in
PBS pH 5.5 indicating that at 24h
andrographolide encapsulated in
nanoparticles released about 17% which was
three times slower than free andrographolide
(41%) (Figure 4). These results showed, the
encapsulation by hydroxyethylcellulose can
Figure 2. HPLC-MS Chromatogram of AP be retarded the releasing time of the active
crude extract (a) and HEC-AP nanoparticles compounds. This might be improved the
(b). biological activities of the active compound
to longer time.
HEC-AP nanoparticles.
The HEC-AP nanoparticles were 50
41.15%
prepared in water giving about 41% loading 40
Percent release

efficiency. The compounds encapsulated in

30
HEC-AP nanoparticles were studied by
HPLC-MS as shown in Figure 2b. It was 20 16.86%
found andrographolide, neoandrographolide 10
and 14-deoxyandrographolide were also
0
detected in HEC-AP nanoparticles that 0 2 4 6 8 10 12 14 16 18 20 22 24
similar to AP crude extract. The morphology
Time (Hours)
of HEC nanoparticles was sphere
nanoparticles observed by SEM (Figure 3). Andrographolide HEC-AP-NPs
The size of HEC nanoparticle was about
270.0 ± 115.13 nm and showed the Figure 4. Percent release of andrographolide
moderately polydispersion index value (PDI) from nanoparticles.
indicating nanoparticles are similar size. The
zeta potential of the HEC nanoparticles are - 4. Conclusion
31.9 ± 7.38 mV, a negative charge on the The major components in crude
surface of the nanoparticles are causing from extract, andrographolide (61%), 14-deoxy-
hydroxyl group on HEC. andrographolide (15%) and neoandro-
grapholide (10%) were detected from acetone
AP crude extract. The encapsulation of
Andrographis paniculata crude extract by
HEC was successfully done in this work. The
loading efficiency of HEC was 41%. The size
(a) (b) of HEC nanoparticles were 270±115.13 nm.
The control release of andrographolide from PC56
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
nanoparticles released about three times References
slower than free andrographolide. These 1. Chang, H. M.; But, P. P. H. Pharmacology
results showed that encapsulation of and Application of Chinese Material Medica;
Andrographis paniculata extract by HEC can World Scientific Press: Singapore, 1987;
be developed to retard the releasing rate of Vol. 1, pp 918–28.
active ingredients in the biological systems. 2. Dusadi, S.; Sujimon, T.; Chittima, M.;
Duangratana, S. Isolation and
Acknowledgements characterization of cellulose from water
hyacinth, sugar cane bagasse, and narrow leaf
The financial of this project was
cattail. Thesis, Faculty of Pharmacy,
supported by the Faculty of Science,
Srinakharinwirot University.
Kasetsart University and Thailand Science
3. Nanthanit, P.; Duangchit, P.; Nuchanart,
Research and Innovation (TSRI), Industry
R.; Tawit, S.; Teerapat, U.; Wanwisa, P.;
devision (RDG6250).
Saichit, T.; Jutamaad, S. Planta Med. 2016,
82, 113–120.

PC57
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The development of plasticization-resistance, membranes for biogas
upgrading
Apiwat Surananthsatian1, Kajornsak Faungnawakij2, Chalida Klaysom1*
1
Center of Excellence in Particle and Material Processing Technology,
Department of Chemical Engineering, Faculty of Engineering,
Chulalongkorn University, Bangkok 10330, Thailand
2
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency,
Pathumthani 12120, Thailand
*E-mail: [email protected]

Biogas is an important renewable energy produced from anaerobic microbial digestion

of organic wastes. Biogas is composed mainly of methane and carbon dioxide and other
miscellaneous gases such as hydrogen, hydrogen sulfide, nitrogen, and steam. To use biogas
as fuel carbon dioxide must be first removed. The gas separation based on membrane
technology has attracted tremendous attention for biogas upgrading. In this work, hollow fiber
composite membrane from poly(ether-block-amide) or (PEBAX®1657) and polysulfone (PSF)
was fabricated. The polymer (PEBAX) of the selective layer was cross-linked using
2,4-toluylene diisocyanate to enhance mechanical stability and the plasticization-resistance of
membranes. The effects of crosslinking time on gas separation performance and plasticization
of the resultant hollow fiber composite membrane in biogas upgrading were also investigated.
The result revealed that the crosslinked Pebax 1 minute of hollow fiber composite membrane
can improve the polymer structure CO2 permeability and CO2/CH4 selectivity from 0.65 to 1.10
GPU and 18.04 to 19.71 respectively. The result showed that at the same operating conditions
were found at 4 bars and 30 oC, the crosslinked Pebax 1 minute provide a better separation
performance compared to non-crosslinked.

1. Introduction sulfide (H2S), nitrogen (N2) and water vapor

Nowadays, the demand for renewable etc. The inert, contaminated acid gases like
energy is increasing along with the growing CO2 and H2S could cause a damage
concern about environmental problems due to the equipment and reduce the heat capacity
to high greenhouse gases (GHGs) by CO2 of the biogas. Therefore, it is of necessary
emissions. Therefore, greener sources of to make the biogas cleaner and free from
energy are required as alternatives to replace the contaminations before being used.3
fossil fuels. Biogas is a renewable energy that The conventional processes for
can be produced by anaerobic degradation of biogas upgrading include pressure swing
organic compounds and could be used as the adsorption, water scrubbing and organic
substitute for fossil fuels and natural gas.1, 2 solvent scrubbing. However, the above-
Biogas contains approximately 60 - 70% of mentioned methods have several drawbacks
methane (CH4) and 20-30% of carbon due to the complicated operation, high
dioxide (CO2). The rests are other gases such energy requirements, difficult to handle and
as hydrogen (H2), oxygen (O2), hydrogen high capital investment and operational PC58
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
costs.4 Membrane separations is one of PSF hollow fiber membrane was
the most effective techniques for gas obtained by dissolving 20 wt% of PSF in
purification with simple process control and NMP under a continuous stirring at room
easy to scale up for industrials. Poly (ether- temperature for 24 hours. After that,
block-amide) with the trade name of this solution was degassed for 4 hours using
Pebax1657 was widely used as a material for ultrasonication bath to remove the trapped
making a membrane for CO2 removal. bubbles from the solution. Then, the prepared
This polymer consists of a polyamide (PA) solution was added into the dope cylinder
segment and a polyether (PE) segment. and distilled water was added into the bore
Polyamide has a remarkable hardness and cylinder of an extruder. The PSF solution and
crystalline structure, which can provide high bore fluid in each cylinder were coextruded
mechanical resistance.5, 6 In contrast, flexible by dry - jet/wet quench spinning process
polyether has high permeability, especially by using the following conditions.8
for polar molecules like CO2. However,  10 cm of an air gap between
the efficiency of membrane normally the spinneret and coagulation bath
reduced from the plasticization effect due to  40 °C of extruder temperature
the presence of high CO2 content in the feed  1.10 g/min of dope cylinder solution
stream, causing the loosen polymer chain mass flowrate
packing. As a result, the membranes lost  0.28 g/min of bore fluid solution
the selective ability and separation mass flowrate.
performance.7 The obtain support layers of hollow
In this work, the plasticization fiber membrane was kept in distilled water
resistance toward the CO2 gas of the for 1day and dried overnight in an oven at
membrane was improved by crosslinking 60 °C and continued to dry in a vacuum oven
the polymer structure of Pebax using at 60 °C. Pebax1657 was mixed with
2,4-toluylene diisocyanate. The effects of H2O/EtOH (30/70 weight ratio) to give
crosslinking time on mechanical properties 5 wt% solution followed by continuous
and separation performance were stirring for 24 hours at room temperature.
investigated. Then, the prepared coating Pebax was added
into a glass cylinder. After that, he prepared
2. Materials and Methods hollow fiber membrane support was dipped
2.1 Materials into the coating solution for 15 minutes.
Polysulfone (PSF, MW 22,000) and Then, it was dried at room temperature for
2,4-toluylene diisocyanate. (TDI, 95%) were 10 minutes. Finally, thin coated composite
obtained from Sigma-Aldrich. Pebax1657 hollow fiber membranes were dried
as the selective layer of the membrane was overnight in an oven at 60 °C. Crosslinking
purchased from Arkema. N-methyl-2- of Pebax1657 was carried out by immersing
pyrrolidone (NMP) was obtained from Acros the hollow fiber membrane in 2% (v/v)
organics, Belgium. Hexane (AR grade) and solution of TDI in hexane for 1 - 10 minute.
ethyl alcohol (EtOH, absolute) were Then, the membranes were removed from
purchased from Rci Labscan co. ltd. the crosslinking agent and washed
2.2 Membrane preparation thoroughly with a distilled water for an hour. PC59
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
The membranes were then dried in a vacuum (𝒚𝒊 /𝒚𝒋 )
oven at 60 °C for 24 hours to remove 𝜶𝒊𝒋 =
(𝒙𝒊 /𝒚𝒋 )
the residual solvent.
2.4 Membrane characterization Where:
Scanning electron microscope (SEM, 𝜶𝒊𝒋 = membrane selectivity
Hitachi S-3400N) was used to observe 𝒚𝒊 = mole fraction of the component 𝒊 in the
the morphology and structure of the prepared permeate side
membranes. The membrane sample was 𝒚𝒋 = mole fraction of the component 𝒋 in the
fractured in liquid nitrogen and gold (Au) permeate side
was coated on the sample by an anion sputter 𝒙𝒊 = mole fraction of the component 𝒊 in the
coater (Hitachi E-1010). Attenuated total retentate side
reflectance - Fourier transform infrared 𝒚𝒋 = mole fraction of the component 𝒋 in the
spectroscopy (ATR-FTIR, Scientific Nicolet
retentate side
6700) was used to measure the chemical
functional group of the samples. For each
3. Results & Discussion
specimen, 35 scans were collected with
3.1 Membrane morphology
a wavenumber resolution of 0.4824 cm-1.
Composite hollow fiber membranes
2.5 Membrane performance test
were successfully fabricated. The
Hollow fiber composite membranes
morphology of the prepared supported and
were packed in a stainless-steel module with
Pebax coated hollow fiber membranes was
30 cm inside packing with epoxy glue.
illustrated in Figure 1-3.
The membrane module was then attached to
the gas performance testing unit. 20 cm3/min
of CO2/CH4 (50:50 mol ratio) mixed gas was
feed from the shell side of the membrane
module, while helium was feed from the tube
side of the membrane module to carrier gas
to gas chromatography (GC, Shimadzu GC-
Figure 1. The cross section of PSF hollow
14B) and film flow meter (Horiba Stec VP-
fiber (top) and its close-up (bottom).
2). All prepared composite membranes were
tested at the isothermal conditions. The range
of pressure is 1-4 bars, respectively
Permeability
𝒋𝒊 × l
P𝒊 =
(𝒑𝒊𝒐 − 𝒑𝒊𝒙 )
Where:
P𝒊 = component 𝒊 gas permeability Figure 2. The cross section of PSF/Pebax
𝒋𝒊 = component 𝒊 gas flux hollow fiber composite membrane (top) and
𝒑𝒊𝒐 − 𝒑𝒊𝒙 = transmembrane pressure of its close-up (bottom).
component 𝒊
l = membrane thickness
Selectivity PC60
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 (a) (b) (c)

(d) (e) (f)

Figure 3. The cross section and close-up of crosslinked PSF/Pebax membrane for 1 minute
(a,d), 5 minutes (b,e), and 10 minutes (c,f) respectively.

The cross-section morphologies of PSF

hollow fiber support showed a highly porous
structure with finger-like macropores.
The outside diameter of PSF fiber was
approximately 670 μm (Figure 1.). Pebax
coated onto PSF support is shown in Figure
2. The coated layer clearly appears dense
with the thickness around 1.05 μm.
Crosslinked Pebax at 1 minute, 5 minutes and
10 minutes, respectively are compared
in Figure 3. similar to the non-crosslinked
membranes, the structures of crosslinked
Figure 4. The ATR-FTIR spectra of pure
Pebax layer were also dense. The average
PSF (a), PSF/Pebax (b) and crosslinked
thickness of the selective layer was
Pebax (c).
approximately 1.10 μm, 1.17 μm and
1.07 μm. For PSF supported layer, peaks at
3.2 Functional intermolecular interactions 1151 cm-1 (–O–S–O stretching), 1244 cm-1 (–
The interactions between the polymer C–O–C stretching) and 1585 cm-1 (–C–C
chains with the crosslinking agent were aromatic), which are characteristics of
investigated by using ATR-FTIR analysis sulfone group, were observed. The
and the results are presented in Figure 4. transmittance at 1020 cm-1 and 830 cm-1
represents (–C–H stretching) of the aromatic PC61
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
ring in PSF. For Pebax coated membrane (a)
without the crosslinking treatment,
the characteristics peaks of Pebax located at
3299 cm-1 (–N–H stretching), 1732 cm-1 (–
C=O stretching), 1638 cm-1 (–C=O in H–N–
C=O), and 1099 cm-1 (–C–O–C stretching)
indicated that the selective layer was
successfully coated on the PSF fiber support.
For crosslinked Pebax, it shows peak
at 3299 cm-1 (–N–H stretching), 1732 cm-1
(–C=O stretching), 2234 cm-1 (–C=O
stretching) and 1615 cm-1 (–C=N stretching).
(b)
The result means that, Characteristic
functional groups of Pebax and TDI appeared
in crosslinked Pebax membrane. It can
approve that crosslinked Pebax is successful.
3.3 Membrane performance
The effects of crosslinking treatment
on the CO2 and CH4 permeability and
selectivity were investigated and illustrated
in Figure 4. The CO2 and CH4 permeance of
all membranes increased with increasing
pressure. The crosslinked membranes (c)
showed much lower CO2 and CH4 permeance
than non-crosslinked due to the close
compaction of polymer chains. The longer
the crosslinking time applied, the denser
the membrane structure and thus the lower
the gas permeability the membranes are.
On the other hand, CO2/CH4 selectivity of
the crosslinked membrane was four times
higher than the non-crosslinked one.
In addition, at higher operating pressure
the membrane with crosslinking treatment
can maintain selectivity while the untreated Figure 4. The effects of crosslinking
membrane lost its ability to separate CO2 treatment on the CO2 and CH4 permeability
from CH4. This implies that the crosslinking operating pressure and feed composition of
treatment can improve mechanical properties CO2/CH4 = 50:50.
and plasticization resistance of the
membrane.
(a, b) and selectivity (c) of the membrane
tested at 30 °C at 1-4 bars o PC62
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
4. Conclusion the Energy Regulatory Commission
This work has demonstrated (OERC).
the possibility of using composite
membrane for CO2/CH4 separation. In all References
membranes, the effects of increased 1. Rasi, S.; Veijanen, A.; Rintala, J.
crosslink time result in a reduction of gas Energy. 2007, 32 (8), 1375-1380.
permeability while the membrane 2. Ullah Khan, I.; Hafiz Dzarfan Othman,
mechanical properties could be enhanced M.; Hashim, H.; Matsuura, T.; Ismail,
due to significant increment in A.; Rezaei-DashtArzhandi, M.; Wan
CO2/CH4 selectivity result from close Azelee, I. Energy Convers. Manage.
2017, 150, 277-294.
compaction of the polymer chain.
3. Ezekoye, V.; Okeke, C. Pac. J. Sci.
For operating at high pressure, gas
Technol. 2020, 7, 176-184.
permeability and CO2/CH4 selectivity trend 4. Chen, X.; Vinh-Thang, H.; Ramirez,
to increase except non-crosslinked has A.; Rodrigue, D.; Kaliaguine, S. RSC
lower selectivity than others, cause the Adv. 2015, 5 (31), 24399-24448.
loose of polymer chain from CO2- 5. Li, T.; Pan, Y.; Peinemann, K.; Lai, Z.
plasticization. J. Memb. Sci. 2013, 425-426, 235-242.
6. Aitken, C.; Koros, W.; Paul, D.
Acknowledgements Macromolecules. 1992, 25 (14), 3651-
The authors gratefully acknowledge 3658.
the financial support from Thailand 7. Ying, Y.; Cheng, Y.; Peh, S.; Liu, G.;
Research Fund (TRF) and the National Shah, B.; Zhai, L.; Zhao, D.. J. Membr.
Nanotechnology Center (NANOTEC). Sci. 2019, 582, 103-110.
8. Suleman, M.; Lau, K.; Yeong, Y.
This work was also partially supported by
Procedia Eng. 2016, 148, 176-183.

PC63
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Isolation of cellulose from natural aquatic weeds: water hyacinth
and cattail
Nattaporn Chutichairattanaphum*, Borwon Narupai, Malinee Leekrajang,
Siriporn Larpkiattaworn
Expert Centre of Innovative Materials, Thailand Institute of Scientific and Technological Research, Khlong
Luang, Pathumthani, 12120, Thailand
*E-mail: [email protected]

Aquatic weeds are a serious environmental problem for Thailand's canals and rivers,
since the plants may obstruct water ways. In this study, Water hyacinth and Cattail which
contains a lot of cellulose, were used for cellulose extraction. The pure cellulose fiber was
isolated by following chemical treatment, wax removal, the 1st, 2nd bleaching process and
hydrolysis process. The extracted cellulose fibers were characterized using Fourier-
Transformed Infrared Spectroscopy (FT-IR) to confirm the change in chemical compositions.
The crystallinity of pure cellulose fibers was investigated using X-Ray Diffraction analysis
(XRD) and thermal properties were examined by Thermogravimetric Analysis (TGA).

1. Introduction treatment. Besides, it has been reported that

the water hyacinth and cattail can be also
Cellulose is one of the most abundant
used as biodegradable polymers and new
biodegradable polymers in the world and has
functional forms in high cellulose content
a low environmental impact in comparison to
(25% to 63%), and low lignin content.11-12
fossil-based polymers. Moreover, they are a
In the present study, the cellulose was
higher economic value, more lightweight and
isolated using three different chemical
have high specific mechanical and thermal
methods following the wax removal, the
properties. There are many plant fibers
bleaching process and hydrolysis process.
available which have potential to be applied
The characteristics of these prepared
in industries as raw materials such as
cellulose were investigated using scanning
pineapple, kenaf, coir, abaca, sisal, cotton,
electron microscopy (SEM), chemical
jute, bamboo, banana, Palmyra, talipot,
analysis, Fourier-transform infrared (FTIR)
hemp, and flex.1-10 Since three main
spectroscopy, X-ray diffraction (XRD), and
components: cellulose, hemicellulose and
thermogravimetric analysis (TGA).
lignin are major plant cell walls. Numerous
research investigations have been undertaken
2. Materials and Methods
on the use of natural fibers as plastic
2.1 Materials
reinforcement to substitute for the synthetic
The raw material used in this study
fibers in medium strength industrial
was the aquatic weeds: water hyacinth and
applications. Aquatic plants such as water
cattail. The plants were obtained from pond
hyacinth and cattail are an invasive aquatic
and river nearby Thailand Institute of
weed causing serious threats to irrigation
Scientific and Technological Research
networks and drainage canals in many
(TISTR). The chemicals used in the wax
countries including Thailand. Various ways
removal was mixed solvent between 99.99%
have been done to solve this problem, either
toluene and 99.8% ethanol. In bleaching
physical removing, chemical and biological PC64
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
process were used sodium chlorite (NaClO2). treated samples from water hyacinth and
And, in extraction process were sodium cattail were referred as “A1” and “B1”,
hydroxide (NaOH) (Sigma-Aldrich), respectively. For this step, lignin could
hydrochloric acid (HCl) (Merck). remove by breaking ether bond and increased
the whiteness degree of fibers.

Figure 1. Diagrammatic scheme of different steps involved in extraction of cellulose from

water hyacinth and cattail.

2.2 Isolation of water hyacinth and cattail Alkaline hydrolysis: hemicellulose was
fiber removed by hydrolysis using 500 ml of
2.2.1 Physical treatment NaOH 1% at 60 °C for 2 h. The treated
Fresh aquatic weeds: hyacinth (Afresh) samples from water hyacinth and cattail were
and cattail (Bfresh) materials were dried at 100 called “A2” and “B2”, respectively.
°C overnight then cut using the cutting Second bleaching process: The samples
machine. were performed to remove the remaining
2.2.2 Chemical treatment lignin through cooking process again using
The diagrammatic scheme of 1% NaClO2 with stirring at 75 °C for 3 h. The
different steps is illustrated in Figure 1. treated samples from water hyacinth and
Following: cattail was called “A3” and “B3”,
Wax removal: Dried water hyacinth and respectively.
cattail samples were first treated using mixed Acid hydrolysis: The last stage was acid
toluene/ethanol of 2/1 for 3 h. at 100 °C then hydrolysis, using 5 % HCl as the catalyst at
washed with ethanol and distilled water after 65°C for 6 h. The treated samples from water
which they were filtered and dried at 40°C for hyacinth and cattail were called “Cellulose
12 h. before use in subsequent experiments. A” and Cellulose B. This step was performed
The treated samples from water hyacinth and to remove the remaining lignin and
cattail were called “A0” and “B0”, hemicellulose.16
respectively. The treated samples of each step were
First bleaching process: the solvent- then washed thoroughly with distilled water
extracted samples were bleached using 3 % and filtered. The process was repeated for 5
NaClO2 in a water bath at 85 °C for 2 h. The times to ensure the complete wash-off of
chemical solvents and obtained a neutral pH. PC65
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
The washed samples were then dried which can be distinctly divided into three
overnight in oven at 40°C before use in stages. First stage is related to the
subsequent experiments. evaporation of moisture which occurs around
2.3 Characterizations 80 – 150 °C and there was a small weight loss
2.3.1 Thermogravimetric analysis (TGA) for all samples. The second stage presented
The thermal characteristics of the the hemicellulose, lignin and pectin, the
samples were investigated using a untreated fibers began to degrade degradation
Thermogravimetric analyzer (TGA), at a around 200-350 °C. At higher temperatures,
temperature range 50–700 °C in a nitrogen a sharper weight drop is observed. Compared
atmosphere at a heating rate of 20 ◦C/min. to untreated and alkali treated fibers, it was
2.3.2 Fourier Transform Infrared (FTIR) observed that the bleaching treatment induces
Spectroscopy an increase in thermal stability. The onset
FTIR spectroscopy was used to thermal degradation temperatures were
characterize the changes in the chemical considered to start at 275.6 C for Afresh, and
composition of the chemically treated fibers 233.9C for Bfresh, and the highest rate of
obtained from water hyacinth and cattail. The weight loss of cellulose A and cellulose B
dried samples were measured by Attenuated occurred at 301.5 and 302.6 C, respectively.
Total Reflectance Fourier Transform Infrared This increasing trend of decomposition
Spectroscopy (ATR-FTIR) to obtain the temperature indicated that the thermal
FTIR spectra. The spectrum was obtained in stability of the cellulose is higher than that of
the transmission mode and the range of 4000 untreated. However, after 315 °C, cellulose A
– 400 cm−1. and cellulose B lost a significant amount of
2.3.3. X-ray Diffraction (XRD) weight up to around 400 °C. The weight
XRD profiles was obtained by using reduction for lignin was measured at
an X-ray diffractometer (XRD; Rigaku temperature around 400–700 °C in Afresh
SmartLab) equipped with a Goebel mirror. and Bfresh were remarkably high which is at
The sample was mounted in a sample holder the range of 40–50%. A suggest that this
and scanned with Cu K-beta radiation at a result confirms that the complete elimination
wavelength of 1.541862 A, with the of hemicellulose and lignin after treatment14.
equipment operated at 40 kV and 40 mA. The The weight fraction of all samples that still
scattered light was detected in the 2θ range existing after heating above 400 ◦C is
between 10 and 50°, and the sample was representative of the carbon content in the
scanned at a speed of 0.8 s per step and an fibers.
angle step increment of 0.02°.

3. Results & Discussion

3.1. Thermogravimetric analysis (TGA)
The results obtained from
thermogravimetric analysis for untreated and
chemically treated water hyacinth and cattail.
As shown in Figures 2 and 3, The TGA curve
of water hyacinth and cattail are very similar, PC66
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 4. FTIR spectra of (Afresh) untreated
Figure 2. thermogravimetric (TG) curves of
water hyacinth, (A0) wax removal, (A1) alkali
the water hyacinth following the various
treated, (A2) 1st bleached, (A3) alkali treated
chemical treatments.
and (cellulose A) acid hydrolyzed.

Figure 3. thermogravimetric (TG) curves of

Figure 5. FTIR spectra of (Bfresh ) untreated
the cattail following the various chemical
cattail, (B0) wax removal, (B1) alkali treated,
treatments.
(B2) 1st bleached, (B3) alkali treated, and
3.2 Fourier Transform Infrared (FT-IR) (cellulose B) acid hydrolyzed.
Spectroscopy Figure 4. and 5 illustrates the Fourier
transforms infrared (FT-IR) spectra of the
untreated and treated water hyacinth and
cattail fibers by different chemical methods.
The peak around at 3,318–3,335 cm-1 and
2,890–2,913 cm-1 are due to O-H and C-H
stretching vibration. In the case of Afresh, the
shoulder at 1,724 cm-1 is attributed to the
C=O stretching vibration for acetyl and ester
groups in the hemicelluloses or carboxylic
group in the ferulic and p-coumeric acids of
lignin. The peak at 1,599 and 1,631–1,643 PC67
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
cm-1 indicates the presence of the C=C group has an amorphous character, while the
of the aromatic ring in lignin and absorbed cellulose is mostly crystalline. The XRD
water. In addition, the peak at 1,245 cm-1 pattern of cellulose A and cellulose B show
corresponds to the C-O out of plane three diffraction peaks around at 2 = 15.3,
stretching of aryl group in lignin. The peaks 21.8 and 34.1 typical of cellulose crystal I
at 1,724 cm-1 and 1245 cm-1 disappears in (natural cellulose)15. The value corresponds
cellulose A and B after chemical treatment to cellulose nanocrystals, which also
showing the removal of non-cellulosic displayed the strongest peak at 2 = 22◦ in
material (A1-cellulose A and B1-cellulose B). cellulose A and cellulose B. The increased
This FTIR result confirms that the complete crystallinity of treated fiber compared to
elimination of hemicellulose and lignin after untreated one was attributed to the
treatment. The spectra of cellulose A and progressive removal of amorphous non-
cellulose B in Figures 4 and 5 provide strong cellulosic materials. The shoulder diffraction
evidence of isolation. The strong bands at peak at 14.6 and a weak peak at 34.0
1,023–1,029 cm-1 and 896 cm-1 were indicates the absence of lignin and
attributed to C-O stretching and C-H rocking hemicellulose in the extracted cellulose. This
vibration of the cellulose structure. is also consistent with the obtained
3.3 X-ray Diffraction (XRD) crystallinity index (CrI) values. Cellulose A
presents a CrI value of 33.12% and cellulose
B presents a CrI value of 44.13%. Therefore,
the crystallinity of chemically treated fibers
can be determined and compared to untreated
fibers to access the effectiveness of the
chemical treatment.

Figure 6. XRD analysis of (Afresh ) untreated

water hyacinth, (A0) wax removal, (A1) alkali
treated, (A2) 1st bleached, (A3) alkali treated
and (cellulose A) acid hydrolyzed.
The XRD results are presented in
Figures 6 and 7 for the untreated and treated
water hyacinth and cattail fibers. XRD
Figure 7. XRD analysis of (Bfresh) untreated
spectra can display the changes in the
water hyacinth, (B0) wax removal, (B1) alkali
crystallinity after different chemical
treated, (B2) 1st bleached, (B3) alkali treated
treatment stages. Chemical treatment
and (cellulose B) acid hydrolyzed.
performed on natural fibers can affect the
crystallinity of cellulose. Normally, the lignin
PC68
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
4. Conclusion longa L. Ind. Crops Prod. 2018, 112,
Based on the results, it can be 556−560.
concluded that the isolation of cellulose from 7. Jung, S.-J.; Kim, S.-H.; Chung, I.-M.
water hyacinth and cattail was successfully Biomass Bioenergy 2015, 83, 322−327.
developed by using wax removal, the 1st, 2nd 8. Reddy, N.; Yang, Y. Bioresour. Technol.
bleaching process and hydrolysis process. 2008, 99 (7), 2449−2454.
9. Fareez, I. M.; Ibrahim, N. A.; Yaacob,
Functional groups of all samples were
W.; Razali, N. A. M.; Jasni, A. H.; Aziz,
inspected by TGA, FT-IR, and XRD. Results
F. A. Cellulose 2018, 25 (8), 4407−4421.
indicate the elimination of hemicellulose and 10. Ovalle-Serrano, S. A.; Blanco-Tirado, C.;
lignin after treatment steps. The present Combariza, M. Y. Cellulose 2018, 25 (1),
investigation has highlighted the utility of 151−165.
water hyacinth and cattail, which are 11. Istirokhatun T, Rokhati N, Rachmawaty
considered as a major cause of polluting in R, Meriyani M, Priyanto S, Susanto H.
many areas. It has also demonstrated the Procedia Environ Sci. 2015, 23,
feasibility of producing cellulose fibers, 274−281.
which can have potential applications such as 12. Sopit, V. J Biol Sci. 2007, 7(1), 218–221.
composites, packing, and membrane 13. Parid, D.M.; Rahman, A. A.; Baharuddin,
applications in the near future. A. S.; Mohammed, M. A. P.; Johari, A.
M.; Razak S. Z. A. BioResources, 13(1),
535-554.
Acknowledgements
14. Monteiro, S. N.; Calado, V.; Margem, F.
The financial support for this project M.; Rodriguez, R. J. S. J. Mater. Res.
was provided by National Research Council Technol. 2012, 1(3),189-199.
of Thailand (NRCT) and Thailand Institute of Bronzato, G.R.F.; Zielgler, S.M.; Silva
Scientific and Technological Research R.C.; Cesarino, I.; Leão, A.L. Mol. Cryst.
(TISTR). Liq. Cryst. 2017, 655, 224-235.
15. Azizi Samir, M.A.S., Alloin, F.,
References Dufresne, A., Biomacromolecules. 2005,
6, 612–626.
1. Singh, A.; Bishnoi, N. R. Ind. Crops 16. Ywu, J.F.;Sheng, W.H.; Kueir, R.L.;Juin,
Prod. 2013, 44, 283−289. Y.L. Effect of physical aging on sorption
2. Asrofi, M.; Abral, H.; Kasim, A.; Pratoto, and permeation of small molecules in
A.; Mahardika, M.; Park, J.-W.; Kim, H.- polyimide membranes. Elsevier.B.V.,
J. Fibers Polym. 2018, 19 (8), 2007, 08; pp 0011-9164.
1618−1625.
3. Sudiarto, S. I. A.; Renggaman, A.; Choi,
H. L. J. Environ. Manage. 2019, 231,
763−769.
4. Phinichka, N.; Kaenthong, S. J. Mater.
Res. Technol. 2018, 7 (1), 55−65.
5. Emmclan, L. S. H.; Zakaria, M. H.;
Bujang, J. S. Bioresources 2018, 13 (3),
5684−5701.
6. Ilangovan, M.; Guna, V.; Hu, C.;
PC69
Nagananda, G. S.; Reddy, N. Curcuma
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Synthesis and characterization of cellulose acetate from tropical cattail
using homogeneous catalyst
Borwon Narupai1*, Malinee leekrajang1, Nattaporn Chutichairattanaphum1, Arisa Jaiyu1,
Siwaruk Chotiwan1,2, Siriporn Larpkiataworn1
1
Expert Centre of Innovative Materials, Thailand Institute of Scientific and Technological Research,
Pathumthani 12120, Thailand
2
Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand
*E-mail: [email protected]

Cattail is an aquatic plant found in many rivers and dams. It causes a number of the
problems which relate to an unbalanced ecosystem. In this research, a cattail was taken to
produce cellulose acetate (CA) in order to increase the added values of this aquatic plant.
Cellulose was isolated from the cattail to produce CA. The cellulose from cattail was acetylated
with vinyl acetate (VA) by using sulfuric acid as a catalyst. Acetylation was carried out for 6,
8 and 17 h at 80 oC under agitation. The key functional groups of CA was investigated by
Fourier transform infrared spectroscopy (FTIR). The FTIR spectra showed that there was a
replacement of free OH groups by acetyl groups. The thermal behaviour was determined by
using thermogravimetry (TGA) and differential scanning calorimeter (DSC). These results
showed that cellulose acetate was successfully synthesized from cattail and it is similar to
cellulose acetate available commercially.

1. Introduction hydroxyl groups.16 Chemically modifying

hydroxyl groups produce cellulose derivative
Cellulose acetate (CA) is a derivative
partially or completely to acetate group in
of cellulose which is a natural polymer,
esterification process.
consisting of anhydroglucose repeating
The present work focused on the
units.3 CA has been widely used for the
synthesis and characterization of CA from
production of textiles, filters, photographic
the cattails at different reaction times. The
films, plastic materials, pharmaceuticals, and
CA samples through acetylation times at 6, 8
packaging.1 The properties of the applied
and 17 h were referred to as CA6, CA8 and
cellulose acetates are very important for these
CA17, respectively. The composition of
applications. Especially, CA is suitable in
cattail consists of 40% fibre, 8.9 % moisture
membrane application because of the
content, 63 % cellulose, 8.7 % hemicellulose,
advantages such as moderate flux, non-
9.6 % lignin, 1.4 % wax and 2 % ash.15 A new
toxicity and cost effectiveness.2
and very powerful solvent for cellulose
CA is obtained by acetylation of
consists of a mixture of dimethylsulfoxide
cellulose that it was isolated from plant and
(DMSO) and tetrabutylammonium fluoride
agricultural residues. CA may be synthesis
(TBAF). It is an efficient solvent and can
through homogeneous or heterogeneous
dissolve cellulose.5 CA was synthesized
reactions.4 However, chemical modification
through the homogeneous reaction by using
under homogeneous reactions. has many
vinyl acetate (VA) in the presence of sulfuric
advantages, e.g. uniform distribution of the
acid as a catalyst. The structures and acetyl
functional groups along the polymer
group substitution of CA were characterized PC70
backbone and good accessibility of the
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
by fourier transform infrared spectroscopy 2.3.1 Fourier transform infrared
(FTIR). The thermogravimetry (TGA) and spectroscopy (FTIR)
differential scanning calorimeter (DSC) were The chemical examination of
used to determine the thermal properties of functional groups for cellulose acetate was
CA. determined by using Fourier transform
infrared spectroscopy (FTIR, Spectrum
2. Materials and Methods Perkin technology). Initially, the products
2.1 Materials were dried at 60 oC in oven and then cooled
The cellulose samples were produced for 30 min in a vacuum desiccator.
from the cattails in our group. Vinyl acetate
was purchased from Alfa Aesar.
Tetrabutylammonium fluoride trihydate
(TBAF) and Dimethyl sulfoxide (DMSO)
were purchased from Aldrich Co., Ltd.
Sulfuric acid (95-97%, Merk) and other
chemicals were used as received.
2.2 Acetylation of cellulose
Preparation of cellulose acetate was
accomplished by using 1 g of cellulosic
resource (Cattail). Cellulose was dissolved
by adding into a mixture solution of TBAF
and DMSO. A high viscous solution is
formed for 15 mins at room temperature
under stirring of 20 rpm. Then, Vinyl acetate
and sulfuric acid were loaded into the
solution and the mixture was kept in heating
mantle at 80 oC for different times as 6, 8 and
17 h under stirring. The cloudy mixture was
poured in 200 ml isopropyl alcohol after 50
ml water was filled into the cloudy mixture to
dissolve the inorganic salts. The suspended
white precipitate in the mixture was
separated by filtration. The product was wash
with 200 ml isopropyl alcohol and filtered
off. The obtained sample was dried in the
oven at 50 oC to a constant mass following to
Figure 1.
2.3 Characterization of cellulose acetate
Cellulose acetate prepared at different Figure 1. The schematic diagram of cellulose
reaction times was characterized by FTIR, acetylation experiment procedure.
DSC and TGA.
PC71
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.3.2 Thermogravimetric analysis (TGA) followed by decomposition of hemicellulose
The thermal stability of cellulose components and cellulose components.18
acetate was determined by carrying out TGA Cattail cellulose has the degradation
measurements using a STA 449 F3 Jupiter. temperature at 50 % weight loss (Td50) at 328
o
Initial weight of product (3 mg) was heated C. The thermal degradation of CA6, CA8
from room temperature to 600 oC at a heating and CA17 started at 302 oC, 312 oC, and 335
rate of 10 oC/min, under a nitrogen o
C and ended at 351 oC, 361 oC, and 370 oC,
atmosphere (Flow = 50 ml/min). The weight respectively. This thermal degradation
loss being investigated as a property of indicates pyrolytic decomposition of
product. cellulose acetate polymer chain skeleton,
2.3.3 Differential scanning calorimetry followed by deacetylation together with the
(DSC) decomposition of hemicellulose and lignin
The thermal analysis of the products chains.6,17 The degradation temperature at
was performed using a Differential scanning mass loss 50 % (Td50) of CA6, CA8 and
calorimeter (DSC 200 F3, NETZSCH). The CA17 corresponded to temperature at 328 oC,
tests performed at heating rate of 10 oC/min, 337 oC and 355 oC, respectively.
under a nitrogen atmosphere with flow rate of The third stage that is the
20 ml/min, from ambient to 400 oC. decomposition cattail cellulose, CA6, CA8
and CA17 observed at the temperature range
3. Results & Discussion between 438 - 540 oC, 440 - 552 oC, 448 -553
o
3.1 TGA C and 460 - 558 oC, respectively. The
The thermal characterization of carbonization of degradation products
cattail cellulose and cellulose acetate occurred in this phase.7 The degradation
products (CA6, CA8 and CA17) by TGA is temperature at 50 % weight loss of cattail
illustrated in the graph of Figure 2. The TGA cellulose and cellulose acetate products
curve reveals three stages and the curve for obtained by different acetylation times are
each product distinct characteristics. related in Table 1.
The first mass loss of the TGA curve Table 1. Thermal degradation analysis data
for cattail cellulose, occurring from 30 to 160 on cattail cellulose and cellulose acetate
o
C is due to humidity evaporation or the loss products by different acetylation times.
of other volatile components.1 TGA curve for
Sample Td50
CA6, CA8 and CA17 revealed the mass loss
in the region of 60 - 175 oC, 64 - 178 oC, 63 - Cattail cellulose 328 oC
178 oC, respectively, related to loss of water. CA6 328 oC
So, the first stage indicates the evanescence
CA8 337 oC
of hydrogen bond link water molecules.
The second stage on the TGA curves CA17 359 oC
related to the thermal degradation of
anhydrous material in cattail cellulose, CA6,
CA8 and CA17. The second event occurring
at around 303 – 346 oC is characteristic of
thermal degradation of cattail cellulose, PC72
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.2 DSC crystals begin to fall apart. In addition, The
The thermal properties of cattail DSC plots of CA6, CA8 and CA17 show the
cellulose and cellulose acetate products board exothermic peak around 321 oC, 336
o
(CA6, CA8 and CA17) were examined by C and 360 oC, respectively. The board
DSC technique, as shown in Figure 3. The exothermic peaks could be caused by
DSC plot of cattail cellulose shows an decomposition.8 The thermal decomposition
endothermic peak around 274 oC that is of cellulose acetate products can be attribute
melting temperature (Tm) and an exothermic to the degradation of the hemicellulose
peak around 327 oC which is assigned to the derivatives and acetylated lignin.12 The
degradation temperature (Td).8 A weak degradation of cellulose acetate products can
transition is presented around 138 oC, that be confirmed by TGA curves of samples due
may be due to the glass transition temperature to the quick weight loss of the products in
(Tg). Then, the CA6, CA8 and CA17 present Figure 2 that related with DSC plots. DSC
the endothermic peaks around 235 oC, 275 oC thermograms of CA6, CA8 and CA17 show
and 296 oC, respectively, which may be mainly the same characteristics. The
attributed to a melting temperature (Tm) of principal differences are rated to the position
cellulose acetate products. Because cellulose of the exothermic terms and endothermic
acetate has to add energy or absorb heat to the terms.
polymer to make it melt, those polymer

120
Cattail cellulose
CA6
100 CA8
CA17
80
% Loss weight

60

40

20

0
30 130 230 330 430 530
Temperature (°C)

Figure 2. TGA plots of cattail cellulose, CA6, CA8 and CA17.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 12
CA17
Heat Flux (W/g)

10

CA8
8

6
CA6

2 Cattail cellulose
Exo

0
30 80 130 180 230 280 330 380

Temperature (°C)

Figure 3. DSC plots of cattail cellulose, CA6, CA8 and CA17.

CA17
-CH 113
C=O CH3
C-O
% Transmittance (a.u)

stretching
CA8
-CH CH3
-OH C=O C-O 103
stretching
-CH CH3 CA6
C=O
-OH C-O

stretching
Cattial 93

-CH cellulose
C-O of cellulose
-OH

83
4000 3500 3000 2500 2000 1500 1000 500 0

Wavenumber (cm-1)

Figure 4. FTIR spectra of cattail cellulose, CA6, CA8 and CA17.

PC74
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.3 FTIR appeared in CA17 spectrum. As the
acetylation time was increased, the intensity
Infrared spectroscopy was used to
of band around 3,400 cm-1 for synthesized
investigate the functional groups and also to
cellulose acetates was decreased, suggesting
evaluate the efficiency of cellulose acetate
the characteristic of a more acetylated
synthesis process from cattail cellulose. The
materials.9 The observed result was ascribed
FTIR results of functional groups on the
to the substitution of hydroxyl groups by
products show in Figure 5. The FITR
acetyl groups during the reaction. This FTIR
spectrum of cattail cellulose has a significant
results were proved that the acetylation
difference compared to those of cellulose
process of cattail cellulose into cellulose
acetate spectra. The enlargement of
acetate has been successfully carried out.
absorption peaks was normally observed in
the range of 3,300 cm-1 – 3,500 cm-1, related
4. Conclusion
to the stretching of intermolecular hydrogen
Cellulose acetate was successfully
bonds of hydroxyl group (-OH). The FTIR
synthesized from homogeneous acetylation
spectra of cattail cellulose shows two
of cattail cellulose using sulfuric acid as
distinctive peaks at 3,334 cm-1 and 1,028 cm-
1 catalyst for 6, 8 and 17 h. The thermal
, corresponding to the O-H stretching and C-
analysis revealed that the melting
O stretching in cellulose, respectively.2,6,9-
11,13 temperature (Tm) and the degradation
The new characteristic peaks of CA6
temperature (Td) of synthesized cellulose
sample appear at 1,727 cm-1, 1,370 cm-1, and
acetate increased slightly when the longer
1,238 cm-1, which are attributed to C=O
acetylation time was applied. The FTIR
stretching of acetyl (carbonyl ester), C-H
results confirmed the replacement of the free
bond at the acetyl [-O (C=O + CH3] and C-O
OH group by acetyl group in the synthesis of
stretching of acetyl group, respectively.1-
2,6,13-14 cellulose acetate and the intensity of OH
FTIR spectrum of CA8 shows the
group of cellulose decreased with an increase
characteristic bands attributed to the
of acetylation times. These results indicated
vibration of the acetate group including C=O
that the degree of acetylation increased with
stretching of acetyl, C-H deformation (-CH3)
an increase of reaction times. Therefore, the
and C-O stretching (acetate) at 1,734 cm-1,
variation of the acetylation time may control
1,367 cm-1 and 1,222 cm-1, respectively.1-
2,9,13-14 the choice of the use of the cellulose
For CA17 spectrum, the sharp peaks at
products.
wavelength of 1,734 cm-1, 1,367 cm-1, and
1,222 cm-1 are characteristic to the carbonyl
Acknowledgements
stretching (C=O), methyl bending (C-CH3)
and C-O stretching of acetyl group, The authors gratefully acknowledge
respectively.2,6,12-14 Moreover, the O-H Thailand Institute of Scientific and
stretching of cellulose peaks, which is Technological Research (TISTR) for
occurred at 3,361 cm-1 and 3,415 cm-1 for financial, material and instruments support.
both CA6 and CA8 samples, are smaller than
that of the cellulose reference but this O-H
stretching of cellulose peak is hardly
PC75
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
References 10. Istirokhatun, T.; Rokhati, N.;
1. Andrade, A.; Matheus, D.; Cleiber, C. Rachmawaty, R.; Meriyani, M.;
M.; Jose, L.; Danilo, M.; Suely, M.; Priyanto, S.; Susanto, H. Procedia
Diego, P.; Roberta, S. Int. J. Biol. Environ Sci. 2015, 23, 274-281.
Macromol. 2019, 135, 877-886. 11. Saputra, A. H.; Hapsari, M.; Pitaloka,
2. Candido, R. G.; Godoy, G. G.; A. B. Contemp. Eng. Sci. 2015, 8,
Adilson, R. G. Carbohydr. Polym. 1571-1582.
2017, 17, 1-32. 12. Filho, G.R.; Monterio, D.S.;
3. Li, Y.; Tian, J.; Yang, C.; Hsiao, B. S. Meireles, C. S.; Assuncao, R. M. N.;
Polym. J. 2018, 10, 1052-1066. Cerqueira, D. A.; Barud, H. S.;
4. Wu, S.; Qin, X.; Li, M. J. Ind. Text. Ribeiro, S. J. L.; Messadeq, Y.
2013, 44, 85-98. Carbohydr. Polym. 2008, 73, 74-82.
5. Heinze, T.; Dicke, R.; Koschella, A.; 13. Istiokhatun, T.; Rokhati, N.;
Kull, A. H.; Khohr, E. A.; Koch, W. Rachmawaty, R.; Meriyani, M.;
Macromol. chem. Phys. 2000, 201, Priyanto, S.; Susanto, H. Procedia
627-631. Environ. Sci. 2015, 23, 274-281.
6. Shaikh, H.M.; Pandare, K. V.; Nair, 14. Rahmawati, F.; Fadillah, I.;
G.; Varma, A. J. Carbohydr. Polym. Mudjijino, M. J. Mech. Eng. Sci.
2009, 76, 23-29. 2017, 8, 389-397.
7. Chen, X.; Yu, J.; Zhang, Z. 15. Vetayasupong, S. J. Biosci. 2007, 7,
Carbohydr. Polym. 2011, 85, 245- 218-221.
250. 16. Achtel, C.; Heinze, T. Macromol.
8. Luo, J.; Sun, Y. J. Appl. Polym. 2006, chem. Phys. 2016, 217, 2041-2048.
100, 3288-3296. 17. Huang, M.; Li, X. J. Appl. Polym. Sci.
9. Hernane, S. B.; Adalberto, M.; Carla, 1998, 68, 293-304.
S.; Guimes, R. F.; Younes, M.; 18. Radzi, A. M.; Sapuan, S. M.; Jawaid,
Ribeiro, J. L. Thermochim. Acta. M.; Mansor M. R. J. Mater. Sci.
2008, 471, 61–69. Technol. 2019, 8, 3988-3994.

PC76
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 Cellulose/oligo-chitosan hydrogel: preparation and water-absorption
behavior
Patipat Kongroiyu, Wanchai Lerdwijitjarud*
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakhon Pathom 73000, Thailand
*Corresponding Author E-mail: [email protected]

Hydrogel, a water-containing crosslinked hydrophilic polymer, is used in many

applications such as scaffold, drug delivery system, and disposable diaper. In the present study,
we focus on the preparation and water-absorption behavior of bio-based and biodegradable
hydrogel produced from cellulose and oligo-chitosan. The cellulose/oligo-chitosan ratio in the
hydrogel synthesizing step was varied at 100/0, 80/20, 60/40, 50/50, and 40/60. The
crosslinking agent in all studied systems was epichlorohydrin. The obtained products were
characterized by fourier-transform infrared spectroscopy, scanning electron microscopy, and
water-absorption testing. The equilibrium absorption values of all oligo-chitosan/cellulose
contained hydrogels were higher than that of the pure-cellulose hydrogel. The increment of
water-adsorption efficiency was found with increasing the content of oligo-chitosan in the
hydrogel preparing step until the cellulose/oligo-chitosan ratio reached 60/40. However, the
decline in water absorption efficiency was observed when the percentage of oligo-chitosan in
the preparing step was higher than 40%. This observation may result from the higher
possibility of a self-crosslinking reaction between oligo-chitosan molecules. The hydrogel
with an optimum value of cellulose/oligo-chitosan ratio in the synthesizing step of 60/40
exhibited the maximum value of water absorption at around 780%.

2-4
1. Introduction There are some natural polymers, which
Nowadays, a hydrogel is applicable in contain hydrophilic groups in their molecular
many fields such as disposable diaper, soil structures such as starch, cellulose, and
filler, scaffold, and drug delivery system. A chitosan. These materials are bio-based and
hydrogel is typically a water-containing also biodegradable polymers.
material crosslinked polymer. High water- Cellulose, polymeric material of
absorption capacity of hydrogel arises from a glucose unit, is the most abundant organic
large number of hydrophilic functional materials presented in the world. It exhibits
groups presented in polymer molecules. many excellent properties such as high
Usually, most hydrogels are synthesized strength, biodegradability, and hydrophili-
from synthetic polymers such as poly(acrylic city. Chitin is also one of the most abundant
acid), polyacrylamide, and poly(vinyl organic materials. Chitin can be easily
alcohol).1 However, the use of these non- converted into chitosan by deacetylation
biodegradable polymers is suspected to be a reaction. Chitosan is hydrophilic and
major cause of plastic pollution. biodegradable. Chitosan has been proposed
In order to relieve this environmental for applications in food, pharmaceutical, and
problem, many research works try to replace chemical industries. Acid solution is
petroleum-based non-biodegradable hydro- normally recommended for dissolving
gels with hydrogels synthesized from chitosan. However, oligo-chitosan can be
naturally-occurring biodegradable polymers. able to dissolve in water. Oligo-chitosan is PC77
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
thus chosen for the ease of use and A procedure to prepare oligo-chitosan
convenient in present study. was modified from the method described by
Although a cellulose hydrogel has Huang et al.7. Briefly, the chitosan solution
good biodegradable and high water was prepared by dissolved chitosan (5g) in
absorption properties, it has high potential to 100 mL of acetic acid solution (1% v/v).
easily attack by microorganisms. Some Hydrogen peroxide (25ml) and
literatures reported that chitosan and its phosphotungstic acid hydrate (0.0625 g)
oligomer can inhibit the growth of bacteria.5, were subsequently added dropwise to the
6
Therefore, the hydrogel produced by aqueous solution of chitosan under stirring at
incorporation of oligo-chitosan with 70 oC for 1.5 h. The mixture was washed
cellulose is expected to have an additional with deionized water until the pH was
antibacterial activity. Both cellulose and neutral. The solution was precipitated in an
oligo-chitosan are therefore suitable to be excess of ethanol and the oligo-chitosan
precursors for preparing a biodegradable powder was obtained. The oligo-chitosan
hydrogel. was finally dried in a vacuum oven at 50 oC
In this research, we focus on the until it reached the constant mass.
preparation of bio-based and biodegradable 2.3 Hydrogel preparation
hydrogel produced from cellulose and In order to study the effect of
chitosan. The effect of the precursor’s weight cellulose/oligo-chitosan weight ratio on the
ratio on morphology and water absorption properties of hydrogel, the content of
behavior of hydrogels was investigated. cellulose and oligo-chitosan used in the
hydrogel preparation step was varied and
2. Materials and Methods shown in Table 1. The solvent of cellulose
2.1 Materials and oligo-chitosan was firstly formulated by
Microcrystalline cellulose (Avicel® mixing 7%wt of NaOH, 12%wt of Urea, and
PH-101, Fluka) and chitosan (Marine Bio 81%wt of water together. Afterwards, the
Resources, degree of deacetylation ≥ 90%) desired amounts of precursors were added
were used as hydrogel precursors. The into NaOH/urea/water mixture to form 5%wt
crosslinking agent was epichlorohydrin solution. The mixture was stirred in a cooling
(purity ≥ 98%, SigmaAldrich). The bath at -20 oC until the solid powders were
NaOH/urea/water based solvent was made completely dissolved. Then epichlorohydrin
from Urea (AR grade, Qrec), sodium was added dropwise into the mixture and
hydroxide pellet (purity ≥99%, Ajax stirred for 30 minutes. A crosslinking
finechem) and deionized water. Hydrogen reaction was allowed at 60 oC for 24 h.
peroxide (30%w/w, Qrec), phosphotungstic Finally, the hydrogel was treated by Soxhlet
acid hydrate (reagent grade, SigmaAldrich) extraction with acetone for 24 h and dried in
and glacial acetic acid (purity ≥ 99.8%, a vacuum oven at 50 oC for 2 h.
Qurec) were used to prepared oligo-chitosan.
All chemicals were used as received without
further purification.
2.2 Preparation of oligo-chitosan
PC78
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 1. A content of precursors in a phosphotungstic acid hydrate as a catalyst.
preparation step and a percentage yield of The average molar mass of oligo-chitosan
cellulose/oligo-chitosan hydrogel. was examined by intrinsic-viscosity
Oligo- determination at a temperature of 25 oC. The
Cellulose K and a values used in Mark-Houwink-
Sample chitosan % Yield
(%wt) ̅ va , were
(%wt) Sakurada equation, [] = KM
CL100 100 0 100 19.9×10-2 mL/g and 0.59, respectively.9 The
CL80/CS20 80 20 99
viscosity-average molar mass of prepared
CL60/CS40 60 40 83
CL50/CS50 50 50 76 oligo-chitosan was 315 g/mol.
CL40/CS60 40 60 65 A FTIR spectrum of oligo-chitosan is
2.4 Characterization of hydrogel illustrated in Figure 1a. A strong absorption
The functional groups in the peak at 3378 cm-1 corresponds to N-H
synthesized hydrogel were examined by stretching and O-H stretching of oligo-
fourier-transform infrared spectroscopy, chitosan molecule. The characteristic peaks
FTIR (Vertex70, BRUKER) in the of C-H stretching vibration and N-H bending
wavenumber region of 4000-400 cm-1 using vibration appear at 2887 and 1665 cm-1,
KBr pellets. The elemental analyzer respectively. The absorption peak at 1064
(CHN623 series, LECO) was employed to cm-1 is attributed to C-O stretching. Figure 1b
determine the elemental composition of the shows a FTIR spectrum of cellulose. The
hydrogel. A scanning electron microscope vibrations of the hydroxyl functional group
(MIRA3, TESCAN) was used to study the appear at the wavenumber of 3500-3200
morphology of hydrogel. The specimens for cm-1. The absorption peak at 2897 cm-1
morphology observation were prepared by represents C-H stretching vibration. The
freeze-drying technique and coated with stretching vibration for the ether linkage (1,4-
gold. β-D-glucoside) of cellulose shows at a
2.5 Water adsorption behavior of hydrogel wavenumber of 1165 cm-1. 10, 11
The specimen with a dried mass
around 0.01 g was used to investigate the
water adsorption ability of hydrogel. A dried
specimen was immerged into deionized water
at 303 oC for 48 h. The water-containing
hydrogel was taken out and subsequently
weighted. A water absorption value was
calculated as the following equation.8
Water absorption (%) = (Ws-Wd)/Wd× 100%
; where Ws  the weight of swelled hydrogel
Wd  the weight of dried hydrogel
3. Results & Discussion Figure 1. FTIR spectra of (a) oligo-chitosan
3.1 Characterization of oligo-chitosan and and (b) cellulose.
cellulose
Oligo-chitosan was produced by
oxidative degradation of chitosan using PC79
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 2. The expected crosslinking reaction
between cellulose and oligo-chitosan
molecules using epichlorohydrin as a Figure 3. FTIR spectra of CL100,
crosslinking agent to produce hydrogel. CL80/CS20, CL60/CS40, CL60/CS40, and
CL40/CS60.
Table 2. Elemental composition of cellulose,
The yield of hydrogel as reported in
oligo-chitosan and cellulose/oligo-chitosan
Table 1 was calculated as a ratio between the
hydrogel.
dried mass of hydrogel and summation mass
of hydrogel precursors (cellulose and oligo-
% Nitrogen/ chitosan) and epichlorohydrin. The
Sample %Carbon %Nitrogen
%Carbon
Cellulose 42.05 0.00 0
percentage yield decreased with increasing
Oligo- the oligo-chitosan/cellulose ratio in the
chitosan
37.86 6.34 0.17
synthesizing step. When the percentage of
CL100 40.00 1.10 0.03
CL80/CS20 32.19 2.77 0.09
oligo-chitosan in preparation step increased,
CL60/CS40 34.44 3.75 0.11 the higher in the possibility of a reaction
CL50/CS50 31.63 4.14 0.14 between oligo-chitosan and oligo-chitosan
CL40/CS60 36.59 3.63 0.10 was expected. The self-reaction between
oligo-chitosan molecules might create a
3.2 Characterization of cellulose/oligo- relatively small molecular weight species that
chitosan hydrogel could not solidify in a precipitation step.
Oligo-chitosan and cellulose were The FTIR spectra of hydrogel
used as hydrogel precursors and prepared from various oligo-
epichlorohydrin was used as a crosslinking chitosan/cellulose ratio are illustrated in
chemical. The crosslinking reaction between Figure 3. All hydrogel spectra represent the
cellulose and oligo-chitosan molecules was characteristic peaks corresponding to the
intentionally expected as shown in Figure 2. characteristic peaks of their precursors, i.e.
However, the binding reactions between cellulose, and oligo-chitosan. The
cellulose and cellulose molecules or oligo- characteristic peaks presented in the FTIR
chitosan and oligo-chitosan molecules could spectrum of both cellulose and oligo-chitosan
also occur. are very similar since the functional groups
of their molecules are nearly identical.
Therefore, the spectra of all hydrogels
formulated from different precursor ratios
cannot be clearly distinguished. PC80
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The composition of carbon, maximum value of water absorption at
hydrogen, and nitrogen elements of around 780%.
hydrogels investigated by elemental analysis
is provided in Table 2. From elemental
analysis results, the weight ratio of nitrogen
atom/carbon atom of the oligo-chitosan
sample was 0.17 which was well consistent
with the theoretical value of 14/72.12 The N/C
ratio increased when the percentage of added
chitosan in the hydrogel preparation step
increased from 20 to 50%. However, the
reduction in value of the N/C ratio was
observed for the CL40/CS60 hydrogel. This
result confirmed the assumption that the
increase in the amount of un-precipitated Figure 4. SEM images of (a) CL100, (b)
self-binding oligo-chitosan species might CL80/CS20, (c) CL60/CS40, (d)
arise during the preparation step of the CL50/CS50, and (e) CL40/CS60.
CL40/CS60 system.
3.3 Water absorption of hydrogel
All prepared cellulose/oligo-chitosan
hydrogels could absorb a high amount of
water because there were a large amount of
hydrophilic groups, i.e. hydroxyl and amino
groups, existed in both cellulose and oligo-
chitosan molecules. The porous morphology
is another important factor supporting a water
absorption capacity. Figure 5 illustrates the Figure 5. Equilibrium percentage of water
water absorption percentages of hydrogels absorption of cellulose/oligo-chitosan
after immersing in deionized water at a hydrogel.
temperature of 303 oC for 48 hours. The 4. Conclusion
water absorption of the pure-cellulose Water-absorbing material was
hydrogel, CL100, was around 400%. Water synthesized from cellulose, oligo-chitosan,
absorption of all cellulose/oligo-chitosan and epichlorohydrin in NaOH/urea aqueous
hydrogels was higher than that of cellulose solution. The cellulose/oligo-chitosan
hydrogel. CL60/CS40 and CL50/CS50 weight ratio in the preparation step was
hydrogels showed relatively high values of varied from 100/0 to 40/60. The
water absorption compared with other accomplishment of hydrogel formation was
hydrogels because of the small pore size and confirmed by fourier-transform infrared
the high degree of open-cell structures. The spectroscopy and elemental analysis. The
hydrogel with cellulose/oligo-chitosan ratio morphology of all synthesized hydrogels was
in the synthesizing step of 60/40 revealed the a porous structure. The material prepared
with a cellulose/oligo-chitosan ratio of 60/40 PC81
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
displayed the highest water absorption at 6. Benhabiles, M. S.; Salah, R.; Lounici, H.;
around 780%, which was approximately two Drouiche, N.; Goosen, M. F. A.; Mameri,
times higher than that of the pure-cellulose N. Food Hydrocoll. 2012, 29 (1), 48-56.
hydrogel. 7. Huang, Q. Z.; Wang, S. M.; Huang, J. F.;
Zhuo, L. H.; Guo, Y. C. Carbohydr.
Acknowledgements Polym. 2007, 68 (4), 761-765.
8. Ramazani-Harandi, M. J.; Zohuriaan-
The authors would like to thank the
Mehr, M. J.; Yousefi, A. A.; Ershad-
supports from Department of Materials
Langroudi, A.; Kabiri, K. Polym. Test.
Science and Engineering, Faculty of 2006, 25 (4), 470-474.
Engineering and Industrial Technology, 9. Costa, C. N.; Teixeira, V. G.; Delpech,
Silpakorn University. M. C.; Souza, J. V. S.; Costa, M. A. S.
Carbohydr. Polym. 2015, 133, 245-250.
References 10. Wan Ngah, W. S.; Hanafiah, M. A. K.
1. Caló, E.; Khutoryanskiy, V. V. Eur. M.; Yong, S. S. Colloids Surf. B: 2008, 65
Polym. J. 2015, 65, 252-267. (1), 18-24.
2. Chang, C.; Duan, B.; Cai, J.; Zhang, L. 11. Lin, Q.; Chang, J.; Gao, M.; Ma, H. J.
Eur. Polym. J. 2010, 46 (1), 92-100. Environ. Sci. Health A Tox. Hazard.
3. Bashari, A.; Rouhani Shirvan, A.; Subst. Environ. Eng. 2017, 52 (2), 106-
Shakeri, M. Polym. Adv. Technol. 2018, 116.
29 (12), 2853-2867. 12. Sivashankari, P. R.; Prabaharan, M., 5 -
4. Narayanan, A.; Kartik, R.; Sangeetha, E.; Deacetylation modification techniques of
Dhamodharan, R. Carbohydr. Polym. chitin and chitosan. In Chitosan Based
2018, 191, 152-160. Biomaterials Volume 1, Jennings, J. A.;
5. No, H. K.; Young Park, N.; Ho Lee, S.; Bumgardner, J. D., Eds. Woodhead
Meyers, S. P. Int. J. Food Microbiol. Publishing: 2017; pp 117-133.
2002, 74 (1), 65-72.

PC82
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Influence of surfactant on a preparation of poly(acrylic acid)/styrene-
butadiene-rubber hybrid material via high internal phase emulsion
technique
Natcha Ployeam, Wanchai Lerdwijitjarud*
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakhon Pathom 73000, Thailand
*E-mail: [email protected]

A bi-continuous hydrophilic/hydrophobic hybrid polymer has been increasingly

interested in absorption and controlled release applications. We focus on the effect of
emulsifier on a synthesis of poly(acrylic acid)/styrene-butadiene-rubber hybrid material in
present study. A high internal phase emulsion (HIPE) method was chosen to prepare the
material. The studied materials were synthesized by using three types of non-ionic surfactants,
i.e. polyoxyethylene (40) nonylphenyl ether (IGEPAL CO-890), polyoxyethylene (80) sorbitan
monooleate (TWEEN80), and sorbitan monooleate (SPAN 80). An oil phase composed of
styrene-butadiene rubber (SBR), toluene, benzoyl peroxide, and surfactant. Acrylic acid,
ammonium persulfate, N-N' methylenebisacrylamide, and water were mixed to form an
aqueous phase. To achieve a more stable emulsion, a pre-polymerization of an aqueous phase
was preferred until the viscosities of both oil and aqueous phase were comparable. The success
of material preparation using HIPE technique occurred for the reaction system using sorbitan
monooleate as a surfactant, whereas the systems using polyoxyethylene (40) nonylphenyl ether
or polyoxyethylene (80) sorbitan monooleate exhibited a phase separation. This phenomenon
may due to the relatively low value of hydrophilic-lipophilic balance (HLB) value of sorbitan
monooleate molecule, which is more suitable for the studied emulsion system.

1. Introduction external/internal phase bi-continuous

Materials with hydrophilic/ structure.
hydrophobic bi-continuous structure are A success on a preparation of
considerably useful for controlled release material using HIPE technique depends on
and absorption fields. The absorption rates many factors such as polarity of both
of these materials can be tailored by internal and external phases,2
adjusting a ratio of hydrophilic/ external/internal phase volume ratio,3
hydrophobic phase and their structures. relative viscosity of external/internal
One of the interesting ways to prepare these phase,4 and reaction temperature5. Another
hybrid materials is double high internal key parameter in HIPE formulation is
phase emulsion method. High internal emulsifier type and content. Zhang and
phase emulsion (HIPE) method is typically Zhu3 reported that the emulsion stability
a method used to construct an emulsion increased with increasing surfactant
with high volume fraction of internal content. The use of mixed surfactant system
phase.1 If the external phase of HIPE is for poly(HIPE) formulation was also
solidified, a material with high porous addressed.2
structure is obtained. Moreover, if both In present work, we focus on a
external and internal phases are hardened, preparation of poly(acrylic acid)/styrene-
we will get a hybrid material with butadiene rubber hybrid material using PC83
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
double poly(HIPE) technique. The was dissolved in toluene to prepare 3 % w/v
influence of emulsifier type on an solution. BPO (0.6g) was put into SBR
achievement of material synthesis is solution as an initiator. The desired
investigated. We also describe the effect of surfactant (2g) was added prior to mix both
pre-polymerization of aqueous phase on phases together. For an ease of dissolving,
morphology of obtained products. IGEPAL CO-890 or TWEEN80 was
applied in aqueous phase, whereas SPAN80
2. Materials and Methods was put in organic phase.
2.1 Materials The internal-phase solution was
The hydrophobic polymer used in dropped into the external-phase organic
external phase was styrene-butadiene solution with continuous stirring at room
rubber (grade 1502, BSTE). Benzoyl temperature. The prepared mixture was
peroxide (BPO) (synthesis grade, Merck) continuously stirred for 1 hour. The
was used as a curing agent of rubber phase. obtained emulsion was then heated to 80 oC
Chemicals used in an internal phase were for 24 h. The purification of cured product
acrylic acid monomer (synthesis grade, was done by Soxhlet extraction with
Loba Chemie), N,N'-Methylenebis- acetone for 24 h. and with water for 24 h.
acrylamide (MBA) (Labolatory grade, The monolith hydrogel was dried in a
Acros Organics) co-monomer, ammonium vacuum oven at 50 oC until a constant
persulfate (APS) (AR grade, KEMAUS). weight was reached.
Solvent used for organic and aqueous phase 2.3 Characterization
were toluene (AR grade, QRёC) and A stability of an emulsion during a
deionized water, respectively. double poly(HIPE) synthesizing step was
Polyoxyethylene (40) nonylphenyl ether investigated by physical observation. A
(IGEPAL CO-890), polyoxyethylene (80) product yield was calculated from a ratio
sorbitan monooleate (TWEEN80), and between dried mass of hydrogel and a
sorbitan monooleate (SPAN 80) were used summation of AA, MBA, and SBR mass.
as surfactants. All chemicals were used as The functional groups of product
received. was investigated by fourier-transform
infrared spectroscopy, FTIR, spectrometer
2.2 Synthesis (Vertex70, BRUKER) using KBr pellets.
2.2.1 Double poly(HIPE) synthesis Scanning Electron Microscopy (SEM)
A volume ratio between aqueous (MX-2000, CamScan) was used to examine
internal phase and organic external phase the morphology of poly(HIPE) products.
was 75/25. The aqueous phase was firstly The samples for SEM testing were
prepared by dissolving acrylic acid produced by freeze drying and
monomer (0.15g) and MBA co-monomer subsequently sputtered with gold.
(0.022g) into 15 mL of deionized water. An
initiator, APS, was subsequently added. For 3. Results & Discussion
pre-polymerization system, the aqueous A bi-continuous poly(acrylic
phase was heated at 80 oC for 30 min. For acid)/SBR material was prepared using
organic external phase formulation, SBR double poly(HIPE) technique. Three types PC84
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
of surfactant, i.e. polyoxyethylene (40) the synthesizing double poly(HIPE)
nonylphenyl ether (IGEPAL CO-890), systems using IGEPAL CO-890 and
polyoxyethylene (80) sorbitan monooleate TWEEN80 as emulsifiers. However, the
(TWEEN80), and sorbitan monooleate stability of the reaction system stabilized by
(SPAN80), were applied to stabilize the SPAN80 was presented throughout the
emulsions during the material formulation reaction process. This phenomena may due
step. The chemical structures of used to the difference in hydrophilic-lipophilic
surfactants is illustrated in Figure 1. Figure balance (HLB) value of each surfactant.
2 exhibits the chemical reactions developed Surfactants are normally amphiphilic
in both internal aqueous phase and external species. They comprise of hydrophilic and
organic phase. A copolymerization lipophilic part in their molecules. HLB
reaction of acrylic acid monomer (AA) and value is the number that simply represented
N,N'-Methylenebisacrylamide co-mono- the ratio of water-loving part to oil-loving
mer was occurred in aqueous phase, part of surfactant molecule. The HLB
whereas a curing reaction of styrene- numbers of IGEPAL CO-890, TWEEN80,
butadiene rubber with peroxide was arisen and SPAN80 are 17, 15, and 4.3,
in organic phase. respectively.6,7 The emulsion system in
present study is water in oil (w/o) emulsion
(a) since the droplets of acrylic-acid aqueous
solution are surrounded by SBR dissolved
in toluene phase. The molecular structure
(b)
of SPAN80 contains relatively small
hydrophilic part and long-chain
hydrophobic part, which corresponds with
low HLB value. Thus, SPAN80 was an
(c) effective surfactant for the studied emulsion
systems. The percentage yields of the
products received from the reaction
stabilized with different type of surfactant
are shown in Table 1. A highest yield
obtained from the emulsion system using
Figure 1. Chemical structures of (a) SPAN80 as a stabilizer. The difference in
polyoxyethylene (40) nonylphenyl ether phase viscosity is one of important causes
(IGEPAL CO-890), (b) polyoxyethylene for emulsion instability. For our system,
(80) sorbitan monooleate (TWEEN80), the internal phase was aqueous solution of
and (c) sorbitan monooleate (SPAN80) monomer and co-monomer, whereas the
The images of reaction mixtures outer phase was solution of SBR. At the
using different surfactant after 2 hours of beginning of reaction, the viscosity of
reaction are presented in Table 1. When the
progression of reaction reached two hours,
the destabilization of emulsions in some
parts of reaction mixture were observed for PC85
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
internal aqueous phase was rather low
comparing with that of outer organic phase.

(a) (b)

Figure 2. (a) Copolymerization reaction in aqueous phase, and (b) curing reaction in organic
phase.
(c) poly(acrylic acid)/styrene-butadiene-rubber
Table 1. Images of reaction mixture after 2 hybrid material
hours of reaction and % yield of reaction
product. (b) SBR
Transmittance%

Images of reaction
Surfactant mixture after 2 hours of % Yield
reaction

IGEPAL 22.5 (a) acrylic acid

CO-890

Wave number (cm-1)

Figure 3. FTIR spectra of (a) acrylic acid,
(b) SBR, and the synthesized (c)
TWEEN80
19.2 poly(acrylic acid)/SBR hybrid material.
step is shown in Table 2. The addition of
pre-polymerization step in material
formulation process could increase the
SPAN80
60.7 product yield.

Table 2. Product yield received from the

In order to increase the emulsion reaction with pre-polymerization step and
stability and the product yield, a pre- Product yield gained from the reaction
polymerization of aqueous solution was without pre-polymerization step.
performed. For pre-polymerization system, System % Yield*
the aqueous phase was heated at 80 oC for With pre-polymerization 76.2  6.74a
30 minute prior to put into the organic Without pre-polymerization 60.7  9.12b
*
Different superscript letters within the same column
phase. The comparison between product indicate significant differences between
yield received from the reaction with pre- formulations (p < 0.05).
polymerization step and that gained from
the reaction without pre-polymerization PC86
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The FTIR spectra of the synthesized material appear at wavenumber 3018 cm-1
poly(acrylic acid)/styrene-butadiene rubber and 1706 cm-1 .7 The peaks at wave number
hybrid material and its main precursors, i.e. around 3100-3000 cm-1 corresponded to
acrylic acid and SBR, are illustrated in CH stretching of alkene group in the
Figure 3. The important characteristic spectrum of hybrid materials (Figure 3(c))
peaks presented in the hybrid material are a is relatively lower than those of its starting
combination of the characteristic peaks of precursors (Figure 3(a) and 3(b)), due to the
acrylic acid and SBR. In figure 3(c), the occurrence of polymerization reaction of
peaks at wavenumber 172 3 cm-1 and 354 5 acrylic acid and the vulcanization of SBR.
cm-1 reveal the vibrations of C=O in Therefore, the success the preparation of
carboxylic group and –OH group of acrylic- poly(acrylic acid)/styrene-butadiene rubber
acid constituent part of hybrid material6, hybrid material is approved.
whereas the characteristic peaks
corresponded to the vibrations in aromatic
ring of SBR constituent part of hybrid

Figure 4. SEM photographs of (a)-(a´) SBR prepared with poly(HIPE) technique, (b)-(b´)
poly(acrylic acid)/SBR hybrid material prepared without pre-polymerization step, and (c)-(c´)
poly(acrylic acid)/SBR hybrid material prepared with pre-polymerization step.

PC87
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
The SEM micrographs of synthesized emulsifier since the SPAN80-stabilized
materials are depicted in Figure 4. The emulsion system displayed the highest
morphology of SBR prepared with normal product yield and a phase separation did not
poly(HIPE) technique is shown in Figure exist throughout the course of reaction. The
4(a)-(a´) as a reference. The morphology of relatively low value of HLB number of
poly(acrylic acid)/SBR hybrid material SPAN80 is seem to be suitable for our
prepared without pre- polymerization step water-in-oil emulsion system. The
is shown in Figure 4(b)-(b´). Figure 4(c)- additional pre-polymerization of aqueous
(c´) display the SEM images of the hybrid phase prior to mix with organic phase could
material prepared with pre-polymerization promote a highly interconnected porous
step. The SEM images of hybrid materials morphology. The present study presents the
demonstrated the fibrous structure of route to prepare the hybrid material with
poly(acrylic acid) located inside the SBR hydrophilic/ hydrophobic bi-continuous
interconnected-porous shell. The pre- structure. The developed material may
polymerization step of aqueous phase useful for a controlled release application.
created the material with relatively high The hydrophilic part can act as the
interconnected porous morphology. Grace absorbing site of a polar active specie,
reported that the droplet of dispersed phase while the hydrophobic part can supply the
can be easiest braked up into smaller tortuous pathways used to retard the
droplets under flow field of continuous releasing phenomena.
phase when the viscosity ratio, i.e. the ratio
of viscosity of dispersed to continuous Acknowledgements
phase, of the immiscible fluid is unity.8 The
The authors would like to thank the
pre-polymerization process resulted in the
supports from Department of Materials
enhancement of aqueous-phase viscosity.
Science and Engineering, Faculty of
Thus, the difference in viscosity between
Engineering and Industrial Technology,
external oil phase and internal aqueous
Silpakorn University. The freeze drying
phase was smaller than that of the emulsion
facility form the Department of
system without pre-polymerization step.
Biotechnology, Silpakorn University is
The smaller droplet size of pre-polymerized
gratefully acknowledged.
aqueous phase was generated during the
emulsion preparation. After curing step, the
References
relatively high-interconnected small porous
structure of material prepared with pre- 1. Cameron, N. R. Polymer 2005, 46 (5),
polymerization step was induced. 1439-1449.
2. Saiwan, C.; Muchan, P.; deMontigny, D.;
4. Conclusion Tontiwachwutikul, P. Energy Procedia
The poly(acrylic acid)/SBR hybrid 2014, 63, 2312-2316.
material was formulated using double 3. Zhang, R.; Zhu, Y.; Zhang, S.; Chen, J.
poly(HIPE) technique. Three different MATEC Web of Conferences 2016, 67,
01014.
types of surfactant, i.e. IGEPAL CO-890,
4. Masalova, I.; Kharatyan, E.; Tshilumbu,
TWEEN80, and SPAN 80, were selected to
N. N. Colloid J. 2013, 75 (5), 579-585.
stabilize the emulsion during a reaction 5. Zhang, S.; Chen, J.; Perchyonok, V. T.
period. SPAN80 was the most effective Polymer 2009, 50 (7), 1723-1731. PC88

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
6. Todica, M.; Stefan, R.; Cornel, P.; Olar,
L., I. Acta Phys. Pol. A 2015, 128, 128-
135.
7. Orlov, A. S.; Kiselev, S. A.; Kiseleva, E.
A.; Budeeva, A. V.; Mashukov, V. I.,
J.Appl. Spectrosc. 2013, 80 (1), 47-53.
8. Grace, H. P. Chem. Eng. Commun. 1982,
14 (3-6), 225-277.

PC89

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Homogeneous acetylation of cellulose with acetyl chloride to cellulose
acetate from water hyacinth
Malinee Leekrajang*, Borwon Narupai, Nattaporn Chutichairattanaphum,
Siriporn Larpkiattaworn
Expert Centre of Innovative Materials, Thailand Institute of Scientific and Technological Research,
Pathum Thani 12120, Thailand
*E-mail: [email protected]

Water hyacinth has a high cellulose content using as a raw material for cellulose- based
polymer. The purpose of this research was to synthesize cellulose acetate (CA) from water
hyacinth by acetylation reaction with acetyl chloride. The extracted cellulose was purified by
removing wax, bleaching and hydrolysis treatments. The homogeneous acetylation of cellulose
was carried out in N,N-dimetylacetamide (DMAc) in combination with lithium chloride (LiCl).
The acetylation conditions, such as time and temperature, were optimized for yielding high
levels of degree of substitution (DS). The degree of substitution was evaluated by proton
nuclear magnetic resonance (1H NMR) spectroscopy. The cellulose acetate products were
characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis
(TGA), and X-ray diffractometry (XRD).

1. Introduction bioproducts. Recent reports have shown that

Cellulose acetates (CA) are derivatives this weed has high fiber content and contains a
of cellulose, which are obtained by reaction of high percentage of cellulose in its shoots and
cellulose with acetic anhydride in the presence roots. WH contains almost 20% of cellulose,
of catalyst. CA are applied to a wide variety of 48% of hemicelluloses and 3.5% of lignin. The
applications including cigarette filters, films, high hemicellulose and cellulose content of the
filtration membranes, laminates and fibers. As WH can be explored for the production of
a fiber application, CA is one of the most various value-added products. The cellulose is
favorable polymer for electrospinning because extracted from WH using bleaching and
of its ability to fabricate nanostructures with hydrolysis treatments in order to remove
unique properties such as high flexibility and hemicellulose and lignin.8-10
durability, chemical resistance, good CA is usually synthesized from
mechanical strength, and low cost. Therefore, cellulose under heterogeneous reaction.
using cellulose acetate has gained a lot of Purified cellulose is subject to an acetylation
attentions for producing composite nanofibers, reaction with acetic anhydride, which is used
to the important applications as a biological as an acetylating agent; acetic acid is used as a
material.1-3 solvent, and either sulfuric acid or perchloric
Generally, CA preparation has been acid is used as a catalyst. The use of sulfuric
easily produced from processed natural acid leads to residual sulfur in final products.11-
14
sources and other agricultural residues such as Recently, much attention has been focused
corn stalk, rice husk, wood and sugarcane on the use of ionic liquids as green solvents for
bagasse.4-7 The abundant aquatic weed species homogeneous reaction with a controllable the
water hyacinth (WH) can be used as raw DS value. Therefore, there is still interest in
material for CA preparation which is a developing homogeneous reaction of cellulose
renewable and sustainable source provided for the production of cellulose esters,
inexpensive and environmentally friendly especially.15-16 Homogeneous acetylation PC90

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
reaction which mixed solvent N,N- studied for acetylation to evaluate the optimum
dimethylacetamide (DMAc) with lithium reaction conditions. The second step is the
chloride (LiCl) has been commonly used for acetylation step, acetyl chloride (3 mol/mol
homogeneous esterification. The CA obtained anhydroglucose unit, AGU) was added slowly
from homogeneous acetylation has more to the WH-C solution, and this solution was
uniform structure and DS depending on the heated to 50,60 and 70 C namely WH-CA50,
adjusting reaction conditions.17-18 WH-CA60 and WH-CA70, respectively.
In this work, the study was performed Subsequently, the solution was left at 50 C for
for the optimization conditions of water 3,4 and 5h namely WH-CA3, WH-CA4 and
hyacinth cellulose acetate (WH-CA) WH-CA5, respectively. Finally, the product
homogeneous acetylation reaction including was isolated by precipitation in methanol. The
the various of temperature and time. The WH-CA was centrifuged, vacuum filtered and
products of WH-CA were characterized by washed several times with methanol. The
measurement of TGA, XRD, NMR and ATR- obtained WH-CA was dried under vacuum for
FTIR. 24 h at 40 °C.

2. Materials and Methods

2.1 Materials and chemicals
Cellulose was extracted from water
hyacinth (WH-C) by bleaching and hydrolysis
treatments. Chemical separation of cellulose
was carried out to remove lignin,
hemicellulose and other components. WH-C
used as raw materials were obtained from our
laboratory. The materials were dried in oven Figure 1. Homogeneous acetylation of WH-C
and stored at room temperature. All reagents in LiCl/DMAc.
and chemicals using in our study were 2.3 Characterization of the water hyacinth
analytical reagent grades such as acetyl cellulose acetate (WH-CA)
chloride, N,N-dimetylacetamide (DMAc), The WH-CA were evaluated functional
lithium chloride (LiCl), methanol, and other group and chemical structure by Attenuated
chemicals. The reagents were used without Total Reflectance Fourier Transform Infrared
further purification. Spectroscopy (ATR-FTIR) using a prestige 21
2.2 Preparation of cellulose acetate from Shimadzu FT-IR spectrometer. FTIR spectra
WH-C were collected in the transmittance mode
The Preparation of WH-CA from WH-C in the region from 4000 to 600 cm−1. The
is two-step processes. The homogeneous thermal properties were determined by
acetylation is shown in Figure 1. First, thermogravimetric analysis (TGA) with a
dissolution of WH-C in LiCl/DMAc. WH-C (5 heating rate of 10◦C/min from 30◦C to 600◦C
wt%) was dissolved by DMAc and this under nitrogen flow. The crystallinity of WH-
solution was stirred at 120 °C for 2 h. Then, the CA was analyzed using X-ray diffractometer
solution was cooled to 80 °C. Subsequently, (XRD) with Cu K radiation in the range of 2
LiCl were added to the mixture. The mixture = 5–50◦, and the scanning rate is 5◦/min. NMR
after overnight stirring at room temperature spectra were recorded on Advance III
was changed to clear solution. The reaction HD/Oxford 500 MHz FT-NMR
parameters; time and temperature, were spectrometer from Bruker Instruments. The PC91

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
degree of substitution (DS) of WH-CA was
determined by 1HNMR spectroscopy. The
area between 3.6 and 5.2 ppm corresponded to
the seven anhydroglucose protons and the area
between1.9 and 2.2 ppm corresponded to the
three acetyl protons.
Table 1. Degree of Substitution of WH-CA
Acetylation peaks at 3.6-5.2 ppm corresponded to the
Acetylated WH-C
conditions
Samplea WH- WH-CA60 WH- seven anhydroglucose protons. The DS
CA50 CA70 values were calculated by the ratio of 1/3 of
Temperature 50 60 70 the acetyl area to 1/7 of the anhydroglucose
(C)
area. As can be seen from Table 1, the
DS 2.05 1.57 1.74
Sampleb WH- WH-CA4 WH- effects of various conditions such as
CA3 CA5 reaction time and temperature on the DS of
Time (h) 3 4 5 WH-CA was investigated. At the reaction
DS 1.27 1.18 1.05
a: Time (h) = 2h temperature 50 C, the calculated DS value
b: Temperature was 2.05 for WH-CA50. The reaction
(C) = 50 C temperature was evidenced by the product
with DS of 1.57 (WH-CA60) and 1.74
3. Results & Discussion (WH-CA70) when the reaction was
3.1 1H-NMR Spectroscopy performed at 60 C and 70C respectively.
The increasing reaction temperature from
50 C up to 70C, WH-CA products of
lower DS values were obtained by
acetylation at high temperatures. The
acetylation reaction under high temperature
can cause some decomposition of cellulose
backbone during the reaction, this result
showed that a low operating temperature
was mild condition and potentially more
efficient. Therefore, the temperature at 50
C was selected. Then, under the fixed
Figure 2. 1H-NMR of WH-CA50 (DS 2.05)
condition of rection temperature at 50 C,
in DMSO-d6.
when the reaction time was changed from 3
The optimum conditions for
h to 5 h. To increasing reaction time, the DS
homogeneous acetylation of WH-C were
of WH-CA was decreased. Therefore, the
investigated in terms of different reaction
1
optimum condition for homogeneous
time and temperature. H-NMR
esterification reaction was 50 C for 2 h.
spectroscopy was used to examine the
distribution of acetyl moieties within the
modified AGU and DS values. The 1H-
NMR spectra for WH-CA samples recorded
in DMSO-d6 are presented in Figure 2. The
Peaks 1.9-2.2 ppm were assigned to three
methyl protons of the acetyl groups and the PC92

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 and WH-CA can be seen in Figure 4. The
FTIR spectrum of the WH-CA was shown
major changes in the spectra as compared to
the WH-C. The successful and effective
acylation of WH-C was evidenced by the
appearance of characteristic bands assigned
to the ester group at 1731 cm-1 (C=O
stretching of ester), 1370 cm-1 (C-H
stretching in -OCOCH3) and 1225 cm-1 (C-
O stretching of acetyl group). A strong band
at 1027 cm-1 corresponds to the C-O-C
Figure 3. TGA curves of various WH-CA pyranose ring skeletal. The absorbance
in reaction temperature for 2 h. band at 3335 cm-1 was assigned to the -OH
Figure 3 shows the TGA curves of stretching of WH-C. The decrease of WH-
various WH-CA products. The thermal CA spectrum at 3335 cm-1 (hydroxyl -OH
stability of WH-CA was determined by its stretching) because the O-H groups was
onset of degradation temperature. The replaced by acetyl group in the cellulose
increasing trend of decomposition structure. The decrease in the intensity of
temperature indicated that the thermal the peak at 1639 cm−1 indicated that WH-
stability of WH-CA50 was greater than CA represented a hydrophobic nature. The
WH-CA60. The presence of DS value FTIR spectra were demonstrated that the
significantly was influenced thermal homogeneous acetylation of WH-C into
stability of WH-CA by shifting the onset WH-CA has been successfully carried out.
temperatures to lower values.
3.2 FTIR analysis

Figure 5. TGA and DTA curve of WH-C

and WH-CA.
3.3 Thermal analysis
Figure 4. FT-IR spectra of (a) WH-C and The thermal properties of WH-C
(b) WH-CA. and WH-CA were determined by TGA and
The most characterization for the DTA in the temperature range 30-600 ◦C at
evidence of structural features of WH-CA a rate of 10◦C/min under nitrogen flow. The
was examined by ATR-FTIR spectroscopy. TGA and DTA curve of WH-C and WH-
The results of functional groups on WH-C CA were illustrated in Figure 5.
PC93

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The thermal degradation of WH-C
and WH-CA occured in various steps such
as desorption of water and other volatile
components. The TGA curves of samples
displayed a minor weight loss at 30-120 °C,
which was attributed to evaporation of
water or moisture content present in the
samples. In the second region, significant
weight loss was observed due to thermal
decomposition. For WH-C, 86% weight
loss happened at 302-341 °C. Compared to
WH-CA, 93% weight loss the degradation Figure 6. XRD curve of WH-C and WH-
was high temperature range (328-367 °C). CA.
The increase of thermal degradation
indicated enhancing thermal stability of 4. Conclusion
WH-C after acetylation. Also, the
exothermic peak corresponds to the heat The preparation of WH-CA from
release from the compounds at maximum water hyacinth was performed under mild
temperature of 302 ◦C for WH-C and 340◦C condition by homogeneous reaction with
for WH-CA in the DTA curve. This clearly acetyl chloride. The DS of acetylation of
showed that the thermal stability of WH- WH-C was influenced by the reaction
CA is higher than that of the WH-C. temperature and time. In our experimental
condition, the reaction was kept at 50 C for
3.4 XRD analysis 2 h. The degree of substitution, functional
The XRD results of the WH-C and group, thermal stability and crystallinity of
WH-CA are presented the changes in the cellulose acetate were characterized by
crystallinity in Figure 6. The WH-C showed measurement of 1H NMR, FT-IR, TGA and
three diffraction peaks at 2 = 15.5, 21.6 XRD. Moreover, the results obtained
and 34.1 characteristic of cellulose I. The confirm that water hyacinth represents a
shoulder diffraction peak at 16.0 and weak raw material with high potential for the
peak at 34.0 could be interpreted that the production of cellulose derivatives.
absence of lignin and hemicellulose in WH-
C. The intensity of the peaks has no distinct Acknowledgements
sharp peak and it may be attributed to the
The financial support for this
semi-crystalline nature of the WH-CA. The
project was provided by National Research
weak diffraction peak appeared around
Council of Thailand (NRCT) and Thailand
19.3 in the diffraction pattern of cellulose Institute of Scientific and Technological
acetate. The WH-CA displayed a low Research (TISTR).
degree of crystallinity compared with WH-
C due to the substitution of the hydroxyl References
groups by acetyl groups. 1. Sun, X.; Lu, C.; Zhang, W.; Tian, D.;
Zhang, X. Polymers, 2013, 98, 405–
411.
PC94

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2. Candidoa, R.G.; Goncalves, A.R. 12. Li, J.; Zhang, L.P.; Peng, F.; Bian, J.;
Carbohydr. Polym. 2016, 152, 679– Yuan, T.Q.; Xu, F.; Sun, R.C.
686. Molecules. 2009, 14, 3551-3566.
3. Egot, M.P.; and Alguno, A.C. Key Eng. 13. Cao, Y.; Zhang, J.; He, J.; Li, H.;
Mater. 2018, 772, 8-12. Zhang, Y. Prod. Eng. Chem. Technol.,
4. Cerqueira, D.A.; Filho, G.R.; Meireles, 2010, 18, 515-522.
C.S. Carbohydr. Polym. 2007, 69, 579- 14. Edgar, K.J.; Buchanan, C.M.;
582. Debenham, J.S.; Rundquist, P.A.;
5. Kannamba, B.; Gopinath, K.; Jahnai, Y. Seiler, B.D., Shelton, M.C.; Tindall, D.
Int. J. Multidiscip. Avc. Res. Ted. 2015, Prog. Polym. Sci. 2001, 26, 1605-1688.
2, ISSN : 2349-7408. 15. Pinkert, A.; Marsh, K.N.; Pang, S.S.;
6. Das A.M.; Ali, A.A.; Hazarika, M.P. Staiger, M.P. Chem. Rev. 2009, 109,
Carbohydr. Polym. 2014, 112, 342-349. 6712–6728.
7. Cheng, H.N.; Dowd, M.K.; Selling, 16. Ragauskas, A.; Williams, C.K.;
G.W.; Biswas, A. Carbohydr. Polym. Davison, B.H.; Britovsek, G.; Cairney,
2010, 80, 449-452. J.; Eckert, C. A.; Frederick, W. J.;
8. Sindhu, R,; Binod, P,; Pandey, A.; Hallett, J. P.; Leak, D. J.; Liotta, C. L.;
Madhavan A.; Alphonsa, A.J.; , Vivek, Mielenz, J. R.; Murphy, R.; Templer,
N.; Gnansounou, E.; Castro, E.; Faraco, R.; and Tschaplinski, T. Science, 2006,
V. Bioresour Technol. 2017, 230, 152- 311, 484–489.
162. 17. McCormick, C.L.; Callais, P.A.;
9. Sundari, M. T.; Ramesh, A. Hutchinson, B.H. Macromolecules.
Carbohydr. Polym. 2012, 87, 1701- 1985, 18, 2394-2401.
1705. 18. Ramos, L.A.; Morgado, D.L.; Seoud,
10. Istirokhatun, T.; Rokhati, N.; O.A. E.; Silva, V.C.; Frollini, E. 2011,
Rachmawaty, R.; Meriyani, M.; 18, 385-392.
Priyanto, S.; Susanto H. Procedia
Environ. Sci. 2015, 23, 274-281.
11. Biswas, A.; Saha, B.C.; Lawton, J.W.;
Shogren, R.L.; Willett, J.L. Carbohydr.
Polym. 2006, 64, 134-137.

PC95

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Preparation and characterization of chitosan-activated carbon-poly(vinyl
alcohol) composite films for controlled release of 1-naphthaleneacetic acid
Pimpaka Chanchettanadi1, Nannapat Kaewnukulkit2, Duangkamon Viboonratanasri4,
Lapporn Vayachuta4, Pakorn Opaprakasit3, Panida Prompinit4*
1
Interdisciplinary Graduate Program in Sustainable Energy and Resources Engineering,
Thammasat University, Pathum Thani 12120, Thailand
2
Interdisciplinary Graduate Program in Sustainable Energy and Resources Engineering, Kasetsart University,
Bangkok 10900, Thailand
3
School of Biochemical Engineering and Technology, Sirindhorn International Institute of Technology (SIIT),
Thammasat University, Pathum Thani 12121, Thailand
4
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency
(NSTDA), Khlong Luang, Pathum Thani, 12120, Thailand
*E-mail: [email protected]

Food security is a current global problem. Therefore, plant growth regulators have been
introduced to maintain availability of sufficient food quantity with appropriate quality. 1-
Naphthylacetic acid (1-NAA) is widely used as a plant growth regulator. However, high
concentration of 1-NAA inhibits plant growth, contaminates in environment, and affects human
health. Here, we report a novel chitosan (CS)-activated carbon (AC)-poly (vinyl alcohol)
composite film for controlled release of 1-NAA. It was found that neutralization by diluting
ethanol solution for four cycles promoted 1-NAA absorption. This was because it could largely
promote the presence of ammonium form (NH3+) in CS structure. XPS results showed that as
AC/CS ratios in the composite films increased, the -NH3+/NH ratios decreased corresponding
to the reduction of CS content in the films. Performance of the developed composite film was
evaluated using 1-NAA absorption and release studies. It showed that the film with AC/CS
ratio at 24:16 exhibited maximum 1-NAA absorption capacity (12.34±0.24 mgּ g-1) and it also
could effectively slow release of 1-NAA in water and reached 11% after 14 days. Although the
developed composite film could absorb 1-NAA lower than pure chitosan film by 1.3 times, it
could slower release of 1-NAA than that of the pure chitosan film by ~3 times. This was caused
by the presence of both electrostatic and π–π interactions for 1-NAA attraction in the composite
film structure.

1. Introduction accelerate plant growth resulting in food

The world is facing a perilous contamination.1 Therefore, adequate and
convergence in depleting natural resources of clean food with good nutrition for everyone
water, good land, nutrient, and stable is urgent issue as a global requirement.
climates. This phenomenon is caused by an Various technologies have been
increasing in the world’s population which is introduced to increase crop yield
predicted to quickly increase by about 2 qualitatively and quantitatively including
billion from 2019 to 2050. This results in the utilization of plant growth regulators (PGRs).
world's demand for food increase affecting PGRs include hormonal substances of natural
food security problems. Climate change is occurrence (phytohormones) and their
another cause that affects food production. synthetics.2 1-Naphthalene acetic acid (1-
The farmers have to use agrochemicals to NAA) is one of PGRs and synthetic auxin PC96

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
that has been widely used in plants due to its properties of the synthetic composite films
modest cost and rapid action. 1-NAA affects were studied.
cell elongation, fruit formation, apical
dominance, geotropism and photoperiod. 1- 2. Materials and Methods
NAA with 20-100 mgּ L-1 is normally used as 2.1 Materials
PGRs and fungicide.3 Although 1-NAA has a Chitosan (CS) (degree of
half-life in soil of 10 days attributed to deacetylation 90%, viscosity 100-300 cps)
microbial degradation,4 excessive 1-NAA in was obtained from Marine Bio Resources
agricultural uses can leach into groundwater Company. Poly(vinyl alcohol) (PVA)
and soil resulting in uncontrollable adverse (polymerization degree in range of 1500-
environmental impact. Toxicology of 1-NAA 1800; hydrolysis degree of 99%) was
has been studied and reported to be harmful purchased from FUJIFILM Wako Chemical
to animal and human health. This was shown Corporation. Sodium metasilicate
when tested via oral ingestion (LD50) at 1 g pentahydrate (Na2SiO3·5H2O, ≥95.0%) was
ּ kg-1 on rat and 0.743 gּ kg-1 on mouse. It can obtained from Aldrich Chemical
cause skin and serious eye irritations at long Corporation. Acetic acid glacial was
length of contact time.5 Therefore, controlled purchased from Carlo Erba Reagents
release system is highly desirable for Company. All chemical reagents were used
increasing utilization of 1-NAA as well as as received without further purification.
reducing environmental pollutions.6 2.2 Preparation of activated carbon-
In this study, a chitosan-activated chitosan-poly (vinyl alcohol) films
carbon-poly(vinyl alcohol) composite film In a typical procedure, 30 ml of 5%
was fabricated for controlled-release of 1- w/v of chitosan in acetic acid was prepared at
NAA. Considering 1-NAA molecular room temperature. The weight of 0.12, 0.24,
structure, it possesses two main parts which 0.36, 0.48 and 0.60 g of activated carbon
are (i) a carboxylmethyl group (CH2CO2H) were added into 50 mL of 2% PVA solution
linked to (ii) the "1-position" of naphthalene. followed by stirring for 2.30 h to obtain
Chitosan (CS) has a polycationic nature in acid AC/CS/PVA solutions. After that, 10 mL of
media, hence, it could potentially bind with a sodium metasilicate solution was slowly
negatively charged carboxylmethyl group added to AC/CS/PVA solution and stirred to
(CH2CO2H) of the 1-NAA via electrostatic obtain a homogeneous solution with 0.6%
attraction.7 Activated carbon (AC) contains w/w SiO2. The solutions were mixed and
aromatic structures and C=C double bonds sonicated for 15 min to obtain homogenous
which could strongly bind with the solutions. Then the solutions were degassed
naphthalene part of the 1-NAA through the by vacuum pump at 30-50 mbar and
interactions with π-electrons.8 Therefore, the sonicated using degas mode for 15 min. After
presence of CS and AC in the film was that AC/CS/PVA solutions were poured into
expected to improve absorption capacity as 9×9 cm2 aluminum molds and dried in an
well as release rate of 1-NAA. Appropriate oven at 70°C for 1.30 h. The film thickness
condition for composite film preparation and was controlled by solution volume. The
effect of AC/CS ratio on its performance in above experiment was conducted by fixing
absorption and release of 1-NAA were the ratio of (AC+CS): PVA as (40):60 to get
investigated. Physical and chemical the films with different compositions by
PC97

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
varying ratios between activated carbon (AC) solutions were analyzed using UV-Vis-NIR
and chitosan (CS) of 8:32, 16:24, 24:16, and spectroscopy at a wavelength of 282 nm.
32:8 and were denoted as Then the 1-NAA solutions were replaced by
AC8/CS32/PVA60, AC16/CS24/PVA60, fresh 5 mL of 10-4 M 1-NAA solutions.
AC24/CS16/PVA60, and AC32/CS8/ Numbers of absorption cycles were carried
PVA60, respectively. out and the remained 1-NAA contents were
2.3 Film neutralization calculated to obtain absorption capacity of
Effect of neutralization condition on the films. For 1-NAA desorption, 1×1 cm2 of
generation of -NH3+ group on chitosan film the AC/CS/PVA films were immersed in 4
for 1-NAA absorption was investigated. Pure mL of DI water and the solutions were
chitosan film was used for this study. The collected at 60 min, 1, 3, 5, 7, 11 and 14 days.
dried films were immersed in 80% v/v The amount of 1-NAA absorbed and released
ethanol solution (EtOH) for 10 min by by the composite films were calculated by the
varying number of immersion cycles. The following equation:13
neutralized films were denoted as CS-1 cycle,
CS-2 cycles, CS-3 cycles, CS-4 cycles and (C0 -Ce )V
qe =
CS-5 cycles for treatment at 0, 1, 2, 3, 4 and W
5 cycles, respectively. For the dried where qe is an amount of 1-NAA absorbed
AC/CS/PVA films, they were neutralized onto a unit amount of film (mg·g-1), C0 is an
using an optimum condition obtained from initial concentration of 1-NAA (mg·L-1), Ce
above experiment. is a final or equilibrium concentration of 1-
2.4 Film characterizations NAA (mg·L-1), V is a volume of 1-NAA
Surface chemical analysis was carried solution (L), and W is a weight of dried
out using X-ray photoelectron spectroscopy composite film (g).
(XPS) at BL5.2 in the Synchrotron Light
Research Institute, Thailand. The XPS 3. Results & Discussion
spectra were calibrated using the C 1s signal 3.1 Effect of neutralization cycles on
at 284.4 eV. Thermogravimetric analysis chitosan film structures.
(TGA) of all samples were performed using The effect of neutralization cycles on
the Thermogravimetry (TG)/Differential chitosan (CS) film structures was studied
Thermal Analyzer (DTA) on a Diamond TG- using XPS technique in N 1s region as shown
DTA 6300 thermal analyzer using an Al2O3 in Figure 1. The CS film before treatment
crucible (150 μL) with a sample mass (Fig 1a) showed major N 1s contributions at
approximately 4.0 mg, heating rate of 5 399.3 eV, 400.3 eV, and 401.3 eV
°C·min-1, dry air flow of 60 mlּ min-1 and the corresponding to non-protonated amine,
temperature ranged from 30 to 800 °C. amide groups (N-C=O),9 and amino groups in
2.5 1-NAA absorption and controlled ammonium form (NH3+),9 respectively.
release studies These three main peaks were also observed in
1-NAA absorption experiments were CS films after neutralization with all
carried out by immersion of 1×1 cm2 of the conditions (Figure 1b-1f). The presence of a
AC/CS/PVA films in 5 mL of 10-4 M 1-NAA positively charged ammonium form (NH3+)
solutions at room temperature. After is important for strong binding with negative
absorption, 1-NAA contents remaining in the charged 1-NAA molecules. Therefore, peak PC98

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
area ratio of -NH3+/NH was calculated for 3.2 Effect of AC/CS ratios on AC/CS/PVA
consideration. It was found that as composite film structures.
neutralization cycles increased from 1 to 4 Effect of AC/CS ratios on
cycles the -NH3+/NH ratios increased from AC/CS/PVA composite film structures was
0.10 to 0.44 and dramatically decreased to be studied using XPS technique in N 1s region
0.11 after 5 cycles of neutralization. as shown in Figure 2. The spectrum of pure
Furthermore, all samples were used for 1- CS film after treatment with EtOH was
NAA absorption test (data not shown). It was shown in Figure 2a for comparison. It
found that the maximum absorption capacity composed of three main peaks at 399.3 eV,
was also obtained from the film neutralized 400.3 eV, and 401.3 eV, which are attributed
for 4 cycles. Hence, film treatment with to non-protonated amine (NH), amide groups
dilute EtOH for 4 cycles was an optimum (N-C=O), and amino groups in ammonium
neutralization condition used for further form (NH3+), respectively. These peaks were
study. also observed in most of composite films. In
this study, peak area ratio of -NH3+/NH was
calculated for comparison of the film
N1s NH3+ N-C=O
N-H (a) properties. It showed that as AC/CS ratios in
400.3
0.93 401.3 399.3 the composite films increased from 0:40,
NH3+/NH = 0.05
8:32, 16:24, 24:16, 32:8, and 40:0, the -
0.62
(b) NH3+/NH ratios decreased from 0.15 to 0 (Fig
1.26
2b-2g). Decreasing in -NH3+/NH ratios
NH3+/NH = 0.10
0.63 corresponded to the reduction of CS content
Intensity (CPS) / 103

(c) in the films.

1.32

NH3+/NH = 0.13
0.66

1.00 (d)
NH3+/NH = 0.40
0.75

(e)
1.15
+
NH3 /NH = 0.44
0.92

(f)
1.18
NH3+/NH = 0.11
0.59
404 402 400 398 396
Binding energy (eV)

Figure 1. XPS spectra of (a) chitosan film,

chitosan films after neutralization with EtOH
solutions for (b) 1 cycle, (c) 2 cycles, (d) 3
cycles, (e) 4 cycles, and (f) 5 cycles.

PC99

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 composite film system, absorption capacities
of all films were lower than that of pure CS
film. As AC/CS ratios in the composite films
increased from 0:40 to 24:16 (with the
reduction of CS and NH3+ contents),
absorption capacities were surprisingly
slightly increased and reached the maximum
value at 12.24±0.80 mgּ g-1, as obtained from
sample with AC/CS ratio at 16:24. High
absorption capacity of this sample was likely
caused by a combination of (i) electrostatic
attraction between 1-NAA and CS 7 and (ii)
π–π interaction between 1-NAA and AC
structures. 8 At high AC/CS ratio of (32:8 and
40:0), the absorption obviously decreased
because of low CS content.
Cumulative release profiles of the AC
powder, PVA film, CS film, and composited
films as a function of immersion time in
water were investigated for over 14 days as
Figure 2. N 1s spectra of (a) chitosan film presented in Fig 4. No release profile was
and (b) AC0/CS40/PVA60, (c) AC8/CS32/ obtained from PVA film and
PVA60, (d) AC16/CS24/PVA60, (e) AC24/ AC40/CS0/PVA60 because they were not
CS16/PVA60, (f) AC32/CS8/PVA60, and stable and finally dissolved in water. There
(g) AC40/CS0/PVA60 films after EtOH was also no release profile obtained from AC
neutralization. because AC powder could release very small
3.4 Absorption and release of 1-NAA using amount of 1-NAA leading to difficulty in
the composite films detection. It was found that 1-NAA was
1-NAA absorption behaviors of the gradually released in water from all samples.
composite films prepared at different AC/CS Among all films, the samples with AC/CS
weight ratios compared with raw materials ratios of 24:16 and 32:8 exhibited slowest
(AC powder, PVA film, and CS film) were release of 1-NAA and reached 11% and 12%
investigated as shown in Figure 3. Figure 3a after 14 days (336 h), respectively. This could
showed that 1-NAA absorption capacities of be explained in terms of the presence of high
all samples steadily increased as time amount of AC in the films which could
increased to reach a maximum value at 90 effectively reduce 1-NAA release.
min. After this period, the absorption Thermal stability of all films was
capacities were slightly decreased for most of investigated using thermogravimetric
all samples. Figure 4b showed the absorption analysis (TGA) (data not shown). It was
capacities of all samples after 90 min. It was found that maximum point of the degradation
found that CS film could absorb highest or the temperature of the highest reaction rate
amount of 1-NAA (15.45±0.47 mgּ g-1) (Tmax) of all AC/CS/PVA composite films
whereas AC powder could adsorb very low
amount of 1-NAA (0.92±0.01 mgּ g-1). In the PC100

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
was not significantly different and they were 4. Conclusion
in the range of 270±16.46 °C. We have shown that a novel chitosan-
activated carbon-poly(vinyl alcohol)
20
(a) composite films were synthesized and used
for controlled release of 1-NAA. Treatment
1-NAA absorption capacity (mg g-1)

15
of the films with ethanol solution for 4 cycles
CS100 pure
AC24/CS16/PVA60
AC16/CS24/PVA60
AC0/CS40/PVA60
was a suitable neutralization condition for the
AC32/CS8/PVA60
10
AC8/CS32/PVA60 films because it could largely promote the
presence of ammonium form (NH3+) and
5
effectively absorb 1-NAA. XPS results
AC100 powder
showed that as AC/CS ratios in the composite
0 PVA100 pure
0 30 60 90 120
AC40/CS0/PVA60
150 films increased, the -NH3+/NH ratios
Time (min)

20
decreased, which corresponded to the
(b)
reduction of CS content in the films. For the
1-NAA absorption capacity (mg g-1)

15
performance of the composite films, the film
with AC/CS ratio at 24:16 exhibited high 1-
10 NAA absorption capacity and it also could
effectively slow release of 1-NAA in water.
5 Slower release of 1-NAA from the composite
film than that from pure CS film could be
0
0/100 0/40 8/32 16/24 24/16 32/8
**
40/0 100/0
because of the presence of balanced
AC/CS ratios as fixing PVA at 60 interactions between electrostatic attraction
Figure 3. (a) Absorption behavior of the (between 1-NAA and CS) and π–π
composite films prepared at different AC/CS interaction (between 1-NAA and AC) in the
weight ratios compared with raw materials composite film structure.
(AC powder, PVA film, and CS film). (b)
Absorption capacities of all samples after 90 Acknowledgements
min. The authors would like to thank
Thailand Advanced Institute of Science and
80
Technology and Tokyo Institute of
1-NAA cumulative release (%)

AC0/CS40/PVA60
Technology (TAIST-Tokyo Tech) for
60
funding, Sirindhorn International Institute of
Technology (SIIT), Thammasat University
40

CS100 pure
for suggestions, and Synchrotron Light
AC8/CS32/PVA60

20 AC16/CS24/PVA60
Research Institute for technical help in using
AC32/CS8/PVA60
AC24/CS16/PVA60
XPS. This work was supported by the
0
AC100 powder
PVA100 pure National Nanotechnology Center
AC40/CS0/PVA60
0 2 4 6 8 10
Time (day)
12 14 16 18 20
(NANOTEC) (P 1651720), NSTDA.
Figure 4. Cumulative release profiles of 1-
NAA in water from the composite films
prepared at different AC/CS weight ratios
compared with raw materials (AC powder,
PVA film, and CS film). PC101

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
References 6. Saosamniang, P. S., S.;
1. FAO, World agriculture summit on Viboonratanasri, D.; Vayachuta, L.;
food security 2009. Prompinit, P. July 1 1 ; Petty patent
2. Jamwal, K.; Bhattacharya, S.; Puri, application: 2019.
S., J. Appl. Res. Med. Aroma. 2018, 9, 26-38. 7. Yang, X.; Tu, Y.; Li, L.; Shang, S.;
3. Mancuso, S.; Rinaldelli, E.; Mura, P.; Tao, X. M., ACS Appl. Mater. Interfaces
Faucci, M.; Manderioli, A. J. A. i. H. S., 2010, 2 (6), 1707-13.
1997, 153-157. 8. Wu, T.; Cai, X.; Tan, S.; Li, H.; Liu,
4. JB, W., In Encyclopedia of J.; Yang, W., Chem. Eng. J. 2011, 173 (1),
Environmental Management, Four Volume 144-149.
Set, Ann Arbor Press, 1994; pp 15-41. 9. Brugnerotto, J.; Lizardi, J.;
5. Material Safety Data Sheet,1 - NAA Goycoolea, F.; Argüelles-Monal, W.;
MSDS. http://www.dcfinechemicals.com. Desbrieres, J.; Rinaudo, M. J. P., 2 0 0 1 , 4 2
(8), 3569-3580.

PC102

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Thermal properties of polycaprolactone blended with benzoxazine resins of
different functionalities
Chanidapa Rachniyom1, Suphachok Angsuworapurk2, Sarawut Rimdusit3,
Sunan Tiptipakorn1*
1
Forensic Science Program, Department of Chemistry, Faculty of Liberal Arts and Science,
Kasetsart University, Nakhon Pathom 73140, Thailand.
2
SIG combibloc, Eastern seaboard industrial estate, Rayong, 21140, Thailand.
3
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University,
Bangkok 1330, Thailand
*E-mail: [email protected]

In this research, three benzoxazine types of different functionalities (Ph-a, BA-a, and
TrisP-a) were blended with polycaprolactone (PCL) at the contents varied from 0-30wt%. After
heating the blends, their chemical structures of the curing samples were determined via Fourier
transform infrared spectroscope (FTIR). It could be noticed that for all three blending systems,
the hydroxyl group of polybenzoxazine and carbonyl group of polycaprolactone were
observed. The results from differential scanning calorimeter (DSC) presented that the glass
transition temperature (Tg) of the blends was increased with the PCL content. The benzoxazine
monomer with greater functionalities could provide the higher Tg value. The results from
thermogravimetric analysis revealed that the increase of PCL content could lead to the higher
value of decomposition temperature. These blends could be potentially used in higher
temperature than pure polybenzoxazine, such as potential application as friction materials.

1. Introduction 2. Materials and Methods

Polybenzoxazines are a class of noble 2.1 Materials
thermosetting resins with good mechanical Bisphenol-A (99% purity),
and high thermal properties. In general, many formaldehyde (95% purity), aniline (99%
advantages of these polymers have been purity), phenol (99% purity), 1,1,1 tris(4-
reported, i.e. no need of catalyst to synthesize hydroxyphenyl)) ethane (99% purity) and
the polymer, no by-product generated upon polycaprolactone (Mn =10000 Dalton) were
curing.1,2 However, the brittleness of these purchased from Sigma-Aldrich. All
polymer could limit their range of chemicals were used as received.
applications. The addition of 2.2 Synthesis of the blends
polycaprolactone (PCL) to polybenzoxazine Ph-a type of benzoxazine monomer
has been reported to enhance the toughness was synthesized by mixing phenol, aniline,
of the polymer blends.3 However, there have and formaldehyde at the mol ratio of 1:1: 2.
not been reported about the thermal BA-a type of benzoxazine monomer
properties of the different types of was synthesized by mixing bisphenol-A,
polybenzoxazine blended with PCL before. aniline, and formaldehyde at the mol ratio of
In this research, the thermal properties of the 1: 4: 2.
blending systems between three types of TrisP-a type of benzoxazine
polybenzoxazines (i.e. Ph-a, BA-a, and monomer was synthesized by mixing 1,1,1
TrisP-a) and PCL were determined. PC103

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
tris(4-hydroxyphenyl)ethane, aniline, and
formaldehyde at the mol ratio of 1: 3: 6.
In order to obtain the monomers, all
A
three mixtures were heated at ca. 110 (for Ph-
a, and BA-a monomer types) and-ca. 130oC
(for trisP-a monomer type) for 45 minutes.
After that, the monomers were blended with
PCL in the aluminum pans at 110oC for 10
minutes.
2.3 Characterizations
The chemical structures of the curing
samples blends were determined with fourier
transform infrared spectroscope (FTIR,
BRUKER Tensor 27 model). The scan
number was 16 and resolution was 4 cm-1. B
The glass transition temperatures (Tg) of the
blends were determined with differential
scanning calorimeter (DSC, Mettler Toledo
DCS822e model). The analysis was
conducted with the heating rate of 20oC/min
under the nitrogen atmosphere. The
decomposition temperature of the blends was
determined with thermogravimetric analyzer
(TGA, Mettler Toledo, TGA/DSC 2 model).
The analysis was conducted with the heating
rate of 20oC/min under the nitrogen
atmosphere.
C
3. Results & Discussion
3.1 FTIR analysis
The FTIR spectra of the PCL blended
with monofunctional benzoxazines (Ph-a),
bifunctional benzoxazines (BA-a), and
trifunctional benzoxazines (TrisP-a) at
different PCL contents were presented in
Figure 1(a), 1(b), and 1(c), respectively. It
could be noticed that the peaks at
wavenumber of ca. 3438 and 3370 cm-1 were
shifted towards when increasing PCL
contents. This could indicate the hydrogen Figure 1. FTIR spectra of PCL blended with
bonding between two polymeric domains as Ph-a (A), BA-a (B), and TrisP-a (C) at
correlated to the previous study.3 different PCL contents: 0 wt% (a), 10 wt%
(b), 20 wt% (c), and 30 wt% (d).
PC104

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.2 DSC determination

, C)
390

o
The values of glass transition

d10
temperature (Tg) of the blends between PCL

Decomposition temperature (T
380
and different benzoxazines types are
exhibited as shown in Figure 2. It could be
370
seen that the addition of PCL could lead to an
increase in Tg. The synergy behaviors of Tg
were observed in all three blending systems. 360
This could be attributed to the fact that the Ph-a
BA-a
hydrogen bonds between PCL and three 350 TrisP-a

benzoxazine types could hinder the

movement of the polymeric chains. 340
Moreover, it could be seen that the 0 10 20 30
benzoxazine monomer with greater PCL content (wt%)
functionalities could provide the higher Tg Figure 3. Td10 values of the PCL blended
value. with Ph-a (), BA-a (), and TrisP-a () at
250 different PCL contents.
Glass transition temperature ( C)

4. Conclusion
o

200
Three benzoxazine types of different
functionalities (Ph-a, BA-a, and TrisP-a)
150 were blended with polycaprolactone (PCL) in
this study. FTIR spectra presented the
100
Ph-a
BA-a
hydroxyl group of polybenzoxazine and
TrisP-a
carbonyl group of PCL for all three blending
systems. The DSC thermograms showed the
50 synergy of Tg values for all three blending
0 10 20 30
PCL (wt%) systems. The Tg values were increased with
increasing PCL content. The benzoxazine
Figure 2. Tg values of the PCL blended with monomer with greater functionalities could
Ph-a (), BA-a (), and TrisP-a () at provide the higher Tg value. The TGA results
different PCL contents. showed that adding PCL could increase
3.3 TGA analysis decomposition temperature.
The values of decomposition
temperature at 10 % weight loss (Td10) of the Acknowledgements
blends between PCL and different This work is financially supported
benzoxazines types are exhibited as shown in from the Research Promotion and
Figure 3. It could be seen that the addition of Technology Transfer Center (RPTTC),
PCL could lead to an increase in Td10 value. Faculty of Liberal Arts and Science,
This could be due to different intermolecular Kasetsart University, Thailand.
forces between two polymeric domains
having effects on the thermal stability of the
blends.
PC105

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
References
1. Ishida, H.; Lee, Y. H. J. Appl. Polym. Sci.,
2001, 39,736-749.
2. Takeichi, T., Takuya, K., Tarek, Agag.
Polymer 2005, 46, 12172.
3. Tiptipakorn, S.;,Keungputpong, N.;
Phothiphiphit, N.; Rimdusit, N. J. Appl.
Polym. Sci., 2015, 41915.

PC106

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Modified nanocrystal cellulose as green fillers to improve crystallization
property of poly (L- lactide) bionanocomposite films
Chutima Banthao1, Yodthong Baimark1, Sujitra Wongkasemjit2, Kansiri Pakkethati1*
1
Department of chemistry, Faculty of science, Mahasarakham University, Mahasarakham 44150, Thailand
2
Petroleum and petrochemical college, Chulalongkorn University, Bangkok 10330, Thailand
*E-mail: [email protected]

Modified nanocrystal cellulose which were extracted from rice straw by hydrolysis method
improved crystallization property of poly (L-lactide) bionanocomposite films. The nanocrystal
cellulose were obtained a diameter between 50 and 600 nm by particle size analyzer. The
bionanocomposite films were prepared by solution casting method using poly (L-lactide) and modified
nanocrystal cellulose with different weight ratios (100/0, 99/1, 97/3, 95/5). The films were characterized
by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction
(XRD) and scanning electron microscopy (SEM). The thermal properties and crystallinity of
bionanocomposite films were increased by increasing the amount of modified nanocrystals cellulose.
The results of this study showed that modified nanocrystal cellulose from rice straw can enhance the
thermal properties and crystallinity of bionanocomposite films.

1. Introduction density renewability, very large surface area

In current, "green chemistry" is popular all abundance in nature, biocompatibility and
over the world. The tendency to use biodegradability.
biodegradable polymers is increasing in various The CNCs are very promising for
industries to reduce the accumulation of fossil using as reinforcement in high-performance
plastic waste and to protect the green nanocomposite with sustainable appeal. The
environment. Biodegradable polymers can be large surface area and the presence of abundant
divided according to their source into 3 types: surface hydroxyl groups allow the
naturally produced renewable polymers, functionalization of CNCs. In previous work,
synthetic polymers derived from renewable Aihua3 has improved the crystal properties of
resources, and synthetic polymers derived from PLL. To compare properties of composite, PLL
petroleum-based resources.1 Polylactide (PLL) is were added CNCs and modified CNCs (n-
a popular biodegradable polymer due to its dodecyldimethylchlorosilane) using solution
outstanding properties as high mechanical, casting. The results show that the modified CNCs
biodegradability, transparent, low density and have higher crystallinity than CNCs. Consistent
biocompatibility. However, it presents some with the research of Orellana2 that they
disadvantages, such as low thermal stability, compared the properties of PLL by filling their
brittleness and low crystallization rate, which material with CNCs and modified
hinders its use in many applications.2 Thus CNCs(cetyltrimethylammonium bromide and
improving the properties of the PLL is using decylamine). Cohuo4 has modified nanocrystal
nucleating agents. The crystallization behavior of cellulose(CNCs) using 2-ethyl hexyl acrylate (2-
polylactic acid (PLA) was studied in the presence EHA). The results showed that the crystallinity
of a crystal nucleating agent. index decreased. The aim of this work is to
The nanocrystal cellulose (CNCs) is enhance the crystallization of PLL by the addition
classified as a nucleating agent, which has of mCNCs [3- (2,3-Epoxypropoxy) -propyl]-
interesting properties such as high strength, low trimethoxysilane). PC107

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 PLL was added 10 ml of CH2Cl2 under
2.Materials and Methods stirring for 1 h. Then it was mixed with modified
2.1 Materials nanocrystal cellulose for 0.5 h. The PLL/
The PLL was supported by Assoc. Prof. modified nanocrystal cellulose was poured into
Dr. Yodthong Baimark (Mn =100,000 g/mol). the petri dish and left at room temperature. After
The nanocrystal cellulose was synthesized from that, PLL/modified nanocrystal cellulose was
rice straw (jasmine rice, Mahasarakham perfumed by an oven vacuum for 24 h. The ratio
province). The chemicals were used extraction of of PLL/modified nanocrystal cellulose in this
nanocrystal cellulose, modified, and composite research were 100/0, 99/1, 97/3 and 95/5 (w/w).
films H2O2 (30-32%, ANaPURE), NaOH (AR 2.3 Characterization
grade, Ajax Finechem, Australia), H2SO4 (98%, The particle size and distribution of the
ANaPURE), CH2Cl2 (99.8%, AR grade, Fisher modified nanocrystal cellulose were evaluated by
Chemical) and [3- (2,3-Epoxypropoxy)-propyl]- a particle size analyzer (Malvern instruments,
trimethoxysilane (Merck, China). Zetasizer Nano S90). The study of the
2.2 Experiment crystallinity of the samples was measured using a
2.2.1 Extraction of nanocrystal cellulose from Bruker D8 Advance X-ray diffractometer at
rice straw room temperature using CuKα radiation at 40 kV
Rice straw was cut into small sizes, and 40 mA. The scanning angle range of 2θ = 5°–
approximately 1-2 cm. It was washed with tap 40° at a scan speed of rate 0.2 sec/degrees was
water and was dried in an oven at 80 °C. Next, used to determine the crystalline structures. The
these straws were eliminated hemicellulose using crystallinity index, CrI was determined using
5% NaOH and were removed lignin by 18.5% Segal’s formula as given below6
H2O2. The cellulose fibers were hydrolyzed using CrI (%) = I002 – Iam / I002
64% H2SO4 at 45 °C for 1 h. according to a
where I002 is the overall intensity of the peak at 2-
previously reported method5 under constant
theta about 16°, Iam is the intensity of the baseline
stirring. After the hydrolysis, the solution was
at 2-theta about 19°.
diluted with cold water to stop the hydrolysis
The thermal properties of samples were
reaction. The nanocrystal cellulose powder was
measured out using differential scanning
dried by a freeze-dry machine and then stored in
calorimeter (Perkin-Elmer, Pyris Diamond).
a desiccator.
Samples were first heated to 200 °C at 10 °C /min
2.2.2 Modified nanocrystals cellulose
of heating rate and held for 2 min, and then
Step I, in the process of preparation
cooled down to -40 °C at the same rate. Second
silanols, it was prepared by adding water to [3-
heating was performed from 20 to 200 °C. All
(2,3-Epoxypropoxy)-propyl]-trimethoxysilane,
operations were studied under a nitrogen
then adding 95% ethanol, stirring for 30 min.
atmosphere. Also, the thermal stability properties
Step II, coupling agents were prepared from
of the samples were carried out using
silanol and nanocrystals cellulose, at 120 °C for 2
thermogravimetric Analyzers (TA-Instrument,
h., then reduced the temperature to 105 °C for 12
TG SDT Q600). The sample was heated from
h. The modified nanocrystal cellulose powder
50 to 800 °C at a heating rate of 20 °C/min under
was stored in a desiccator.
a nitrogen purge.
2.2.3 Fabrication PLL/ modified nanocrystal
The morphology of the samples was
cellulose bionanocomposite films
analyzed using scanning electron microscope;
SEM (JEOL, JSM-64606V). The sample was PC108

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
fractured in liquid nitrogen, and the fracture The XRD analysis of pure film and
surface was coated with gold to enhance bionanocomposite films were shown in Figure 3.
conductivity before scanning. CNCs and mCNCs presents a small and broad
peak at 2𝜃 = 14°, 22°, and 34°8. PLL shows a
3. Results & Discussion small and broad peak at 2θ=16°, 19°, and 22.7°9
3.1 The particle size distributions When mCNCs was composited with PLL, the
crystallization was increased. This may be due to
The particle size distributions of CNCs
the mCNCs being nucleating agent.
were shown in Figure 1. The peak observed in the
mass distribution was located at approximately
50- 600 nm.

Figure 3. XRD analysis of CNCs, mCNCs, PLL

films and bionanocomposite films
3.4 DSC and TGA analysis
Figure 1. Particle size distributions of CNCs. The study of thermal properties of
bionanocomposite films was shown in Figure 4.
3.2 The morphology analysis and Fig.5. The addition of mCNCs showed that
The cross-sectional surface of a the Tg decreased, but Tm and Tcc increased with
bionanocomposite was measured using a SEM addition of mCNCs. When increasing the
shown in Figure 2. It shows that the surface area concentration of mCNCs affected thermal
of the PLL films without mCNCs were smooth stability of bionanocomposite increase. Because
and uniform. while bionanocomposite films were
the interaction between mCNCs and PLL.10
irregularly and found mCNCs in the polymer
matrix. Similar to the research of Xu et al.7

Figure 4. Heating DSC curves of (a) PLL100

and bionanocomposite films (b) PLL99/
Figure 2. SEM cross-section images of (a) mCNCs1, (c) PLL97/mCNCs3 and (d)
PLL100 and bionanocomposite films (b) PLL95/mCNCs5.
PLL99/mCNCs1,
(c) PLL97/mCNCs3 and (d) PLL95/mCNCs5.
3.3 XRD analysis PC109

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 References
1. Ashter, SA.; Types of Biodegradable Polymers.
In: Introduction to Bioplastics Engineering. 2016,
81-151.
2. Luis, OJ.; Wichhart, D.; Kitchens, CL.
J.Nanomater. 2018, 4, 1-12.
3. Pei, A.; Zhou, Q.; Berglund, LA. Compos. Sci.
Technol. 2010, 70 (5), 815-821.
4. Pech-Cohuo, SC.; Canche-Escamilla, G.;
Figure 5. TGA and DTG curves of PLL films Valadez-González, A.; Fernández-Escamilla,
and bionanocomposite films.
VVA.; Uribe-Calderon, J. Int. J. Polym. Sci. 2018,
4. Conclusion 2, 1-14.
Modified nanocrystal cellulose, which 5. Du, L.; Wang, J.; Zhang, Y.; Qi, C.; Wolcott,
was extracted from rice straw by hydrolysis MP.; Yu, Z. Nanomaterials. 2017, 7 (3), 1-12.
method improved crystallization property of PLL 6. Liu, Z.; He, M.; Ma, G.; Yang, G.; Chen, J.
bionanocomposite films. The crystallinity index
was increased from 37 to 87.5% when increasing Palpu Chongi Gisul/J. Korea Tech. Assoc. Pulp
mCNCs (1-5% w/w). The thermal properties of Pap. Ind. 2019, 51(2), 40-48.
bionanocomposite films were slightly increased 7. Xu, C.; Chen, J.; Wu, D.; Chen, Y.; Lv, Q.;
Tm (174-175 oC) and Tcc but decreased Tg. Wang, M. Carbohydr. Polym. 2016, 146, 58-66.
8. Bagheriasl, D.; Carreau, PJ.; Riedl, B.; Dubois,
Acknowledgements
C. Polym. Compos. 2018, 39(8), 2685-2694.
This research was financially supported by
Thailand Research Fund (THF). The Center of 9. Bagheriasl, D.; Safdari, F.; Carreau, PJ.; Dubois,
Excellence for Innovation in Chemistry (PERCH- C.; Riedl, B.; Dubois, C. Polym. Compos. 2019, 39
CIC), Ministry of Higher Education, Science, (8), 2685-2694.
Research and Innovation is gratefully 10. Miao, C.; Hamad, WY. Carbohydr. Polym.
acknowledged. The department of chemistry,
2016, 153, 549-558.
Faculty of Science, Mahasarakham University

PC110

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Enhanced dye adsorption by UiO-67 loading of cellulose acetate composite
film
Jarinphorn Pukkao, Penwisa Pisitsak, Thitirat Inprasit*
1
Department of Material and Textile Technology, Faculty of Science and Technology, Thammasat University,
Pathum Thani 12120, Thailand
*E-mail: [email protected]

Composite films of UiO-67 and cellulose acetate were prepared and tested for dye
adsorption. UiO-67 type metal-organic frameworks (MOFs), consisting of Zr6O4(OH)4 clusters
and 4,4’-biphenyldicarboxylic acid (BPDC) ligands were produced by sonochemical synthesis.
Zirconium tetrachloride (ZrCl4), hydrochloric acid (HCl), and BPDC were dissolved in
dimethylformamide (DMF) at 80°C under ultrasonic agitation. The UiO-67 structure and
particle size were characterized by x-ray diffraction, Fourier-transform infrared (FTIR)
spectroscopy, and scanning electron microscopy (SEM). The synthesized UiO-67 was mixed
with the cellulose acetate solution and the composite films were cast. The chemical structure
and composition of the composite films were investigated using FTIR and SEM-energy-
dispersive X-ray spectroscopy. Morphology and UiO-67 distribution were studied using SEM.
Dye adsorption was explored using ultraviolet (UV)–visible spectrophotometry. Two types of
dye were used: methylene blue and methyl orange. The composite films absorbed higher
amounts of methylene blue than methyl orange. The adsorption capacity also increased as the
UiO-67 concentration increased.
1. Introduction studied, especially as absorbent materials.
The main wastewater MOFs have high porosity and large specific
contamination from textile factories is surface areas. Because their structure can
caused by synthetic dyes. They are resistant be modified by changing the type of metal
to heat, light, and are not biodegradable, cluster and ligands, they are highly
reduce the light passing into the water, and effective and very specific in their
decrease the amount of oxygen present. absorption.4 UiO-67 is a Zr-based MOFs
This directly affects photosynthesis by consisting of Zr6O4(OH)4 clusters and 4,4’-
aquatic plants, algae, other organisms that biphenyl-dicarboxylic acid (BPDC)
5
live in the water, and aquatic animals. It is ligands. Qingfeng et al. reported that it is
also harmful to human health. In addition, more resistant to water, heat, and acids than
some dyes are carcinogenic and otherwise other types of MOFs as well as having
1-2
harmful to human health. Wastewater dye higher absorbency than typical absorbent
treatment has three main methods: materials. It can absorb synthetic and water
chemical treatments such as photocatalysis, soluble dyes such as Congo red (1236.9 mg
biological treatments such as degradation g-1) and Malachite green (357.3 mg g-1).5
by microbes or enzymes, and physical- However, UiO-67 is powder with a very
chemical treatments such as adsorption. small particle size, and is therefore difficult
Although adsorption by absorbent such as to use in certain applications. Compositing
activated carbon is the most popular UiO-67 with a polymer matrix for ease of
method, it has disadvantages, including the use is an interesting potential strategy.
3
high cost of preparation and recycling. Cellulose acetate is a biopolymer
Novel materials known as metal organic derived from the acetylation of cellulose. It
frameworks(MOFs) are increasingly is widely used in industry being cheap, PC111

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
insoluble, biodegradable, and easily at 80°C with different sonication times and
available.6-7 In this research, the mixing dried under vacuum at 90°C for 4 h.
UiO-67 with cellulose acetate by casting 2.4 Fabrication of UiO-67/cellulose
into composite film aimed to be a possible acetate films
route to a more efficient as a dye absorbent UiO-67/cellulose acetate composite
for methylene blue and methyl orange. films were fabricated through film casting,
by dissolving cellulose acetate (10 g) in
2. Materials and Methods acetone (150 ml) and then adding UiO-67
2.1 Materials at concentrations of 1, 2 and 3%wt. The
Zirconium tetrachloride (ZrCl4) and mixtures were stirred for 1 h and sonicated
biphenyl-4,4’-dicarboxylic (BPDC) were for 1 h. The mixture was poured into a Petri
purchased from Acros organics (USA). dish and dried at 60°C for 4 h.
Cellulose acetate (CA), Mn ̴ 30,000 was 2.5 Dye adsorption
purchased from Sigma-Aldrich chemistry. Methylene blue (MB) and methyl
N,N-Dimethylformamide ((CH3)2NOCH) orange (MO) were prepared at five
and absolute anhydrous ethanol were concentrations from 2-10 mg/L by dilution
purchased from Carlo Erba (Italy). Acetone of stock solution (10 mg/L) in DI water.
and hydrochloric acid (HCl) 35.4% were The calibration curves of both dyes were
purchased from Loba chemie. Methylene calculated using UV-visible spectrophoto-
blue was purchased from Daejung (Korea). metry at wavelengths of 560 nm for MB
Methyl orange was purchased from Fisher and 609 nm for MO. UiO-67 concentration
Scientific (UK). DI water was used and adsorbed time were investigated. The
throughout the study. various concentrations of UiO-67/CA
2.2 Characterization. composite films were tested using 0.5 g
The structure and particle size of the sample with square size of 1×1 inch. All
synthesized UiO-67 was characterized by samples were soaked in flasks with 50 ml
X-ray diffraction (XRD, PANanalytical of dye solution at a fixed concentration
X’Pert PRO), at a rate of 5° min-1 over the (10mg/L) in a shaker bath at 25C. Then,
range 3-40° (2θ) at a 0.02° step angle. The the adsorption values were measured at
morphology of the UiO-67 powder and various times up to 24 h. The adsorption
UiO-67/cellulose acetate film was capacity was calculated using Eq.1:
investigated using FE-SEM (JEOL JSM-
7800F). FTIR (Perkin Elmer Model S50x) (Ci − C0 )V
qe =
was used to investigate the chemical m
(1)
structure and composition of the composite
films. Dye adsorption was investigated
where qe is the amount of dye being
using ultraviolet (UV)–visible
absorbed per gram of absorbent material. Ci
spectrophotometry (SHIMADZU UV-
(mg L-1) is the initial concentration of
2600).
solution, C0 (mg L-1) is the final concen-
2.3 Synthesis of MOFs
tration of solution, V (L) is the volume of
UiO-67 was produced following a
solution, and m is the mass (g) of film
previous report8 with slight modification.
adsorbent.
ZrCl4 (0.27 mmol), HCl (0.5ml), and BPDC
(0.38 mmol) were dissolved in DMF (15ml)
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 stretching, O=C=O stretching, and C=O
stretching. Characteristic peaks of the UiO-
67 powder were found at 3397 cm-1, 1593
cm-1, and 1412 cm-1, corresponding to O-H
stretching, C=C stretching, and O-H
bending. In the cast of the 1% and 2% UiO-
67 films, only the group of peaks
corresponding to the cellulose acetate
matrix was investigated. This hardly
appeared in the UiO-67 spectra, perhaps
because the loading was insufficient. The
3% film produced a broad peak at 3485 cm-
1
and pattern corresponding to the peaks of
Figure 1. X-ray diffraction (XRD) patterns pristine UiO-67.
of UiO-67 Figure 3 shows FE-SEM images of
the neat cellulose acetate and UiO-
3. Results & Discussion 67/cellulose acetate composite film. The
3.1 Characterization of UiO-67 cellulose acetate film (Figure 3a) had a
The crystallinity of the synthesized relatively smooth surface, whereas the
UiO-67 powder was characterized and surface of the composite film was rough,
compared with the XRD finding. A due to the distribution of UiO-67 across the
comparison of the XRD patterns of the surface (Figure 3b and c).
synthesized UiO-67 with a computer-
simulated UiO-67 by Mercucy version (e)
3.5.1 Cambridge Crystallographic Data (d)
Centre (CCDC) (Figure1) showed that the
peak characteristics of the UiO-67 ( c)
synthesized matched well. This confirmed (b)
that the UiO-67 was successfully
(a)
synthesized with a purity phase. The
particle characteristics of the synthesized
UiO-67 were analyzed using FE-SEM. The
UiO-67 powder exhibited a polygonal
structure with a particle diameter of
approximately 100 nm. Figure 2. FTIR spectra of (a) cellulose
3.2 Characterization of UiO-67/Cellulose acetate film, (b) 1% UiO-67, (c) 2% UiO-
Acetate Composite Film 67, (d) 3% UiO-67 in CA films, and (e)
Figure 2 shows the FTIR spectra of UiO-67 particle.
cellulose acetate film with UiO-67 3.2 Dye Adsorption of UiO-67/Cellulose
concentrations of 1%, 2%, and 3% by Acetate Composite Film
weight. Characteristic peaks of the Figure 4a compares MB adsorption
cellulose acetate film were found at 3420 by pristine CA film and films with 1, 2, and
cm-1, 2914 cm-1, 2359 cm-1, and 1767 cm-1, 3% UiO-67 loadings. After 24 h, adsorption
corresponding to O-H stretching, C-H reflected the UiO-67 concentration: 0.0113
PC113

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
mg g-1 (0%), 0.0118 mg g-1 (1%), 0.0126
mg g-1 (2%), and 0.0127 mg g-1 (3%).
(a) (b)
(c)

Figure 4. Effect of contact time on the

(c) adsorption capacity of (a) Methylene blue
and (b) Methyl orange.
After the 1st hour, only the CA film
showed an increase in MO adsorption,
reaching equilibrium at 3 h. Adsorption by
Figure 3. FE- SEM image at 3,000X of (a) UiO-67/CA films fell after the 1st hour,
Cellulose acetate film, (b) CA/UiO-67 producing negative qe values. This may be
composite film at 2kV and (c) CA/UiO-67 due to the charges on the surfaces of the
composite film at 10kV. adsorbent and dye solution. When the
composite films were soaked in dye for an
It can be observed that the
extended period, some of the UiO-67 was
adsorption capacity increases rapidly
released. Because UiO-67 contains the
during the 1st hour, reaching adsorption
carboxylic group, this leaching may lower
equilibrium at 3 h. As the UiO-67 loading
the pH of the solution. A highly acidic
increased, dye adsorption also increased.
environment will affect the MO structure,
However, adsorption of MB and adsorption
reducing the negative charge of the –SO3-
of MO seem to be different phenomena.
and producing a weak electrostatic
Figure 4b shows adsorption of MO by
attraction between the adsorbent and MO
pristine CA film, 1% UiO-67/CA, 2% UiO-
(Jiang et al).9 This weak electrostatic
67/CA, and 3% UiO-67/CA composites.
attraction increases dye release from the
absorbent, producing a darker solution with
enhanced absorbance. This was reflected in
the negative qe values (Figure 4b). Overall,
the adsorbents were more effective in
(a) absorbing MB than MO.

4. Conclusions
In this study, we successfully
synthesized UiO-67 with high purity using
a sonochemical method. Composite films
were prepared using cellulose acetate as
matrix and adding the synthesized UiO-67
as filler, with the goal of improving dye
absorption. As the UiO-67 loading was
(b) increased, dye absorption increased. The
3% UiO-67/CA film exhibited the highest
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
MB adsorption capacity (0.0127 mg g-1). International scientific conference,
None of the UiO-67/CA films were able to Gabrovo, November 21 – 22, 2014,
absorb MO as adsorption was strongly 249-252
dependent on pH. Therefore, adsorption of 2. Singhal, A.; Gupta, A.; J. Mol. Liq.
MB (anionic dye) was superior to 2018, 268, 691–699
adsorption of MO (cationic dye). 3. Mella, B.; Puchana-Rosero, M.J.;
Costa, D.E.S.; Gutterres, M.; J. Mol.
Liq. 2017, 242, 137-145
Acknowledgements 4. Zhu, X.; Li, B.; Yang, J.; Li, Y.; Zhao,
This research is gratefully W.; Shi, J.; Gu, J.; ACS Appl. Mater.
supported by Thammasat University under Interfaces 2015, 7, 223-231
TU research (TUGR 2/15/2562), Graduate 5. Yang, Q.; Wang, Y.; Wang, J.; Liu, F.;
with First Placement (009/2559), and Hu, N.; Pei, H.; Yang, W.; Li, Z.; Suo,
Center of Scientific Eauipment for Y.; Wang, J.; Food chem. 2018, 254,
Advance Research of Thammasat 241-248
University and Central Scientific 6. Gavilà, L.; Esposito, D.; Green Chem.,
Instrument Center (CSIC). The authors are 2017, 19,2496
thankful to all staffs of the Department of 7. Gopi, S.; Balakrishnan, P.; Pius, A.;
Materials and Textile Technology, Faculty Thomas, S.; Macromol. Symp. 2018,
of Science and Technology, Thammasat 380, 1800107(1-4)
8. Zhan, X.; Tsai, F.; Xie, L.; Zhang, K.;
University.
Liu, H.; Ma, N.; Shi, D.; Jiang, T.;
Nanomaterials 2018, 8, 655
References 9. Jiang, Y.; Liu, B.; Xu, J.; Pan, K.; Hou,
1. Vineta, S.; Silvana, Z.; Sanja, R.; H.; Hu, J.; Yang, J.; Carbohydr. Polym.
Golomeova, S.; In University Goce 2018, 182, 106-114
Delcev, Processdings of the

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Biocompatible microgel based on poly(lactic acid) and ß-cyclodextrin for
drug release
Arisa Kongprayoon1, Gareth Ross1,2, Sararat Mahasaranon1,2, Sukunya Ross1,2*
1
Program in Industrial Chemistry, Department of Chemistry, Faculty of Science, Naresuan University,
Phitsanulok 65000, Thailand
2
Biopolymer Group, Excellent Center of Biomaterials, Department of Chemistry, Faculty of Science,
Naresuan University, Phitsanulok 65000, Thailand
*E-mail: [email protected]

This work is concerned with the synthesis and characterization of the microgels based
on poly(lactic acid) (PLA) and ß-cyclodextrin (ß-CD), which are both biocompatible and
biodegradable materials. ß-CD is a cyclic derivative of starch and widely used in drug delivery
systems. PLA and ß-CD were modified at their chain-ends by adding a reactive vinyl group
using allyl glycidyl ether (AGE), to create polymerizable PLA (PLAV) and polymerizable ß-
CD (ß-CDV). Microgels of PLAV/ß-CDV were prepared by free radical polymerization with
and without a crosslinker (N’N-methylenebis acryamide). The results showed that the vinyl
groups were successfully modified at the chain ends of PLA and ß-CD, as confirmed by Fourier
transform infrared spectroscopy and nuclear magnetic resonance. Morphology of microgels
was observed by transmission electron microscope. All microgels were spherical in shape with
good size distributions, with the diameter of the crosslinked microgels being 3-4 times larger
than that of the non-crosslinked microgels. The crosslinked microgel showed a continuous
increase in cumulative release of a model hydrophobic drug over 0-12 hours, which then
remained constant at approximately 30%. This crosslinked microgel has potential for use in the
medical field, i.e. incorporation with nanofibers for drug release in tissue engineering scaffolds.

1. Introduction delivery and bio-nanotechnology due to

A drug delivery system (DDS) is a excellent biocompatibility, porosity and
device, formulation or technology in science dimensions, and used in areas spanning from
that enables the transportation of therapeutic human organs and cells in the body.2,3,4
drugs into the body. The systems are usually Microgels and nanogels are generally
designed to provide and maintain a prepared from biocompatible polymers such
therapeutic concentration of drug at the target as poly(lactic acid) (PLA), poly(ethylene
biological site. Recently, nanoparticles glycol) (PEG), poly(N-isopropylacrylamide)
including hydrogels, microgels, nanogels, (PNIPAM), ß-cyclo-dextrin (ß-CD), etc.
nano-capsules, nanospheres, micelles, These polymers can be synthesized into the
liposomes, dendrimers and others are DDSs, forms of micro- or nano-gels through
which have shown great potential for crosslinking methods, hydrogen bonding
encapsulation of drugs. They improve the interactions, hydrophobic interactions and
therapeutic index and reduce the adverse side temperature or pH responsive behaviors.5
effects.1 The designs of hydrogels, microgels Recently, copolymers in the form of
and nanogels are an attractive area of study in micelle microstructures have been of interest
the biomedical field. They have been used for to use for improving drug release rates. For
tissue engineering, biomedical implant, drug example, a new triblock copolymer of methyl
poly(ethylene glycol) ether-b-poly(ß-amino PC116

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
esters)-b-poly (lactic acid) (MPEG-b-PBAE- “polymerizable PLA (PLAV)” and “poly-
b-PLA) self-assembled micelles has been merizable ß-CD (ß-CDV)”. These microgels
synthesized and targeted for use in anticancer were used as a drug carrier. Oil Red O (ORO)
drug delivery.6 The biodegradable amphi- was chosen as a model hydrophobic drug,
philic copolymers of conjugating PDLA onto and the release profiles were measured. ORO
ethylenediamino or diethylenetriamino brid- is a hydrophobic dye, similar to a lipid, which
ged bis(ß-cyclodextrin)s were synthesized
is used for quantitative analysis, with a
into the form of nanoparticles. The release
maximum absorbance at 518 nm.11
profiles of these nanoparticles entrapped with
bovine serum albumin (model protein)
showed a burst effect following by 2. Materials and Methods
continuous release.7 The supramolecular 2.1 Materials
hydrogels based on PLA and CS diblock Poly(lactic acid) (PLA, Mw = 2,250 g/mol), ß-
copolymers with ß-CD were successfully cyclodextrin (ß-CD, Mw = 1,134.98 g/mol)
synthesized. The hydrogen bonds between were used. Allyl glycidyl ether (AGE), zinc
the carbonyl groups of PLA and the hydroxyl (Zn) catalyst, N’N-methylenebisacryamide
groups of CS and ß-CD were observed. The (N’N-mBAAm), N-methyl-2-pyrrolidone
in vitro release rate of heparin sodium (model (NMP), tetramethyl-ethylene diamine
hydrophobic drug) was lower than that found (TEMED), dimethyl sulfoxide (DMSO) and
with the bovine serum (model hydrophilic Oil Red O (ORO) were purchased from
drug).8
Sigma-Aldrich, Singapore. Potassium
Poly(lactic acid) (PLA) is a biodegra-
hydroxide (KOH) and ammonium persulfate
dable and biocompatible polymer made from
(APS) were purchased from Univar
renewable resources that is widely used in the
chemical, New Zealand.
field of biomedical applications, especially in
2.2 Preparation of polymerizable PLA
tissue engineering and drug delivery due to
(PLAV) and polymerizable ß-CD (ß-CDV)
its nontoxicity to cells. In addition, PLA has
2.2.1 Synthesis of PLAV
been approved by the US Food and Drug
PLA was modified at its chain ends
Administration (FDA) and European regu-
by adding a vinyl group using AGE. First,
latory authorities that it is safe to use for food
7.50 g of PLA was dissolved in 150 mL of
and biomedical materials.9 ß-cyclodextrin (ß-
DMSO and then mixed with 390 µL of AGE
CD) is a cyclic oligo-saccharide consisting of
and Zn (0.0375 g) in a close system. The
seven D-gluco-pyranose (glucose molecules)
reaction mixture was heated at 70 oC under
linked by α-1, 4-glucoside bonds.10 It is one
the N2 atmosphere and stirred for 12 h.
type of cyclodextrin (CDs), a series of poly-
Finally, the PLAV product was precipitated
hydroxy compounds which have been used as
using cold de-ionized water (DI water) and
drug carriers due to their low toxicity,
cold methanol, and dried at 60 oC for 48 h.
biocompatibility and biodegradability .
2.2.2 Synthesis of ß-CDV
The aim of this work is to prepare
1 g of ß-CD was dissolved in 20 mL
microgels from PLA and ß-CD that can
DMSO and then mixed with 726 µL of AGE
control the release of a model hydrophobic
and KOH (0.05 g in 0.95 mL of DI water) in
drug. The microgels were prepared from the
a close system. The reaction mixture was
modified polymer chains of PLA and ß-CD
heated at 70 oC under the N2 atmosphere and
by adding vinyl groups from allyl glycidyl
stirred for 12 h. Finally, the ß-CDV product
ether (AGE) at their chain ends, as called PC117

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
was precipitated by cold acetone, and dried at ORO drug from the microgels. The microgels
60 oC for 48 h. were loaded with ORO by soaking 0.01 g of
2.3 Synthesis of PLAV/ß-CDV microgels the microgels in 0.5 mL of a 0.01wt% ORO
with and without crosslinker solution at room temperature for 2 days. Then
0.04 g of PLAV was dissolved in 2 the ORO-loaded microgels were dialyzed in
mL of NMP. 0.04 g of ß-CDV was dissolved 0.5 mL of phosphate-buffered saline (PBS,
in 2 mL of DMSO at 70 oC for 2 h. These two pH 7.4). A microplate reader, UV-Vis Biotek
solutions were then mixed together for 30 Synergy H1 Hybrid Reader, was used to
min before adding N’N-mBAAm (cross- measure the optical density (OD) at 518 nm.
linker) and TEMED and APS (as a redox
pair), and then stirred for 30 mins. The 3. Results & Discussion
microgel product was precipitated by cold DI 3.1 Functional groups and chemical
water and dried at 60 oC for 48 h. The final structures of PLAV and ß-CDV
product was kept in a desiccator before PLAV and ß-CDV, the products of
characterization and use. the func-tionalized PLA and ß-CD by AGE
2.4 Characterization (by adding the vinyl functional group at their
2.4.1 Functional groups of PLAV and ß- chain ends), were characterized for their
CDV functional groups and chemical structures, as
A Fourier Transform Infrared (FTIR) shown in Figure 1 (for PLAV) and Figure 2
Spectrometer from Spectrum GX, Perkin (for ß-CDV).
Elmer was used to characterize the functional
groups of PLA, PLAV, ß-CD and ß-CDV
samples. The samples were dried before
testing by Attenuated Total Reflection (ATR)
mode of FTIR spectroscopy.
2.4.2 Chemical structures of PLAV and ß-
CDV
Nuclear Magnetic Resonance
13 1
(NMR), both C NMR and H NMR spectra
were taken on a Bruker Advance 400 NMR
spectrometer. PLAV was dissolved in
deuterated chloro-form (CDCl3) while ß-
CDV was dissolved in deuterated dimethyl
sulfoxide (DMSO-d6).
2.4.3 Morphology of microgels
The morphology of microgels was
observed by Transmission Electron
Microscope (TEM) from TECNAI12,
PHILIPS. The size and shape of the
microgels were also determined.
2.4.4 Drug release profile
In vitro method was used to
determine the release behaviors of the model
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Figure 1. (a) FTIR, (b) 1H NMR and (c) 13C
NMR spectra of PLAV. Figure 2. (a) FTIR, (b) 1H NMR and (c) 13C
From the FTIR spectra of PLA and NMR spectra of ß-CDV.
PLAV (Figure 1a), the characteristic peaks of From the 1H NMR spectrum of PLAV
vinyl C-H bending (at 952 cm-1and 928 cm-1) (Figure 1b), the proton peaks of the vinyl
and C=C stretching (at 1665 cm-1) in PLAV group are shown at 5.24 (H7) and 5.45 (H8)
are observed. These two peaks are not ppm, and the proton peak of the hydroxyl
observed in PLA. From the FTIR spectra of group from the opening of the epoxide ring in
ß-CD and ß-CDV (Figure 2a), the peak of AGE is observed at 4.06 (H9) ppm. In
C=C stretching of the vinyl group in ß-CDV addition, all proton peaks of PLAV are
is found overlapped with that of OH-bending observed. The 13C NMR spectrum of PLAV
vibration (1711-1640 cm-1) in ß-CD.12 In (Figure 1c) shows carbon peaks at 16.14
addition, the vinyl C-H bending peaks in ß- (C1), 68.64 (C2), 169.11 (C3), 66.71 (C4),
CDV appear at the same frequency bands of 66.54 (C5), and at approximately 70.52 (C6,
C-O stretching (1155-945 cm-1). C7) ppm. These results confirm the
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
successful modification of the chain ends of to entrap the model hydrophobic drug and
PLA with the vinyl group from AGE. From maintain a certain percentage of a cumulative
the 1H NMR spectrum of ß-CDV (Figure 2b), release over a 12-h period.
the proton peaks of the opened epoxide ring
in AGE were observed at 3.29/3.64 (a), 3.74
(b) and 3.94 (g) ppm, and the proton peaks of
the vinyl group were shown at 5.20 (e) and
5.86 (f) ppm. From 13C NMR analysis
(Figure 2c), the methine carbon (C-H) peak
of the opened epoxide ring in AGE is seen at
68.88 ppm (b). These results confirm the
successful modification of the vinyl group
onto the ß-CD chains.
3.2 Morphology and drug release profile of
microgels
Microgels were successfully
synthesized from PLAV/ß-CDV in the
presence of N’N-mBAAm (crosslinker) by
free radical poly-merization. The
morphology of microgels observed by TEM
is shown in Figure 3. The microgels without
crosslinking (Figure 3a) had a small particle
size in fairly spherical shape and a narrow
size distribution in a diameter range of 100-
120 nm whereas the crosslinked microgels
showed better spherical shape and Figure 3. TEM images of (a) non-crosslinked
homogeneity than the non-crosslinked microgels and (b) crosslinked microgels.
microgels. However, the crosslinked
microgels are around four times larger in size
than the non-crosslinked micro-gels (Figure
3b).
An In vitro drug release of
crosslinked PLAV/ß-CDV microgels was
studied, and the result is shown in Figure 4.
The cumulative release of ORO as a model
hydrophobic drug increased continuously to Figure 4. In vitro drug release profile.
30% during the first 12 h, and then gradually
increased to 33% at the 23rd hour. However, 4. Conclusion
when rhodamine B (a dye used as a model The crosslinked microgels of PLAV/ß-CDV
hydrophilic drug) was loaded instead of were successfully prepared using the poly-
ORO, it was observed that the dye was not merizable macromers of PLA and ß-CD that
entrapped in the microgels (data not show). were modified at their chain-ends by adding
Therefore, the crosslinked microgels are able the reactive vinyl group from AGE. The
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
crosslinked microgels are more spherical in 8. Yong, H. Int. J. Biol. Macromol. 2018,
shape and uniform in particle size than the 108, 18-23.
non-crosslinked microgels. The cumulative 9. Ramzi, A. J. Chem. Pharm. Res. 2015,
release of the model hydrophobic drug was 712, 51-63.
33% at the 23rd hour. 10. Yong, C. Chem. Soc. Rev. 2010, 39, 495-
505.
Acknowledgements 11. Nils, A.K.; Benedikt Z. Adipocyte 2016,
This work was supported by Science Lab 5 (4), 351-358.
Centre, Faculty of Science, Naresuan 11. Chao, Y. Carbohydr. Polym. 2015, 118,
University for FTIR, NMR, TEM and 36-40.
microplate reader measurements. Special
thanks to Biopolymer Group, Excellent
Center of Biomaterials, Department of
Chemistry, Faculty of Science, Naresuan
University

References
1. Chong, L. Acta Pharma. Sin. B. 2019, 9
(6), 1145-1162.
2. Jung, K. Prog. Polym. Sci. 2008, 33, 448-
477.
3. Yanjiao, J. Biomater. 2014, 35 (18), 4969-
4985.
4. Tianjiao, J. Nano Today, 2019, 28,
100765.
5. Selin, S. Responsive biopolymer-based
microgels/ nanogels for drug delivery
applications. Stimuli Responsive Poly-meric
Nanocarriers for Drug Delivery Applications.
Biomater., 2018, 453-500.
6. Chufen, Y. Mater. Sci. Eng. C, 2018, 84,
254-262.
7. Gao, H. J. Control. Release 2006, 112,
301–11.

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 Microwave-assisted transesterification of cassava starch with polylactic
acid (PLA)
Hussain Haikal, Wanwipa Siriwatwechakul, Siwarutt Boonyarattanakalin*
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology,
Thammasat University, Pathum Thani 12120, Thailand
*E-mail: [email protected]

This research focuses on the development of a green process for the chemical
modification of native starch to overcome its poor thermal and mechanical properties. The
modification of native starch with polylactic acid (PLA) would result in a biodegradable
material with improved thermoplastic properties. In this study, cassava starch was modified by
microwave-assisted transesterification with PLA in the presence of surfactants sodium laurate
and sodium-1-decanesulfonate. The native cassava starch was pregelatinized at room
temperature with 0.5 M sodium hydroxide (NaOH). The reaction temperature was varied from
90 to 160°C. The structure and physical properties of the modified starch were characterized
by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR),
differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Proton nuclear
magnetic resonance (1HNMR), and scanning electron microscopy (SEM). The modified starch
has a lower glass transition temperature (Tg) value of 92.9 °C compared to that of native starch
105.4 °C. This suggests that the incorporation of PLA provides the chains with end groups that
can move easier hence lowering the Tg. The ATR-FTIR spectrum of modified starch shows the
characteristic absorption of carbonyl stretching of PLA at 1757 cm-1, which indicates the
successful transesterification.

1. Introduction applications of starch are limited due to

Starch is a versatile natural polymer shortcomings in the properties of native
(polysaccharide) consisting of repeating units starch such as having low shear resistance,
of monomers or glucose units linked by α-D- low thermal resistance, high brittleness, and
1,4- glycosidic bond. Starch molecules are high hydrophilicity. These shortcomings
heterogeneous and consist of two main have been overcome by employing methods
microstructures which are amylose and such as blending, physical, chemical, genetic
amylopectin.1 and enzymatic modifications
Interest in starch-based materials has Polylactic acid (PLA) is a biodegr-
increased in the past decade, mostly as a adable polymer produced from renewable
result of depletion of petrochemical resources resources such as starch, sugar, and corn.
and environmental concerns from petro- PLA is biocompatible and highly
chemically derived materials. However, there processable. These properties have made
are some challenges to utilizing starch as an PLA a popular alternative to petroleum-based
alternative to fossil-based products polymers.2 However, there are some
Starch is extensively used in food and disadvantages in the properties of PLA such
industrial applications, as a thickener, stab- as high brittleness, poor hydrophilicity, low
ilizer, binder, gelling agent, pharmaceuticals, heat deflection temperature, and poor impact
and textiles. In addition, one major use of resistance. These unfavorable properties limit
both native starch and modified starch is the industrial applications of PLA. To
blending with other synthetic polymers. The overcome its shortcomings and to reduce the PC122

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
cost of using PLA, several studies have 2.2 Transesterification reaction using PLA
attempted to blend PLA with starch.3,4 The cassava starch was dried in an
Due to the hydrophilic nature of oven at 70 °C for 12 hours prior to the
starch, starch forms weak interphase experiments. All reactions were performed in
interactions with hydrophobic polymers such a closed reaction vessel designed specifically
as PLA, leading to poor mechanical for a microwave reactor. NaOH aqueous
properties of the resulting products.5 solution (0.5 M, 15 mL) was used to
Consequently, an effective catalyst is gelatinize 2 g of dried cassava starch, with
required to facilitate the reaction between the continuous stirring using a magnetic stirrer at
starch and PLA. The catalysts chosen for this 25 °C for 20 min. The weight ratio of PLA
study are sodium laurate and sodium-1- and starch used for the experiments was 1:1.
decanesulfonate which are considered phase Catalysts used in the experiments were
transfer catalysts (PTC). The use of PTC sodium laurate, sodium-1-decanesulfonate.
coupled with microwave irradiation has been The amount of catalyst used in the reactions
proven to be an efficient technique in organic were based on 1:1 anhydroglucose unit
synthesis.6 During the reaction, heat is (AGU) to catalyst molar ratio. The reaction
necessary in order to disperse starch with mixture was stirred using a magnetic stirrer
chemical reagents and create homogeneous to mix in the heterogeneous solid catalysts.
reaction conditions. Apart from the The transesterification reaction was carried
conventional heating method, an alternative out in a Milestone flexiWAVE microwave
heating method of microwave irradiation has synthesis platform. Upon the reaction
gained attention in organic synthesis. The use completion, the products were transferred
of microwave irradiation in organic synthesis from the reaction vessel to a small beaker.
and polymer chemistry provides advantages The product was precipitated with
of short reaction time and uniform heating.7 isopropanol (40 ml) using a magnetic stirrer
This study focuses on the application for 20 min. The product was filtered using
of microwave irradiation for the modification vacuum filtration. To eliminate the unreacted
of starch with PLA by transesterification PLA homopolymer, the product was washed
reaction using phase transfer catalysts. The with tetrahydrofuran (THF) (20 ml) using the
effect of the type of catalyst and reaction magnetic stirrer.8 The washing process was
temperature on the successful trans- repeated for a total of 2 rounds. The starch
esterification were investigated. product was oven-dried at 70 °C for 12 hours,
and the dried products were kept in
2. Materials and Methods desiccators for further analysis. The
2.1 Materials experimental conditions were carried out in
Cassava starch was obtained from SMS duplicates.
Corporation, Thailand. Polylactic acid (PLA) 2.3 Attenuated total reflectance-Fourier
acid (LX175) was obtained from Corbion. transform infrared spectroscopy
Sodium laurate and sodium-1-decanesulf- Infrared spectra of all samples were
onate were purchased from Tokyo chemical obtained using attenuated total reflectance-
industry (TCI) chemicals. All the chemicals Fourier transform infrared spectroscopy
used were reagent grade and were used (ATR-FTIR, Nicolet iS5) with an iD7 ATR
without further purification. accessory with a diamond crystal.
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.4 Thermogravimetric analysis (TGA) ssava starch by PLA. The proposed reaction
Thermogravimetric analysis (TGA) mechanism for the transesterification
was conducted to investigate the thermal reaction is shown in Figure 1. The native
degradation behavior of the samples (Mettler cassava starch was first gelatinized in NaOH
Toledo TGA/DSC1). The analyses were at room temperature before modification to
carried out under a nitrogen atmosphere with destroy of the hydrogen bonds in the semi-
a heating rate of 10 °C/min within the range crystalline structure of starch. The reactions
of 25 °C to 500 °C. were carried out at different temperatures to
2.5 Differential scanning calorimetry determine the optimal temperature. The
(DSC) variation of reaction parameters is shown in
Differential scanning calorimetry Table 1.
(DSC) analysis was conducted on a Mettler Table 1. Variation of reaction parameters
Toledo DSC1. The analysis of starch samples Ester
was carried out in two heating cycles in the Temp peak Product
Sample Catalyst
(°C) (1757 Yield(wt.%)
range from 25 °C to 250 °C with a heating cm-1)
and cooling rate of 10 °C/min. The process P1 SL 90 Absent 80.41
was carried out under nitrogen atmosphere.
Interpretation of the results was done based P2 SL 120 Present 74.07
on the second heating curve in order to reduce P3 SL 140 Present 40.18
the interference from the heating history.
P4 SL 160 Present 31.67
2.6 1H-Nuclear magnetic resonance (1H-
NMR) P5 SD 90 Absent 84.10
Nuclear magnetic resonance (NMR) P6 SD 120 Present 75.83
was used to identify the structure of the
modified starch. 1H-NMR spectra were P7 SD 140 Present 45.25
obtained using a Bruker Fourier 600 (600 P8 SD 160 Present 26.50
MHz), using Dimethyl sulfoxide-d6 *SL: sodium laurate
(DMSO-d6) as a solvent to dissolve the *SD: sodium decane-1-sulfonate
modified starch samples.
2.7 Scanning electron microscopy (SEM) The amounts of the modified starch
Scanning electron micrographs of obtained from the reaction decreased with the
samples were obtained using a JEOL model increase in reaction temperature. From the
JSM5410LV scanning electron microscope experiments carried out, it was noticeable
(SEM) which was operated with a that at the low temperature of 90 °C, a big
magnification of 2000x at 10-20 kV. portion of PLA remained unreacted and were
Analyzed samples were coated with gold and separate from the starch molecules. Higher
palladium. temperatures result in better homogenization
of the PLA with starch. However, the
3. Results & Discussion reaction temperatures above 120 °C resulted
3.1 Transesterification of PLA onto starch in the degradation of starch molecules (burnt
The physical and chemical structure product) and lead to a low yield and thus
of modified starch were studied to verify the hinder the reaction.
microwave-assisted transesterification of ca-
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 1. Microwave-assisted modification of cassava starch with PLA in the presence of
catalysts.
The presence of the peak at 2968 cm-1 further information about the properties of the
which represents C-H aliphatic stretching also product obtained from the reaction.
shows that the reaction was successful. The
band at 1640 cm-1 represents the characteristic
peak of tightly bound water molecules in
starch. The lower levels of intensity of
different samples is an indicator of the starch
gelatinization efficiency. The broad peak
observed at 3289 cm-1(A, B) and 3278 cm-1(C)
in Figure 2 represents the O-H stretching. The
spectra of modified starch show a decrease in
intensity of O-H peak as the hydroxyl groups
are converted to ester linkages due to the
transesterification reaction.
All the conditions presented in Table 1
Figure 2. FTIR spectra of (A) modified starch
except sample P1 and P5 showed the presence
sample P2, (B) modified starch sample P6 and
of the ester bond at 1757 cm-1. However, the
(C) native starch.
intensity of this peak was very low for products
3.4 Differential scanning calorimetry (DSC)
obtained from reactions carried out with
DSC thermograms starch samples are
sodium laurate as a catalyst. The results
shown in Figure 4. The native starch shows a
suggest that sodium decane-1-sulfonate is a
Tg of 105.4 °C, while the starch transesterified
more suitable catalyst for the reaction. The
by PLA (Sample P6) has a lower Tg of 92.9 °C
products obtained using sodium-1-
than the unmodified counterpart. The lower Tg
decanesulfonte showed higher peak intensities
indicates that the incorporation of PLA groups
for the significant peaks. The highest peak
into the starch destroyed the semi-crystalline
intensities were observed for sample P6
granular structure of starch. Hence, providing
(Figure 2B) which was the product obtained
the chains of starch with more mobility,
from the reaction carried out at a temperature
leading to a lower Tg. Additionally, the DSC
of 120 °C. This indicates that the
thermogram of modified starch (sample P6)
transesterification reaction is most successful
also shows a melting endotherm (Tm) at 188.90
at this condition. Further characterizations
°C. This endotherm was not present in the
were done for sample P6 to confirm the
thermogram of native starch, which suggests
successful transesterification and to obtain
that the crystalline phase from PLA is
present in the modified starch. PC125

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 3. TGA (a) and DTG (b) thermograms of native starch and sample P6.

degradation temperature (Td) of native

cassava starch was found at 310.2 °C. For
the modified starch sample, a lower Td of
276.3 °C (Figure 3(b)) was observed. It is
possible that part of the modified starch
molecules may be partially decomposed by
the heat. Consequently, the modified starch
decomposed at the lower degradation
temperature.

Figure 4. The second heating DSC curves

of native starch and sample P6.
3.3 1H-Nuclear magnetic resonance (1H-
NMR)
The 1H-NMR spectra of native
starch and the PLA transesterified starches
were analyzed to confirm the chemical
changes of starch molecules. The NMR
spectra of starch modified with PLA using
sodium-1-decanesulfonate as catalyst
(Sample P6) showed characteristic peaks Figure 5. 1-HNMR Spectra of modified
from the methyl group of PLA moiety starch sample P6.
between 1.055-1.5 ppm (shown in Figure 3.6 Scanning electron microscopy (SEM)
5).10,11 The SEM micrographs of the native
3.5 TGA and modified starch are shown in Figure 6.
TGA thermograms of Native cassava starch granules have round
transesterified starch is compared with to oval shapes with a diameter ranging from
native starch in Figure 3 (b). The thermal 8-13 µm. The granular structure of the PC126

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
starch was destroyed after the modification. University (TUCSEAR) for supporting
The granules transesterified with the PLA facilities and equipment.
turned into particles with cluster-like References
structural features (Figures 6 (b)). In 1. BeMiller, J.; Whistler, R. Starch:
addition, the surface of the starch changed Chemistry and Technology;
significantly from a smooth surface to a BeMiller, J., Whistler, R., Eds.;
Academic Press, 2009; Vol. 53.
2. Ren, J. Biodegradable Poly(Lactic
Acid): Synthesis, Modification,
Processing and Applications; Ren,
J., Ed.; 2010.
3. Koh, J. J.; Zhang, X.; He, C. Int. J.
Biol. Macromol. 2018, 109, 99–113.
rugged one. 4. Huneault, M. A.; Li, H. Polymer
Figure 6. SEM micrographs of (a) native 2007, 48 (1), 270–280.
cassava starch; (b) sample P6. 5. Mittal, V.; Akhtar, T.; Matsko, N.
Macromol. Mater. Eng. 2015, 300
4. Conclusion (4), 423–435.
In this study, a method to 6. Deshayes, S.; Liagre, M.; Loupy, A.;
transesterify cassava starch in an aqueous Luche, J.-L.; Petit, A. Tetrahedron
solution was achieved using phase transfer 1999, 55 (36), 10851–10870.
catalysts, microwave heating, PLA. The 7. Tierney, J. P.; Lidstrom, P.
results show that the successful microwave- Microwave Assisted Organic
assisted trans-esterification of PLA onto Synthesis. 2005, 57 (589), 296.
cassava starch can be carried out at 120 °C 8. Chen, L.; Qiu, X.; Deng, M.; Hong,
using sodium-1-decanesulfonate as a Z.; Luo, R.; Chen, X.; Jing, X.
catalyst at a reaction time of 60 minutes. Polymer 2005, 46 (15), 5723–5729.
The method is a means to modify native 9. Handbook of Composites from
starch into functional materials as potential Renewable Materials, Physico-
fillers for various bio-based polymers in the Chemical and Mechanical
bioplastic industry. Characterization, 3rd ed.; Thakur,
V. K., Thakur, M. K., Kessler, M. R.,
Acknowledgements Eds.; Wiley, 2017.
This work was supported by the 10. Li, H.; Chang, J.; Qin, Y.; Wu, Y.;
National Science and Technology Yuan, M.; Zhang, Y. P. Int. J. Mol.
Development Agency (NSTDA). We thank Sci. 2014, 15 (2), 2608–2621.
the Center of Scientific Equipment for 11. Gong, Q.; Wang, L. Q.; Tu, K.
Advanced Research, Thammasat Carbohydr. Polym. 2006, 64 (4),
501–509.

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 Microwave extraction of oligosaccharides
from Jerusalem artichoke tuber
Yupadee Phethai, Rachnarin Nitisoravut, Siwarutt Boonyarattanakalin*
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology,
Thammasat University, Pathum Thani 12120, Thailand
*E-mail: [email protected]

The main carbohydrate component of Jerusalem artichoke tuber is inulin,

a polysaccharide of D-fructose linked by β-(2→1) glycosidic bond, with a glucose terminal.
The inulin in the form of oligosaccharides has been recognized as an adjuvant and exhibits
prebiotic properties with an advantage of minimal risk for long term deposits.
In this study, oligosaccharides were extracted from a fine powder of Jerusalem artichoke
by a combination of microwave radiation heating and acid hydrolysis (HCl).
The use of microwave radiation provides more heating efficiency and shortens reaction time.
The hydrolysis product was purified by precipitation with ethanol.
The effects of reaction temperature (70, 90 and 110 °C), reaction time (15 and 30 min),
and HCl concentration (0.2, 1, 1.8 and 2M) on the degree of polymerization (DP) of the
extracted saccharides were determined. The extracted saccharides were characterized by using
size exclusion chromatography (SEC) and NMR. The analysis showed
the fructooligosaccharides (FOS) with a DP of 3 to 5 when using 0.2 M HCl at 70 °C
or without using HCl. The maximum FOS yield was 12.87% when performed the extraction
process without using HCl as a catalyst.

1. Introduction (FOSs) are short-chain inulin with degree of

Jerusalem artichoke (Helianthus polymerization (DP) of 3 to 8.
tuberosus L.) is a member of the sunflower Inulin and FOSs have been
family which originated in North America.1 recognized as prebiotic nutrients and
The advantageous characteristics of functional food.3 The β-configuration
Jerusalem artichoke over other crops are high of anomeric C2 carbon renders these
growth rate, resistance to frost and drought, molecules non-digestible in the upper part
resistance to plant diseases and pests with of the human intestinal tract. Consequently,
requirements of minimal to zero fertilizer. they can be fermented by the beneficial
Jerusalem artichoke has been used as food for bacteria in the colon. The fermentation
both humans and animals. influences the activity and/or growth
Alternatively, Jerusalem artichoke is used for of microflora.
the production of functional food ingredients The fermentation process confers
such as inulin. beneficial effects for host well-being such as
Inulin is a polysaccharide consisted improvements of minerals absorption in the
of fructose units linked by β-(2→1)-D- intestinal, reduction of cholesterol levels
fructose and terminated by a glucose unit and improvements of immune system
linked by α-(1→2) bond.2 These molecules efficiency.4 Moreover, fructans also have
are a mixture of oligomer and polymer chains important properties as a substitute of fat and
with a variable number of fructose units. sugar in low-calorie food. FOSs are used as a
Fructan molecules with DP more than 10 are sugar substitute and dietary fiber due to their
known as inulin. Fructo-oligosaccharides sweetness and high solubility. PC128

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The use of advanced extraction (JATP) was mixed with 20 mL of HCl
technique such as microwave-assisted or RO water. The extraction of
extraction (MAE), to obtain extracts that are oligosaccharides from JATP was performed
rich in bioactive, receives more attention in in closed vessels with the use of microwave
recent years. MAE technique provides radiation (Milestone, flexiWAVE, Italy). The
homogeneous heating and high yields with a extraction was performed under several
significant decrease in extraction time when conditions with the following parameters –
compared with conventional extraction. maximal power of 1,800 watts, reaction
In this study, combinations of microwave temperature of 70 – 110 °C (20 °C
radiation heating and acid hydrolysis were increments), reaction time of 15 and 30 min,
used to facilitate hydrolysis and extraction of and HCl concentration (0.2, 1, 1.8 and 2M).
oligosaccharides from Jerusalem artichoke. The crude extract was stirred for 1 h, filtered
HCl is one of the acceptable acid catalysts and neutralized with 10.0M NaOH (in case of
which can be applied in the food industry as using HCl as a catalyst).
a food additive. 2.3 Oligosaccharides Precipitation
This study aimed to evaluate the The aqueous crude extract was
possibility of oligosaccharides extraction precipitated with ethanol (1:5, v/v).
from artichoke by a combination of The sample was incubated in a shaking
microwave radiation heating and HCl as incubator at 4 °C for 18 h with constant
a catalyst. shaking at 150 rpm and followed by
centrifugation at 1459 g for 20 min.
2. Materials and Methods The aqueous crude extract was concentrated
2.1 Materials in a rotary evaporator. The non-precipitated
Fresh Jerusalem artichoke tuber of aqueous crude extract was precipitated for
(JAT) was purchased from the Siam Makro the second time with ethanol (1:10; v/v).
Public Co., Ltd., Khlong Luang branch, The precipitated solution was incubated in
Pathum Thani, Thailand. The husk of fresh a shaking incubator at 4 °C for 18 h with
JAT was removed and the edible part was constant shaking at 150 rpm and centrifuged
sliced into small pieces. The small pieces of at 1459 g for 20 min. The non-precipitated of
JAT were cleaned with tap water and dried at crude extract was concentrated in a rotary
60 °C for 3 days. The dried flakes of JAT evaporator and the precipitated saccharides
were ground with a grinder to a particle size were dried at 60 °C for 3 days and collected
less than 0.25 mm before extraction. for further analysis. The supernatant was
Hydrochloric acid, ethanol, bovine collected and stored in a refrigerator at 4 °C.
serum albumin, and Coomassie Brilliant Blue 2.4 Molecular Weight Determination
G-250 were purchased from Merck The molecular weight of the
(Germany). Sodium hydroxide, D(-)fructose, precipitated saccharide samples were
D(-)glucose, mannose, and arabinose were analyzed by high-performance size exclusion
purchased from Ajax Finechem Pty Ltd. chromatography (HPSEC) using a
(Australia). Orthophosphoric acid was differential refractometer as a detector
purchased from CARLO ERBA (France). (refractive index detector). Deionized water
2.2 Oligosaccharides Extraction was used as a mobile phase at a flow rate of
2 g of Jerusalem artichoke powder 0.9 mL/min. The precipitated saccharide
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
samples were re-dissolved in deionized water test tube was incubated at room temperature
and passed through a 0.2 μm filtered before for 5 min. The absorbance was measured at
injection through a series of three‐tandem PL 595 nm using UV - Vis spectrophotometer
aquagel‐OH 5‐μm columns (7.5×300 mm). (Thermo Fisher Scientific, G10S UV - VIS,
The column temperature was set to 36 °C and USA). The amount of total protein was
the injection volume was 100 µL. calculated based on a standard curve of
2.5 Determination of monosaccharide bovine serum albumin protein.
composition
The monosaccharides compositions 3. Results & Discussion
of the precipitated saccharide samples were 3.1 Molecular Weight Determination
analyzed by high-performance liquid The approximate DP of the
chromatography (HPLC) equipped with precipitated sample is shown in Table 1.
differential refractometer as a detector. The HCl concentrations and temperatures
The deionized water was used as a mobile strongly affected the DP of the precipitated
phase at a flow rate of 0.4 mL/min. sample when the extractions were performed
The precipitated saccharides were re- at higher HCl concentration.
dissolved in deionized water and Table 2. Approximate DP of precipitated
passed through a 0.2 μm filtered before sample.
injection through the carbohydrate column
(Transgenomic CARBOSEP CHO682,
Extracted Temperature Time Approximate
LEAD column) equipped with a guard Solvent (°C) (min) DP
column (Transgenomic CARBOSEP
CHO682, Guar Kit). The column temperature
was set to 80 °C and the 70 4
injection volume was 20 µL. 90 15 4
2.6 13C nuclear magnetic resonance
110 4
spectroscopy RO
The nuclear magnetic resonance 70 4
(NMR) spectra were recorded at 298 K by
90 30 4
Bruker Ascend TM 600 spectrometer that
was operated at 600 MHz. The precipitated 110 4
saccharide samples were re-dissolved in 70 2
99.95% D2O. The chemical shifts (δ) are
expressed in parts per million. The chemical 0.2 M 90 15 2
shifts of FOSs from JAT were compared with 110 2
literature data.
70 2
2.7 Protein Determination
The Bradford method was adopted to 1M 90 15 2
assay the protein content.5 The precipitated
110 2
saccharide samples were re-dissolved in RO
water. 1 mL of aqueous precipitated 70 30
saccharides was mixed with 5 mL 1.8 M 15
90 22
of Bradford reagent in a 16 mL test tube. The
PC130

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 110 18 3.2 Determination of monosaccharide
70 32 composition
In the extraction process of JATP,
2M 90 15 31 the ethanol precipitation of the aqueous
110 21 extract was required to separate high
molecular weight carbohydrates (precipitate
In the presence of 0.2 M and 1 M HCl, fraction) and low molecular weight
the temperatures do not affect the DP carbohydrates (supernatant fraction).
of the precipitated sample. The low The percent yields of the total saccharides of
molecular weight carbohydrates were the extracted samples performed both in the
obtained. With the low acid concentrations, a presence of HCl and without HCl are shown
large number of water molecules are allowed in Figure 1. In the presence of 0.2 M HCl, the
to penetrate through the molecules within the percent yield of the total saccharides
saccharides chain.6 Consequently, the decreased as temperature increased from
reduction of the interaction between the 70 °C to 110 °C because some carbohydrates
molecules might occur. Besides, the dilute might be degraded and converted to other
acid increases the number of water molecules undesired products.
available for microwave irradiation and In the presence of 1 M HCl, the
hence the heat transfer which in turn favors percent yield of the total saccharides
the action of HCl. The hydrolysis increased as temperature increased from
may take place primarily toward the chain 70 °C to 90 °C. However, the percent yield of
terminals. Thus, the extracted total saccharides decreased as temperature
oligosaccharides were shorter chains with increased from 90 °C to 110 °C because some
low molecular weights. The low molecular carbohydrates might be degraded and formed
weight carbohydrates were fructose, a small the undesired products.
amount of glucose and FOSs, respectively. In the presence of 1.8 M and
FOSs were obtained when the extractions 2 M HCl, the percent yield of total
were performed without HCl.7 saccharides decreased as temperature
In the presence of higher HCl increased from 70 °C to 90 °C. However, the
concentrations such as 1.8 M and 2 M HCl, percent yield of total saccharides increased as
the higher molecular weights of extracted temperature increased from 90 °C
saccharides were obtained. In contrast with to 110 °C. It is possible that the degree of
dilute acid, the stronger acid concentrations hydrolysis might be increased as the
are able to hydrolyze the biomass temperature increased within the higher
polysaccharide further away from the range.
terminals. Consequently, larger extracted
oligosaccharides are obtained. Regarding the
effect from the reaction temperature, DP
decreased as temperature increased from
70 °C to 110 °C. The higher reaction
temperature increases the hydrolysis degree
resulting in the smaller size of
oligosaccharides.
PC131

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 correspond to the C1 α-Glcp in the Glcp of
FOS. The signals at 61.33 ppm and 62.23
ppm correspond to C1-Fru and C6-Fru,
respectively. The signals at 103.24 ppm
correspond to the anomeric carbon of
fructose in β-linkage of FOSs (C2-Fru).
The signals at δ 77.36, 74.36 and 81.24 ppm
correspond to C3-Fru, C4-Fru, and C5-Fru,
respectively.

Figure 1. The effect of HCl concentrations

and RO water on the hydrolysis of
Jerusalem artichoke tuber powder.

Figure 7. FOSs 13C-NMR spectra from JAT.

3.4 Protein Determination

Figure 6. The effect of RO water on the A low to zero protein content is
hydrolysis of Jerusalem artichoke tuber preferable in the precipitated sample for the
powder. further prebiotic application. The amount of
The percent yield of total saccharides
the total protein in the precipitated samples is
when performed the extraction process
without using HCl as a catalyst increased shown in Table 2. The Bradford method did
as reaction time and temperature increased. not detect the presence of protein in the FOSs
The degree of hydrolysis may be increased as and high molecular weigt
temperature and reaction time increased. carbohydrates when performed the extraction
Consequently, the FOSs yield also increased in the presence of HCl or without HCl at 70
in the same manner. The maximum FOSs °C and 90 °C. The FOSs and high molecular
yield was 12.87% when performed the weight carbohydrates might either contain no
extraction process at 110 °C for 30 min proteins or the proteins were presented at a
as shown in Figure 2. low concentration beyond the detection limit.
3.3 13C- NMR spectra However, a very small amount of proteins
As shown in Figure 3, all resonances were found in the high molecular weight
presence in the NMR spectra of extracted carbohydrates when performed the extraction
FOSs could be assigned to fructo- by using HCl at 110 °C. It is possible
oligosaccharides as previously described in that the released protein from JATP might
literature.8 occur at higher temperature.
The signals at δ 92.48 ppm PC132

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 3. Percentage of total protein and 2 M HCl. The high molecular
carbohydrates were obtained in the presence
of 1.8 M and 2 M HCl. Besides,
Extracted Temperature Time Average (%)
the temperatures strongly affect the protein
Solvent (°C) (min) Protein
content when performed the extraction with
HCl at high temperatures. The protein
70 0.00±0.10 contents in the extracted saccharides were
90 15 0.00±0.07 very small to almost none.
110 0.00±0.07
RO Acknowledgments
70 0.00±0.06
This work was supported by the
90 30 0.00±0.10 Thailand Research Fund (RSA6280106). We
110 0.00±0.08 thank Center of Scientific Equipment for
0.00±0.06 Advanced Research, Thammasat University
70
(TUCSEAR) for supporting facilities and
0.2 M 90 15 0.14±0.09
equipment.
110 1.02±0.05
70 0.00±0.10 References
0.21±0.08
1. Slimestad, R.; Seljaasen, R.; Meijer,
1M 90 15
K.; Skar, S. L. J. Sci. Food Agric. 2010, 90
110 2.10±0.05 (6), 956-64.
70 0.00±0.10 2. Leroy, G.; Grongnet, J. F.; Mabeau,
1.8 M 90 15 0.77±0.46 S.; Corre, D. L.; Baty-Julien, C. J. Sci. Food
Agric. 2010, 90 (7), 1203-9.
110 1.22±0.20
3. Caleffi, E. R.; Krausova, G.;
70 0.00±0.07 Hyrslova, I.; Paredes, L. L.; dos Santos, M.
2M 90 15 0.49±0.17 M.; Sassaki, G. L.; Goncalves, R. A.; de
1.00±0.23 Oliveira, A. J. Int. J. Biol. Macromol. 2015,
110
80, 392-9.
4. Moreno-Vilet, L.; Garcia-
4. Conclusion Hernandez, M. H.; Delgado-Portales, R. E.;
Based on HPSEC and 13C-NMR Corral-Fernandez, N. E.; Cortez-Espinosa,
spectra, the extraction process without using N.; Ruiz-Cabrera, M. A.; Portales-Perez, D.
HCl as a catalyst provided the low molecular P. Int. J. Biol. Macromol. 2014, 63, 181-7.
weight oligosaccharides. The 5. Bradford, M. M. J. A. b. Anal.
structure of low molecular weight Biochem. 1976, 72 (1-2), 248-254.
carbohydrates from JATP was a chain of 6. Warrand, J.; Janssen, H. G.
inulin-type fructooligosaccharides with DP Carbohydr. Polym. 2007, 69 (2), 353-362.
of 3 to 5. The temperatures do not affect the 7. Jovanovic-Malinovska, R.;
Kuzmanova, S.; Winkelhausen, E. Ultrason.
DP of precipitated saccharides when
Sonochem. 2015, 22, 446-53.
performed the extraction with 0.2 M, 8. Jarrell, H. C.; Conway, T. F.;
1 M HCl or without using HCl as a catalyst. Moyna, P.; Smith, I. C. J. C. R. Carbohydr.
However, the temperatures significantly Res. 1979, 76 (1), 45-57.
affect the DP of precipitated saccharides
when performed the extraction with 1.8 M PC133

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 UiO-66(Zr)/chitosan/polyvinyl alcohol composite films for controlled
release of 1-naphthaleneacetic acid
Nannapat Kaewnukulkit1, Pimpaka Chanchettanadi2, Songwut Suramitr3, Duangkamon
Viboonratanasri4, Chalita Ratanatawanate4, Masatoshi Shioya5, Panida Prompinit4*
1
Interdisciplinary of Sustainable Energy and Resources Engineering, Faculty of Graduate School,
Kasetsart University, Bangkok 10900, Thailand
2
Interdisciplinary Graduate Program in Sustainable Energy and Resources Engineering,
Thammasat University, Pathumthani 12120, Thailand
3
Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand
4
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency
(NSTDA), Khlong Luang, Pathumthani 12120, Thailand
5
Department of Materials Science and Engineering, Major in Materials Science and Engineering, Tokyo
Institute of Technology, Japan
*E-mail: [email protected]

1-Naphthylacetic acid (1-NAA) is widely used as a plant growth regulator. However,

high concentration of 1-NAA inhibits plant growth, contaminates in environment, and affects
human health. To minimize the adverse effect of using 1-NAA, we introduce UiO-
66(Zr)/chitosan/polyvinyl alcohol composite films to improve the performance in controlled
release of 1-NAA. It was found that an increase in the UiO-66(Zr) content could increase 1-
NAA absorption capacity and slow 1-NAA release of the composite films. Among the films,
UiO-66(Zr)/chitosan with ratio of 16/24 revealed an effective slow release rate of 1-NAA at
1.91± 0.49 % after 24 hours which was significantly slower than that of the pure chitosan film
by 4.6 times. This improvement was likely caused by the combined effect between structural
property of UiO-66(Zr) and electrostatic attraction of NH3+ in CS structure in the composite
film matrix.

1. Introduction media. Auxins promote flowering, control

One of the significant global of stem elongation, cell and organ
problems is food security due to rising in enlargement, development of abscission
population growth and climate change. This zone, and gravitropism of roots. 1-
leads to an urgent requirement in an Naphthaleneacetic acid (1-NAA), one of
enhancement of agricultural productivity synthetic auxins, is commonly used in
and the utilization of plant growth horticulture crops. To produce a sufficient
regulators (PGRs) to increase crop yields. biological effect, 1-NAA must be applied in
PGRs are simple molecules that have a concentration of 20-100 ppm of the
specific effects on plant growth and have applied solution.2 Concentration of 1-NAA
many functions such as inhibit or promote lower than this range causes no effect for
leaf and fruit abscission, cell and organ plants while higher concentration than 100
enlargement, germination, and shoot and ppm results in inhibiting growth on the
root growth. There are five types of PGRs plants. Excessive 1-NAA in agricultural
which are auxins, gibberellins, cytokinins, uses can leach into groundwater and soil
abscisic acid, and ethylene.1 Auxins are resulting in uncontrollable adverse
very widely used in plant tissue culture and environmental impact. 1-NAA can also
usually form an integral part of nutrient affect human health such as risk of serious PC134

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
damage to eyes and irritating to respiratory (NANOTEC), National Science and
system and skin. Therefore, controlled Technology Development
release material is highly required to Agency (NSTDA). Chitosan (CS) (degree
increase beneficial use at an optimum of deacetylation 90%) was obtained from
concentration and to prevent environmental Marine Bio Resources Company.
pollution from 1-NAA. Poly(vinyl alcohol) (PVA) (polymerization
The aim of this research is to degree in the range of 1500~1800) was
synthesize a novel UiO-66(Zr)/chitosan/ purchased from FUJIFILM Wako
polyvinyl alcohol composite films for Chemical Corporation. Sodium
controlled release of 1-NAA. UiO-66(Zr), metasilicate pentahydrate (Na2SiO3·5H2O,
is metal-organic frameworks (MOFs), ≥95.0%) was obtained from Aldrich
possesses high specific surface areas, Chemical Corporation. Acetic acid glacial
specific porous size (6 Å), a wide range of was purchased from Carlo Erba Reagents
pH, and structural stability.3 Its beneficial Company. All chemical reagents were used
textural properties could be suitable to as received without further purification.
adsorb and controlled release 1-NAA 2.2 Preparation of UiO-
molecule having molecular diameter 6 Å. 66(Zr)/chitosan/polyvinyl alcohol films
Chitosan (CS) containing a positively charged In a typical procedure, UiO-66(Zr)
ammonium form (NH3+) is expected to was dispersed in deionized water and added
promote a strong attraction of a negatively into 6 ml of 2% w/v of chitosan in acetic
charged 1-NAA molecule. Polyvinyl acid followed by stirring for 30 min. Then,
alcohol (PVA) is a non-toxic, water- 10 ml of 2% w/v PVA solution was added
soluble, and biodegradable polymer with into UiO-66(Zr)/CS solution followed by
good film-forming ability due to abundance stirring for 30 min to obtain UiO-
of OH groups and intermolecular hydrogen 66(Zr)/CS/PVA solution. After that, 2 mL
bonding. The structure of PVA allows a of sodium metasilicate solution was slowly
potential miscibility with CS and MOF as added to the UiO-66(Zr)/CS/PVA solution
well as improvement in water absorption and stirred to obtain a homogeneous
property of the composite film, which is solution with 0.6% w/w SiO2. The
advantageous for agricultural application. composite films were prepared by pouring
The combination between UiO-66 and mixed solutions into 8×5 cm2 silicone mold
chitosan structures in PVA matrix film is and dried in an oven at 70°C for 1.45 h. The
expected to improve the controlled release film thickness was controlled by solution
performance. In this study, effect of UiO- volume. The dried film was neutralized by
66(Zr)/CS ratio on its performance in immersion the film in 80% v/v ethanol
absorption and release of 1-NAA will be (EtOH) solutions for 10 min for four times.
investigated. Physical and chemical In this study, UiO-66(Zr) and
properties of the synthetic composite films chitosan were represented by ‘MOF’ and
will be studied. ‘CS’, respectively, for simplicity. The
sample name and MOF/CS/PVA ratios in
2. Materials and Methods all composite films were summarized in
2.1 Materials Table1.
UiO-66(Zr) was obtained from
National Nanotechnology Center
PC135

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table1. Summary of sample name and 2.4 Film characterizations
MOF/chitosan/PVA ratios in composite Surface chemical analysis was
films. carried out using X-ray photoelectron
spectroscopy (XPS) at BL5.2 in the
Ratio (w/w)
Sample name Synchrotron Light Research Institute,
MOF/chitosan/PVA Thailand. The XPS spectra were calibrated
PVA film 0/0/100 using the C 1s signal at 284.4 eV.
Thermogravimetric analysis (TGA) of all
Chitosan film 0/100/0
samples were performed using the
MOF (Powder) 100/0/0 Thermogravimetry (TG)/Differential
MOF0 film 0/40/60
Thermal Analyzer (DTA) on a Diamond
TG-DTA 6300 thermal analyzer using an
MOF8 film 8/32/60 Al2O3 crucible (150 μL) with a sample mass
MOF16 film 16/24/60 approximately 4.0 mg, heating rate of 5
°C/min, dry air flow of 60 ml/min and the
MOF40 film 40/0/60
temperature ranged from 30 to 800 °C.
2.3 1-NAA absorption and release studies
1-NAA absorption experiments 3. Results & Discussion
were carried out by immersion of 1×1 cm2 3.1 Effect of UiO-66(Zr)/CS ratios on the
of the films in 5 mL of 10-4 M 1-NAA composite film structures
solution for an hour at room temperature. Effect of UiO-6 6 ( Zr)/CS ratios on
After absorption, 1-NAA content remaining the composite film were investigated using
in the solution was analyzed using UV-Vis- XPS technique in O 1s (Fig 1) and N 1s (Fig
NIR spectroscopy at a wavelength of 281 2) regions. Raw materials which are PVA
nm. The remained 1-NAA contents were film, chitosan film, and MOF powder were
calculated to obtain absorption capacity of firstly characterized for comparison. Both
the films. The amount of NAA absorbed by PVA (Fig 1(a)) and chitosan (Fig 1(b))
the composite films were calculated by the films showed major O 1s contributions at
following equation: 531.0 eV and 532.3 eV corresponded to O-
(C0 -Ce )V C and O=C, respectively.4 MOF powder
qe = (1)
W
(Fig 1(c)) showed three main peaks at 530.5
where qe is the amount of 1-NAA absorbed eV, 531.9 eV, and 533.3 eV attributed to Zr-
by the unit amount of the films (mg/g), C0 O-Zr, Zr-O-C, and COOH respectively.5
is the initial concentration of 1-NAA MOF0 film revealed two main peaks which
(mg/L), Ce is the final concentration of 1- are the characteristics of PVA and chitosan
NAA (mg/L), V is the volume of 1-NAA structures. After addition of MOF into the
solution (L) and W is the weight of dried MOF8, MOF16, and MOF40 film matrixes
composite films (g). (Fig 1(e)-1(g)), five main peaks which are
For the release study, the dried films related to PVA, CS, and MOF features were
after 1-NAA absorption were soaked in 5 expected to be observed as shown in Fig
ml of deionized water for 24 hours. The 1(e). However, no significant change in the
released 1-NAA was analyzed using UV- spectra after increasing amount of MOF in
Vis-NIR spectroscopy at a wavelength of the films was clearly found.
281 nm. PC136

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 All samples containing chitosan
were further characterized using XPS
technique in N 1s region as shown in Fig
2(A). Chitosan film in Fig 2(a) showed
three main peaks at 399.3 eV, 400.3 eV, and
401.3 eV, which attributed to non-
protonated amine (NH), amide groups (N-
C=O)6, and amino groups in the ammonium
form (NH3+), respectively. Peak area ratio
of -NH3+/NH was calculated for
comparison of the film properties and
shown in Fig 2(B). It was found that as
M/CS ratios in the films increased from
0/40, 8/32, 16/24, and 40/0, the -NH3+/NH
peak area ratios gradually decreased and
reached zero value in MOF40 sample (no
CS). The decreasing in -NH3+/NH peak area
ratios was directly related to the reduction
of CS content in the films. This result
indicated that amount of a positively charged
ammonium form (NH3+) in the composite
films, which is expected to promote a
strong attraction of a negative charged 1-
NAA molecule, could be possibly followed Figure 1. XPS spectra in O 1s region of (a)
and estimated by monitoring the peak area PVA film, (b) chitosan film (c) MOF
ratio of -NH3+/NH using XPS technique. powder, (d) MOF0 film (e) MOF8 film, (f)
MOF16 film, and (g) MOF40 film.
(a)
(A)

(b) (B)

(c)

(d)

(e)

PC137

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Fig 2. (A) XPS spectra in N 1s region of (a) chitosan film, (b) MOF0 film (c) MOF8 film, (d)
MOF16 film, and (e) MOF40 film. (B) Peak area ratios of NH3+/N-H.
3.2 Thermal stability study MOF0 films. This result indicates that
addition of MOF did not significantly
Thermal gravimetric analyses
improve thermal stability of the composite
(TGA) were carried out to study the thermal
films. This is possibly caused by
stability of raw materials and composite
deformation of crystalline structure of the
films as shown in Fig 3. All samples
MOF in the composite film matrix, which
showed three stages of degradation as
should be further studied using XRD
shown in Figure 3a. In the first stage or the
technique.
first 100 °C, the initial weight-loss stage
occurring in the temperature range of 25- (a)
100 °C was due to the evaporation of
absorbed water moisture and residual acetic
acid. The second stage of degradation in the
temperature range of 250-325 °C was
related to (i) removal of
dimethylformamide (DMF) and the
dehydroxylation of the zirconium oxo-
clusters for MOF powder7 and (ii) rapid
decomposition of polymer segments of
PVA and chitosan due to the thermal
scission of the polymer backbone for all
film samples.8 The third weight-loss stage
starting at 500 °C was attributed to the
decomposition of UiO-66 (Zr) as a result of (b)
the burning of organic linker molecules in
the framework of MOF powder. For the
composite films, weight-loss in this stage
was caused by the degradation of the
byproducts generated by PVA during its
thermal degradation.
Figure 3b showed the summary for
Figure 3a of the thermal parameters of the
onset temperature or extrapolated start
temperature of a process (Tonset) and
maximum point of the degradation or the
temperature of the highest reaction rate
(Tmax). Considering the MOF composite Figure 3. (a) TGA and (b) Tmax and Tonset of
films, it was found that as M/CS ratios in samples.
the composite films increased, Tmax was
slightly increased and reached the
maximum at 325C in the MOF8 film. Then
Tmax was decreased in the MOF16 and PC138

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.3 Absorption and release of NAA using hours) than MOF8. The cumulative release
the composite films of MOF16 was further monitored after 3
1-NAA absorption capacities of the days (data not shown). The cumulative
composite films prepared at different release was slightly increased and reached
MOF/chitosan (M/CS) weight ratios <3%, which was caused by a continuous
compared with raw materials were release after a burst effect. To gain more
investigated as shown in Fig 4. Fig 4(a) information of the release behavior, the
showed that chitosan film could absorb cumulative release profile at different
highest amount of 1-NAA (12.09±2.27
periods of times (hours and days) is
mg/g) while MOF powder showed lowest
currently under our investigation.
adsorption capacity (1.84±0.34 mg/g). For
PVA film, the absorption capacities could Among the composite films,
not be determined because of low stability MOF16 was an appropriate composite film
and dissolution in water. for high absorption capacity (7.62±0.77
Considering the composite films mg/g) and slow release of 1-NAA
with different M/CS ratios, the film without (1.91±0.49% after 24 hours). This
MOF (MOF0) showed maximum performance was more effective than the
absorption capacity for 1-NAA because it results reported in previous literatures4,9 as
contains highest amount of chitosan in the summarized in Fig 4(c). The M/CS ratio of
PVA film matrix. After addition of MOF 16/24 could have such high performance
into the films, the absorption capacities of possibly because of the combined effect
all composite films were obviously between structural property of UiO-66(Zr)
reduced. This was caused by low attraction and electrostatic attraction of NH3+ in CS
from a positively charged ammonium form structure in the composite film matrix.
(NH3+) in chitosan structure for 1-NAA
absorption. For the composite films with (a)
M/CS ratios of 8/32 and 16/24, it showed
that the absorption capacities slightly
increased as the M/CS ratios increased from
8/32 (6.05± 0.80 mg/g) to 16/24 (7.62±0.77
mg/g). This is likely caused by an
increasing in textural effect obtained from
MOF structure. For the film with M/CS
ratio of 40/0 (MOF40), it was not stable and
finally dissolved in water after 60 minutes.
Therefore, MOF40 was not used for 1-NAA
absorption and release studies.
Release performances of the
samples were further investigated as shown
in Fig 4(b). UiO-66(Zr) powder exhibited
slowest release of 1-NAA. Hence, addition
of MOF into the MOF8 and MOF16 films
could obviously delay releasing 1-NAA. It
was found that MOF16 could slower
release of 1-NAA (1.91±0.49% after 24 PC139

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 (b) contents in the composite films. TGA
results revealed that addition of UiO-
66(Zr) did not significantly improve
thermal stability of the composite films.
This is possibly caused by deformation of
crystalline structure of the UiO-66(Zr) in
the composite film matrix, which should
be further studied using XRD technique.
The MOF16 film exhibited high
absorption capacity and slow release rate
of 1-NAA.

(c) Acknowledgements
The authors would like to thank
Thailand Advanced Institute of Science and
Technology and Tokyo Institute of
Technology (TAIST-Tokyo Tech) for
funding, Kasetsart University for
suggestions, and Synchrotron Light
Research Institute for technical help in
using XPS. This work was supported by the
National Nanotechnology Center
(NANOTEC), National Science and
Technology Development Agency
(NSTDA).
Figure 4. (a) Absorption capacities and (b)
References
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the composite films prepared at different 1. Kaur, P.; Mal, D.; Sheokand, A.;
MOF/chitosan weight ratios compared with weta, S.; Singh, L.; Datta, S., Int. J. Curr.
raw materials (chitosan film and MOF Microbiol. App. Sci 2018, 7 (06), 2177-
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previous literature and this study. J. Agric. Food Chem. 1974, 22 (4), 568-
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3. Zou, D.; Liu, D., Materials Today
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Chemistry 2019, 12, 139-165.
We have shown that a novel UiO-
4. Saosamniang, P. S., S.;
66(Zr)/chitosan/polyvinyl alcohol Viboonratanasri, D.; Vayachuta, L.;
composite films were successfully Prompinit, P. , Petty patent application No.
synthesized for controlled release of 1- 1903001802, July 11, 2019.
NAA. XPS results showed the existing of .
amino groups in the ammonium form
(NH3+) which directly related to CS
PC140

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
5. Wang, Y.; Li, L.; Dai, P.; Yan, L.; 7. Yang, Q.; Zhang, H. Y.; Wang, L.;
Cao, L.; Gu, X.; Zhao, X., J. Mater. Chem. Zhang, Y.; Zhao, J., ACS Omega 2018, 3
A 2017, 5 (42), 22372-22379. (4), 4199-4212.
6. Lindberg, B. M., R.; Siegbahn, K.; 8. Yang, J.; Duan, J.; Zhang, L.;
Larsson, R.; Gölander, C. G.; Eriksson, J. Lindman, B.; Edlund, H.; Norgren, M.,
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Molecules 2013, 18 (6), 7239-52.

PC141

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Preparation of nanocellulose/chitosan composite membrane for fuel cell
application
Witsuwat Prasopsab, Aimorn Saksaengwijit, Wunpen Chonkaew*
Department of Chemistry, Faculty of Science, King Mongkut’s University of Technology Thonburi, Bangkok
10140, Thailand
*E-mail: [email protected]

Cellulose nanofiber (CNF)/chitosan composite membranes were prepared as solid

electrolyte membranes for direct methanol fuel cells (DMFCs). CNF was extracted from Para
rubber wood sawdust using acid hydrolysis (64%wt H2SO4 at 45oC for 30 min), followed by
mechanical homogenization. The composites were prepared by dissolving chitosan in 1% v/v
acetic acid and mixed with CNF using a high-speed homogenizer for 2 min. Chemical structure,
thermal stability, and CNF microstructure were investigated using FTIR, TGA, and AFM,
respectively. Membrane characteristics, including water uptake, swelling, methanol
permeability, proton conductivity, and ion exchange capacity (IEC), of composites were
determined. The storage modulus of the composites measured in a 2.5 M methanol bath at 30oC
using dynamic mechanical analysis (DMA) increased as the amount of CNF increased. The
methanol crossover of the chitosan-based membrane reduced after adding only 5% of CNF.
Proton conductivity of composites was comparable to that of the pure chitosan. Chitosan
containing 5%wt CNF showed an interesting promise as an electrolyte membrane.

1. Introduction electrolyte membrane to the cathode.2

Therefore, one of key components to gain
Fuel cells are promising technology
high performance of DMFC is the ability of
for use as a source of renewable energy,
polymer electrolyte membrane. The
which are recently gaining more popularity
electrolyte membrane for DMFC should have
due to their high power effieciency,
a fast pathway for proton transportation (high
cleanliness, environmental friendly by-
proton conductivity) and be able to separate
product, and cost-effectiveness.1 Polymer
methanol from anode to cathode
electrolyte membrane fuel cell (PEMFC) is
compartment (low methanol crossover
an attractive type of fuel cell. It converts the
diffusion through the membrane). One of the
chemical energy from the electrochemical
most common commercial membranes for
reactions to electrical energy. The advantage
DMFC (as well as hydrogen fuel cell) is
of this type of fuel cell is low operating
“Nafion”, which is a sulfonated tetra-
temperature (<90oC) and higher power
fluoroethylene based fluoropolymer-
generation than other types at a given volume
copolymer. Even Nafion has high proton
and weight. The performance of PEMFC is
conductivity, good chemical and mechanical
strongly dependent on how well the
stabilities, it still has some disanvantage such
generated electricity transport through the
as high price per power unit, high methanol
electrolyte membrane to electrodes. In direct
permeability value, and non eco-friendly
methanol fuel cell (DMFC), methanol is
disposal.3
oxidized in the presence of water at the
Chitosan is a bioplastic polymer that
anode, the generated proton from the
can naturally decompose. Due to its high
oxidation will be transported through the PC142
ionic conductivity, thermal stability, and low

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
cost, chitosan has been extensively studied as Nanocellulose was prepared in our
an alternative material for membrane laboratory from Para rubber wood sawdust
electrolytes and electrodes for low and using the acid hydrolysis and followed by
moderate-temperature fuel cells.4 As a mechanical homogenization; the method was
cationic electrolyte polymer, free amino explained elsewhere in details (Laksika
groups in chitosan membrane play an Ongthip & Wunpen Chonkaew, 2018)6.
important role in its ionic conductivity. The The morphology of obtained
fast transportation of proton via free amino nanocellulose suspension was then
groups in chitosan membrane provides high characterized using atomic force microscopy
ionic conductivity. The hydrophilic groups (AFM, Atomic Force Microscope Icon,
(free amino and hydroxyl groups) containing Bruker, USA) with a scan rate of 0.98 Hz and
in the chitosan molecular backbone have a scan size 5 m.
high affinity to water molecules. This results 2.3 Preparation of composite membrane
in high water uptake value for chitosan Chitosan (1% w/v) was dissolved in
membrane. However, chitosan membrane 1% acetic acid solution at 60oC for 12 h. The
still suffers from its low tensile strength and specific amount of nanocellulose was mixed
substantial shrinkage upon dehydration.5 In with the chitosan solution and homogenized
this research, the chitosan membranes were at 23,000 rpm for 2 min, followed by remove
modified with cellulose nanofibers (CNFs) in bubbles with sonicate 30 min to prepare the
order to improve their mechanical properties composites containing 2.5, 5, 10, 20, and
and methanol permeability. The polymer 30%w/w CNFs. The obtained solution was
membranes based on nanocellulose/chitosan poured into Teflon mold at room
composites were prepared and studied the temperature, and dried at room temperature.
membrane characteristics such as the value of The dried membranes were then neutralized
water uptake, degree of swelling, methanol in 2 M NaOH for 5 min and thoroughly
permeability, proton conductivity, and ion washed to get rid of the excess acid.
exchange capacity (IEC) in order to examine 2.4 FTIR
their potential to use as an electrolyte Chemical structures of nanocellulose/
membrane in DMFC. chitosan composites were characterized
using a FTIR spectrometer (Nicolet 6700,
2. Materials and Methods Thermo Scientific, Canada) over a range of
2.1 Materials 4000-400 cm-1 with 16-scan and at the
The sawdust was supplied by the Para resolution of 4 cm-1.
rubber wood furniture company in Thailand. 2.5 Thermal stability
Chitosan (CS) with molecular weight of Thermal stability of cellulose,
310,000-375,000 Da was purchased from chitosan, and composites was investigated
Aldrich. Sodium hydroxide (NaOH), sodium using a thermogravimetric analyzer
sulfide (Na2S), sodium chlorite (NaOCl2), (TGA/DSC 3+, Metter Toledo, Switzerland).
glacial acetic acid, sulfuric acid (H2SO4), The 5 mg of sample was put in a ceramic
hydrochloric (HCl), potassium hydroxide crucible and then heated from 25oC to 750oC
(KOH) and methanol (CH3OH) were with a scan rate of 10oC/min.
analytical grade. 2.6 Dynamic mechanical analysis (DMA)
2.2 Preparation of Nanocellulose PC143

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 DMA with tension mode (DMA1, concentration of HCl standard solution (M),
Metter Toledo, Switzerland) and equipped and m is the weight of the membrane (g).
with an immersion bath was carried out to Methanol permeability was
determine the storage modulus of the determined in a double cell diffusion system
composites in 2.5 M methanol solution at in which the membrane was sandwiched
30oC. between two cells. One cell contained
2.7 Electrolyte membrane charac- distilled water, and the other cell contained
terization 2.5 M methanol. The solution was collected
The dried membranes (Wdry) soaked 1 ml for every hour for 24 h at 30oC. The
in distilled water for 24 hours, then weighed methanol diffusion through the membrane
(Wwet) and calculated for the percentage of was measured using gas chromatography
water absorption as in equation (1). (GC, Hewlett-Packard-HP 6890 GC System,
%water uptake = Wwet-Wdry x100% (1) Agilent Technologies Inc., USA). The
methanol permeability was calculated as in
Wdry
equation (4).
The swelling test was measured by P = (SLV) / (AC) (4)
soaking the dried membranes (Adry) in
where P is the diffusion through methanol
distilled water for 24 hours, then measured
(cm2 .s-1), S is the slope value from the plot
the surface area (Awet), and calculated for the
of methanol concentration and time, C is the
percentage of swell as in equation (2).
initial methanol concentration (M), V is the
%swelling = Awet-Adry x100% (2) volume of methanol (cm3), L and A are the
thickness (cm) and the surface area of
Adry
membrane contacted with the methanol
Ion exchange capacity (IEC) was solution (cm2), respectively.
measured by back titration. About 0.20 g The impedance of membranes was
membrane was soaked in 1.0 M KOH for 24 measured at wet state using Electrical
h, washed with distilled water, and Impedance Spectroscopy (EIS, E4990A,
equilibrated in 40 mL of 0.01 M HCl standard Keysight Technologies, USA ) over a range
solution for 24 h. The obtained solution after of 100 Hz-1MHz at 500 mV. Before the
membrane immersion was titrated with 0.01 measurements, the membranes were soaked
M NaOH standard solution. A 0.01 M HCl in distilled water for 24 h. Product
standard solution was used as a blank. The conductivity (σ, S.cm-1) was calculated using
IEC value (mmol/g) was calculated using equation (5)
equation (3). σ = l / RS (5)

IEC = (Vblank - Vmembrane) CHCl (3) where l is the thickness (cm), S is the
surface area (cm2) of the membrane, and R is
m the bulk resistance of membrane (Ohm)
where Vblank is the volume of NaOH used to determined from the low intercept of high
titrate with blank (ml), Vmembrane is the frequency region of the Nyquist plot.
volume of NaOH used to titrate with HCl
after soaking membranes (ml), CHCl is a
PC144

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3. Results & Discussion molecules in cellulose, C-O stretching, and
3.1 Atomic Force Microscope (AFM) C-O-C stretching of the glycosidic bond
between glucose, respectively6. A similar
spectrum as nanocellulose was found for
chitosan (CS). The CS spectrum showed the
band at 3000-3500 cm-1 attributed to the
overlaps of the O-H stretching and the NH-
stretching. The peaks at 2874 corresponded
to C-H stretching of CH3 groups. The peak
at 1626 cm-1 is associated with imine group
(N–C)7. The peak at 1545 cm-1 corresponded
to the N–H deformations of a primary amine
Figure 1. AFM image of CNFs. group8. After reinforcing CS with
In Figure 1, the nanocellulose nanocellulose, the characteristic peaks of
obtained was a fibrillar structure with the nanocellulose peaks at 1054 and 1032 cm-1
length of 106.9.949  20.374 nm and the assigned to C-O stretching were observed.
diameter of 92.131  10.236 nm. The result Additionally, the peak at 1151 cm-1, assigned
indicated that the nanocellulose type was to C-O-C stretching, was found.
cellulose nanofiber (CNF), which performed 3.3 Thermal stability property
good reinforcement properties. Figure 3 shows the TGA and DTG
3.2 Chemical structure with FTIR thermograms of nanocellulose, chitosan, and
The chemical structures of chitosan, nanocellulose/chitosan composites. The
nanocellulose, and chitosan/nanocellulose composites showed three stages of
composites are investigated in Figure 2. The decomposition. The first decomposition
nanocellulose extracted from the sawdust process started at about 44oC was assigned to
showed the characteristic peaks at 3354 cm-1, the evaporation of water, the second stage
started at 244oC corresponded to the
decomposition of chitosan, and the last stage
started at about 325oC corresponded to the
decomposition of nanocellulose. Therefore
the composites could be used at the
temperature higher than that actually used in
the direct methanol fuel cell (DMFC)
application at 120oC.

Figure 2. FTIR of membrane composites.

2899 cm-1, 1641 cm-1, 1026 cm-1, and 897

cm-1, which attributed to O-H stretching,
C-H stretching, O-H bending of water PC145

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 the starting value. Chitosan has hydrophilic
groups that were susceptible to the absorption
of water solvent; thus, water could diffuse
and plasticize the chitosan membrane. Once
CNF was added, the storage modulus of the
composites significantly increased with the
increasing amount of CNFs. The composite
containing only 5.0%wt CNF had E’ value
(46 MPa) 23 times higher than the neat
chitosan membrane (2 MPa). Besides, the
CNFs in the chitosan matrix acted as barriers
for water diffusion; the E’ of the composites
containing CNF at least 5.0%wt, therefore,
remained unchanged during 30 min of
measurement.
3.5 Membrane Parameters
Table 1 shows %water uptake, IEC,
%swelling, methanol permeability, proton
conductivity of the chitosan/CNFs composite
membranes.
Water uptake decreased as the
Figure 3. TGA (a.) and DTG (b.) of amount of CNFs increased up to 10%
chitosan/CNFs composites. addition, and then the values remained
3.4 Dynamic Mechanical Analysis (DMA) constant after further addition. The results
were attributed to the barrier properties of
CNFs.
Methanol permeation of chitosan was
diminished after adding the CNFs. It was
found that the methanol permeability of
composites containing 20.0%wt CNF was
one order of magnitude lower than the neat
chitosan membrane.
The IEC values of the composites
were slightly lower than that of chitosan. The
result was because the amount of the NH3+
Figure 4. DMA of chitosan and composites. groups in chitosan was replaced (OH)
To imitate the application used as an hydroxyl groups as the amounts of CNFs in
electrolyte membrane in DMFC, the composites increased. The decrease of IEC
storagemodulus (E’) of chitosan-based also reflected proton conduction property of
membranes was measured in immersion baht the membranes. The proton conductivity
containing 2.5 M methanol at 30oC; the decreased with the addition of CNFs.
results show in Figure 4. It was found that E’ The result could be attributed to the
of chitosan slightly reduced as compared to reduction of free volume of water diffusion
PC146

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
for proton transportation by vehicle drag, decrease in proton conduction. The thermal
together with the reduction of ionic sites for and mechanical stabilities were enhanced by
proton hopping. the addition of at least 5.0% wt CNF.
Moreover, the methanol crossover of
4. Conclusion composites containing 5.0%CNF was low,
In this work, the CNFs/chitosan composites and its proton conductivity was comparable
was successfully prepared. Water uptake and to that of the neat chitosan. Even the proton
IEC of the composites were lower as than the conduction of the prepared composites was
neat chitosan. The composites with low not improved, we found that chitosan
methanol permeability but with scarifiction composite containing and suited for being
of their proton conduction were obtained. further develope as an electrolyte membrane
The reduction of water diffusion pathways for DMFC.
for proton transportation by the vehicle drag
mechanism and the reduction of ionic sites
for proton hopping could be attributed to the
Table 1. Results of different composite’s %water uptake, methanol permeability, proton
conductivity and ICE.
Methanol permeability Proton conductivity IEC
%wt CNFs %Water uptake
(10-6cm2.s-1) (S.cm-1) (mmol.g-1)
0 160.43 2.01666 3.18x10-3 0.199  0.014
2.5 146.94 1.3209 1.63x10-5 0.176  0.015
5.0 135.93 1.17287 1.26x10-5 0.159  0.038
10.0 119.69 1.30952 1.89x10-5 0.173  0.005
20.0 119.62 1.37499 2.96x10-5 0.172  0.006
30.0 119.58 0.964488 3.47x10-5 0.143  0.009

Acknowledgements 4. López-Chávez, E.; Oviedo-Roa, R.;

The authors would like to thank the Contreras-Pérez, G.; Martínez-
Capacity Building Program for New Magadán, J. M.; Castillo-Alvarado, F.
Researcher 2019 from National Research L. Int. J. Hydrog. Energy 2010, 35,
Council of Thailand (NRCT) for research 12141–12146.
funding. 5. Cui, L.; Gao, S.; Song, X.; Huang, L.;
Dong, H.; Liu, J.; Chen, F.; Yu, S. RSC
References Adv.2018, 8 (50), 28433-28439.
6. Ongthip, L.; Chonkaew. W.,
1. Barbir, F.; Gómez, T. Int. J. Hydrog.
Srinakharinwirot Sci. J.l 2018, 34 (1),
Energy 1996, 21 (10), 891-901.
263-275.
2. Antonucci, P. L.; Arico, A. S.; Creti,
7. Loh, K. S. Malaysian J. Anal. Sci.
P.; Ramunni, E.; Antonucci, V. Solid
2016, 20 (4), 885-891.
State Ionics 1999, 125, 431–437.
8. Dashtimoghadam, E.; Hasani-
3. DeLuca, N. W.; Elabd, Y. A. J. Power
Sadrabadi, M. M.; Moaddel, H. Polym.
Sources 2006, 163, 386–391.
Adv. Technol. 2009, 21 (10), 726-734.
PC147

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Chemical recycling of degradable polylactide by microwave-assisted
alcoholysis with erythritol
Nim Bunthoeun, Pakorn Opaprakasit*
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology (SIIT),
Thammasat University, Pathum Thani 12121, Thailand
*E-mail: [email protected]

Chemical recycling has attracted vast attention as one of effective solutions to deal with
serious plastic waste problems. In this work, depolymerization of polylactide (PLA) by
alcoholysis has been developed for converting PLA post-consumer products to value-added
raw materials. Alcoholysis was conducted by using erythritol in a presence of
tetrabutylorthotitanate (TBT) catalyst, employing microwave irradiator. Effect of
PLA/erythritol ratios on chemical structures of the alcoholyzed products was examined by
varying the ratio from 1/1 to 7/1 wt/wt, at a fixed TBT content of 2 wt% PLA. Chemical
structures and compositions of the products were investigated by FTIR and 1H-NMR
spectroscopy. ATR-FTIR spectra revealed a decrease in intensity of the C=O mode of lactate
and the O-H band of erythritol, and an appearance of new ester bonds, confirming the
occurrence of transesterification. The products consisted of mono-lactate, dilactate, and poly-
lactates of erythritol, in which erythritol mono-lactate was a major product, with 72.7% yield.
This is much higher than those of dilactate and poly-lactates for all reaction conditions. The
process has high potential for effectively converting PLA wastes to desired oligomers with
hydroxyl terminals, which can be used as biodegradable additives, adhesives, or starting
materials for elastomeric polyurethanes.

1. Introduction problematic to the environment4. Also, given

the limitation of natural feedstock in the near
Polylactic acid or polylactide (PLA)
future, recycling of PLA is considered as an
is biodegradable and biocompatible polymer,
economical approach to conserve the natural
in which its monomer is originated from
resources5. There are many methods applied
renewable resources, such as, corn starch,
in recycling of PLA wastes, i.e.,
wheat, cassava, sugar, and agricultural
mechanical/physical, chemical recycling, and
wastes. PLA has been used to replace
energy recovery. Among these, chemical
petroleum-based polymers1. The material is
recycling is highly feasible for turning high
evolved from lactic acid monomer through
molecular weight PLA waste to its monomer
polycondensation, azeotropic dehydration, or
or oligomer products through
ring-opening polymerization2, 3. Commercial 6, 7
depolymerization pathway .
products of PLA have been used in various
fields, such as, food/non-food packaging, Alcoholysis is one of the promising
medical devices, printing filaments, fibers, chemical recycling processes for PLA wastes
and agricultural mulch films. Although this in an attempt to reduce the environmental
polymer is degradable, which can be concerns by reducing landfill space and
completely degraded from a few months to conserving natural feedstock. This method
years, its industrial and household post- has been applied for most of bio-based
consumer wastes are also judged as polyester wastes via transesterification PC148

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
reaction or reverse polymerization reaction. as temperature, power, pressure, and reaction
Various alcohols with different numbers of time6. Moreover, catalyst plays a key role in
hydroxyl active groups and molecular weight reaction selectivity and efficiency to enhance
are employed for this ester bond cleaving the reaction rate and increase the degree of
process8, 9. PLA can be alcoholyzed to depolymerization17, 18. The transesterification
generate a mixture of lactate (monomer), of PLA with 1,3-propandiol, 1,4-butandiol,
alkyl lactate fragments, and oligo-lactate, and dipentaerythriol, with and without the
with high content of hydroxyl terminated use of tin (II) 2-ethylhexanoate (SnOct)
groups. This product can be used as value- (1w%) catalyst, was examined. In the
added starting material for biodegradable catalytic system, the alcoholyzed PLA
hydroxyl additive compounds or in products had much lower molecular weight,
polyurethane preparation. Alcoholysis of due to higher degree of depolymerization14.
PLA by using various alcohols were reported, Many catalysts have been used to aid the
such as, methanol7, 10, ethanol11, 1-propanol, cleaves of ester bonds of PLA, such as,
1-butanol6, ethylene glycol12, 13, 1,3- titanium isopropoxide (TIP)19, tetrabutyl
propandiol14, 1,4-butandiol15, glycerol, orthotitanate (TBT)20, 21, and cobalt (II)
pentaerythritol16, and dipentaerythritol14. The acetate22.
alcoholysis of PLA is typically conducted at
In this work, erythriol (E) is
high temperatures and pressures, with or
employed in the alcoholysis of high
without the use of catalysts. The alcoholysis
molecular weight PLA. Tetrabutyl
of PLA by ethylene glycol (EG) was
orthotitanate (TBT) is used as a
reported. A mixture of PLA and EG, at a
transesterification catalyst. PLA/erythritol
PLA/EG ratio of 1:2 wt/wt, was
weight ratios are varied from 1/1 to 7/1 wt/wt.
conventionally heated at 170oC for 30 min13
The reaction temperature (240oC), pressure,
and 90 min12 in nitrogen atmosphere. A
and time (10 min) are manually controlled by
partial transesterification of PLA chains was
using a microwave reactor. The resulting
observed, whose product was used in UV-
alcoholized products are then characterized
curable applications, as contained long
by ATR-FTIR and 1H-NMR spectroscopy for
sequences of lactate units.
qualitative and quantitative analyses.
Many heating methods have been
investigated for depolymerization of PLA
wastes, such as, conventional heating and 2. Materials and Methods
microwave-assisted alcoholysis. However,
conventional heating is reported as less 2.1 Materials
effective, due to high energy consumption Polylactide (PLA), erythritol, and the
with low efficiency. The transesterification catalyst were of commercial grade. PLA
was completed at long reaction time, while (4043D) (Mw=120,000-150,000 g/mol) was
the reaction pressure cannot be controlled. In purchased from NatureWork®. Meso-
contrast, microwave-assisted method has Erythritol (E) (Mw=122.12 g/mol, purity
more advantages, owing to its energy saving, 99%) was provided by Acros Organics.
short reaction time, and reaction Tetrabutyl orthotitanate (97%) (TBT) was
selectivity/efficiency. In this method, many obtained from Fluka.
parameters can be precisely controlled, such PC149

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 was applied for structural elucidation and
quantitative analysis.
2.2 Transesterification of PLA
PLA was transesterified by using a
microwave reactor (Discover SP series, CEM 3. Results & Discussion
Mattews NC, USA). The reactor utilizes an
3.1 ATR-FTIR spectroscopy
irradiation at a frequency of 2455 MHz at a
power of 200 W, equipped with an 80 mL ATR-FTIR spectra of the alcoholyzed
vessel tube, a pressure monitor, and a fiber products obtained from various
optic temperature probe. Effect of PLA/erythritol weight ratios (1/1, 2/1, 3/1,
PLA/erythritol ratios on structures and 4/1, and 7/1 wt/wt) are illustrated in Figure 1.
property of the products were examined by The products are denoted as (b) LET11, (c)
varying from 1/1 to 7/1 wt/wt, at a fixed LET21, (d) LET31, (e) LET41, and (f)
amount of TBT catalyst at 2 wt% of PLA. LET71. The spectra show band
The reaction was conducted at a temperature characteristics of lactate sequences at
of 240oC and 10 min reaction time, as as(CH3)-2992 cm-1, s(CH3)-2941 cm-1, and
summarized in Table 1. (CH)-2881 cm-1. Bands of as(CH2),
s(CH2), and (CH) of erythritol reacted with
PLA are also observed at the same location of
Table 4: Summary of experimental sp3 hybridization C-H of lactates. In the
conditions fingerprint region, the bending and stretching
PLA/erythritol Pressure bands of as(CH3), s(CH3), and (-CO-O-)
Sampl
mol/m (240oC, 10 are observed at 1453, 1375, and 1262 cm-1 ,
e code wt/wt
ol min) respectively.

LET11 1:1 1.7:1 80 PSI Important information can be

obtained from changes of the hydroxyl group
LET21 2:1 3.4:1 90 PSI (OH) and carbonyl group (C=O) stretching
LET31 3:1 5.1:1 212 PSI bands. The products, as shown in Figure 1,
have the OH band at different frequencies
LET41 4:1 6.8:1 249 PSI and intensities, depending on the feeding
LET71 7:1 11.9:1 250 PSI PLA/erythritol ratios. LET11 has the highest
OH band intensity, compared to those of
LET21, LET31, LET41, and LET71. Also,
the band position is the lowest at 3382 cm-1,
2.3 Characterization
compared to other products, due to higher
The resulting products were degree of hydrogen bonding from its high OH
characterized by Fourier transform infrared content. In contrast, the corresponding band
(FTIR) spectroscopy in an attenuated total for LET71 is at 3478 cm-1.
reflectance (ATR) mode on a Nicolet iS5
The H-bonding characteristic also
spectrometer, for 64 scans at a resolution of 2
affects band position of the carbonyl (C=O)
cm-1. Nuclear magnetic resonance (1H-NMR)
stretching mode. The higher content of OH
spectroscopy (Bruker 500 Ultrashield Plus)
groups also lead to higher degree of H- PC150

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
bonding to carbonyl group, shifting the band completely eliminated when the overall
to downfield location. The alcoholysis of hydroxyl groups of erythritol are completely
PLA/erythritol is confirmed by new ester reacted with lactate sequence, to form new
bond formation via transesterification, in ester linkages.
which lactate sequences are bonded to the
hydroxyl groups of erythritol. The (-CO-O-)
stretching bands of ester are observed at as(- 3.2 1H-NMR analysis
CO-O-)1185 cm-1, s(-CO-O-)1086 cm-1,
The structure of the products was
and (-CO-O-)868 cm-1. The band intensity
examined by 1H-NMR spectroscopy, as
of these modes increased, when the
shown in Figure 2. The alcoholized PLA
PLA/erythritol ratios were varied from 1/1 to
products are mixtures of 3 possible
7/1 wt/wt. In addition, the hydroxyl bending
structures: (A), (B), and (C). The
(OH) mode at 991 cm-1 of free erythritol depolymerization products contain lactate,
decreases in its intensity, with the increase in dilactate, and poly-lactate sequences, which
the PLA/erythritol ratios. This band is
 (C=O) ras(CH3) s(-CO-O-)
1748 1122 1086
(C-CH3)
as(-CO-O-)
 (C=O) 1041
1185
1742

(-CO-O-) Lactide
(-CO-O-)

(-CO-O-)
1262

(C=O)
s(CH3)
s(CH3) & as(CH2)
1375
2941 as(CH3)
(OH) as(CH3) s(CH2) & (CH) 1735 868 750
1453 935
3478 2992 2881
(g)
(f) 820
(e)
(C-O)

(d)
(c)
900
(b) Twist-(CH2) (C-C)
1271-1252
3382 (a) (CH2) 1456
3203
1076
1051
965

863

1407
(CH) (CC-O)

wavenumber (cm-1)
Figure 8: ATR-FTIR spectra of (a) erythritol, (b) LET11, (c) LET21, (d) LET31, (e) LET41, (f)
LET71, and (g) neat PLA.

4-monolactatebutane-1,2,3-triol 4-dilactatebutane-1,2,3-triol 4-polylactatebutane-1,2,3-triol

1,4-di(polylactate)butane-2,3-diol 1,2,3,4-tetra(polylactate)butane PC151

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 [2]

D2 O

b1,b2,b
[1]

d1,d,d2

a1,a
(a) Erythritol
OH e1 e2 [1]
c1,c e4
h1 e3
(b) LET11
h2 [2]
h4 h3
(c) LET31
CDCl3

Cat-CH3
OH

(d) LET71

Chemical Shift (ppm)

Figure 9: 1H-NMR spectra of (a) erythritol (in D2O), (b) LET11, (c) LET31, and (d) LET71 in
CDCl3.

Table 5: Summary of product compositions of LETxx, calculated from 1H-NMR spectra.

Structure fraction
Sample % lactate % dilactate % poly-lactate
%(A) %(B) %(C)

LET11 72.7 17.0 10.3 83.2 6.8 10.0

LET31 70.5 19.6 9.9 49.1 23.6 27.3
LET71 63.3 27.0 9.7 34.9 32.6 32.6

are bonded to hydroxyl group of erythritol. ppm and methine signals at d~4.38 ppm and
These results in further differences in c~5.18 ppm, respectively. The product in
lactate sequences of (A), (B), and (C) structure (A) has methylene signals at
products, for example at least 3 different e1~4.28 ppm and e2~3.83 ppm and methine
structures are obtained for structure (A) signals at h1~4.52 ppm and h2~3.93 ppm.
products, as shown in Figure 9. The mono- The structure (B) has methylene signal at
lactate has methyl signal at b2~1.45 ppm e3~4.15 ppm and methine signal at h3~4.66
and methine signal at d2~4.34 ppm. The ppm. The structure (C) has methylene
dilactate has two methyl signals at b1~1.48 signal at e4~4.08 ppm and methine signal at
ppm and a1~1.58 ppm and two methine h4~4.76 ppm.
signals at d1~4.40 ppm and c1~5.28 ppm, 1
H-NMR spectra of LET11, LET31,
respectively. The poly-lactate sequence has
and LET71, as shown in Figure 9, were PC152
methyl signals at b~1.41 ppm and a~1.56

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
used for quantitative analysis of the successfully developed by alcoholysis
depolymerization yields and compositions reaction in a presence of erythritol. ATR-
of the alcoholized PLA products. The FTIR spectra of the products confirmed the
compositions were calculated by using the success of the alcoholysis reaction, i.e.,
methyl signals of lactate sequences and formation of new ester bonds, reflecting by
signals of methyl end group (b2), (b1), and changing in band positions of the hydroxyl
(b), respectively. The integration values and carbonyl bands, and the elimination of
were used for conversion yield calculation. free erythritol. The main products contain
The mono-lactate product was estimated lactate, dilactate, and poly-lactate, in three
based on the equation [%( lactate) = different structures (A), (B), and (C). The
(b2*100)/(b1+b2+b)]. The results, as results from 1H-NMR quantitative analysis
summarized in Table 5, show that the yield confirmed that high molecular weight PLA
of lactate is higher than those of dilactate is converted to mono-lactate for up to
and poly-lactate, reflecting that high 72.7%, and dilactate, and poly-lactate. The
molecular weight PLA is transformed to structure (A) occurs dominantly for LET11
mono-lactate with the conversion yields of system, which was prepared by an excess
72.7%, 70.5%, and 63.3% for LET11, amount of erythritol. These products
LET31, and LET71, respectively. possess high contents of hydroxyl terminal
Significant amounts of dilactate are groups, which have potential for use as
detected in these products, whose functional materials in various applications,
conversion yield is about 27% for LET71. especially biodegradable hydroxyl additive
The yield of poly-lactate is not much compounds, adhesives, and starting
different for all products, which are materials for elastomeric polyurethanes.
constant at around 10%.
The structural fraction is also
Acknowledgements
examined by the equation
[%(A)=(h1*100)/(h1+h3+h4)] for structure The authors gratefully acknowledge
(A) calculation. For LET11, the structure financial supports from the Research
(A) is a major product, whose content is University network (RUN) grant, provided
much higher than those of structures (B) from the National Research Council of
and (C). For LET31 and LET71, however, Thailand (NRCT) and the Center of
all structures are generated at similar yield Excellence in Materials and Plasma
compositions. This is likely because when Technology (CoE M@P Tech), Thammasat
an excess amount of the sugar was used in University, Thailand. B.N. is grateful to the
LET11 system, its more reactive primary supports from the Excellent Foreign
hydroxyls have higher probability to react scholarship (EFS) program provided by
with lactate sequences than the secondary SIIT.
counterparts.

References
1. Lunt, J., Polym. Degrad. Stabil. 1998,
4. Conclusions
59 (1), 145-152.
A depolymerization process for 2. Ryner, M.; Stridsberg, K.; Albertsson,
high molecular weight PLA has been A.-C.; von Schenck, H.; Svensson, M.,
PC153

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Macromolecules 2001, 34 (12), 3877- 17. Liu, C.; Lin, S.; Zhou, C.; Yu, W.,
3881. Polymer 2013, 54 (1), 310-319.
3. Achmad, F.; Yamane, K.; Quan, S.; 18. Zhou, L.; Zhao, G.; Jiang, W., Indust.
Kokugan, T., Chem. Eng. J. 2009, 151 Eng. Chem. Res. 2016, 55 (19), 5565-
(1), 342-350. 5573.
4. Kolstad, J. J.; Vink, E. T. H.; De Wilde, 19. Miller, K. R.; Soucek, M. D., Eur.
B.; Debeer, L., Polym. Degrad. Stabil. Polym. J. 2012, 48 (12), 2107-2116.
2012, 97 (7), 1131-1141. 20. Lin, S.; Guo, W.; Chen, C.; Ma, J.;
5. Castro-Aguirre, E.; Iñiguez-Franco, F.; Wang, B., Mater. Des. 2012, 36, 604-
Samsudin, H.; Fang, X.; Auras, R. Adv. 608.
Drug Deliv. Rev. 2016, 107, 333–366. 21. Wang, Z.; Zhang, M.; Liu, Z.; Zhang,
6. Hirao, K.; Nakatsuchi, Y.; Ohara, H., S.; Cao, Z.; Yang, W.; Yang, M., J.
Polym. Degrad. Stabil. 2010, 95 (6), Appl. Polym. Sci. 2018, 135 (11),
925-928. 46009.
7. Song, X.; Zhang, X.; Wang, H.; Liu, F.; 22. Olewnik, E.; Czerwiński, W.;
Yu, S.; Liu, S., Polym. Degrad. Stabil. Nowaczyk, J.; Sepulchre, M.-O.;
2013, 98 (12), 2760-2764. Tessier, M.; Salhi, S.; Fradet, A., Eur.
8. Leibfarth, F. A.; Moreno, N.; Hawker, Polym. J. 2007, 43 (3), 1009-1019.
A. P.; Shand, J. D., J.Polym. Sci. A
Polym. Chem. 2012, 50 (23), 4814-
4822.
9. Al-Salem, S. M.; Lettieri, P.; Baeyens,
J., Waste Manage. 2009, 29 (10), 2625-
2643.
10. Song, X.; Wang, H.; Zheng, X.; Liu, F.;
Yu, S., J. Appl. Polym. Sci. 2014, 131
(19), 40817.
11. Petrus, R.; Bykowski, D.; Sobota, P.,
ACS Catal.2016, 6 (8), 5222-5235.
12. Musidang, A.; Jiratumnukul, N., Key
Eng. Mater. 2015, 659, 570-574.
13. Torpanyacharn, O.; Sukpuang, P.;
Petchsuk, A.; Opaprakasit, P.;
Opaprakasit, M., Polym. Bull. 2018, 75
(1), 395-414.
14. Plichta, A.; Lisowska, P.; Kundys, A.;
Zychewicz, A.; Dębowski, M.;
Florjańczyk, Z., Polym. Degrad. Stabil.
2014, 108, 288-296.
15. Li, L.; Liu, X.; Niu, Y.; Ye, J.; Huang,
S.; Liu, C.; Xu, K., J. Biomed. Mater.
Res. B Appl. Biomater. 2017, 105 (5),
1200-1209.
16. Yi, W.-J.; Li, L.-J.; Hao, Z.; Jiang, M.; PC154
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Eng. Chem. Res. 2017, 56 (16), 4867-
4877.

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Encapsulation of 2-methylanthraquinone by ethyl cellulose for use as controlled-release
anti-termite materials
Sovivort Horn1, Chariya Kaewsaneha1*, Duangporn Polpanich2, Paiboon Sreearunothai1,
Pakorn Opaprakasit1,*
1
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology (SIIT),
Thammasat University, Pathum Thani 12120, Thailand
2
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency,
Pathum Thani 12120, Thailand
*E-mail: [email protected], [email protected]

2-Methylanthraquinone (MeQ), an active compound found in Tectona grandis

heartwood (teak heartwood), exhibits high anti-termite and anti-rot fungi activity. To provide
controlled and prolonged activity in practical use, a process for encapsulation of the compound
by using ethyl cellulose (EC) has been developed. Ultrasonication was employed in the
preparation of the nanocapsules, using poly[vinyl alcohol] (PVA) and/or sodium dodecyl
sulfate (SDS). Nanodroplet of dichloromethane (oil phase) in the presence of MeQ and EC was
generated in an aqueous continuous phase. The subsequent evaporation of the oil phase resulted
in the precipitation of MeQ and EC into the spherical nanocapsules. The MeQ:EC weight ratio
of 1:8 and the use of PVA and/or SDS at 0.1 wt% promoted the formation of monodisperse
spherical particles with high stability. The presence of MeQ embedded into the EC matrix was
confirmed by Fourier transform infrared (FTIR) spectroscopy. The encapsulation efficiency,
loading capacity, and release behaviors of the active compound from the nanospheres and their
anti-termite and/or anti-rot fungi properties are for further investigation.

1. Introduction Many tropical plants are known to

Termites are considered as one of the have a wide range of chemical compounds
most problematic pests threatening to either that act as natural insecticides by which they
agriculture or urban structures, causing play a role as antifeedants, repellent,
significant losses each year.1 inhibitors and oviposition behavior.5 Teak
Dichlorodiphenyltrichloroethane (DDT), (Tectona grandis), tropical trees commonly
aldrin and dieldrin have been known as found in Asia, such as Thailand, Myanmar,
synthetic insecticides used in effective India and Indonesia, are considered as one of
termite infestation protection. On the other the plants that produce secondary metabolic
hand, these have been banned in many products. 2-methylanthraquinone (MeQ) is
countries, as their residuals have negatively one of the main components, which has been
affected the environment.2 Moreover, the identified in teak wood extracts. Moreover,
drawbacks of using chemical insecticides to this compound also exhibits insecticidal and
control termites are residue problems, antimycotic activity.6, 7 Furthermore, many
harmful on non-target organisms, resistance studies indicated that MeQ was responsible
in the treated pests, and increased cost of for providing durability to teak wood, against
insecticide application, leading to serious termite infestations and fungi.8, 9 Ismayati et
public’s concerned.3, 4 To deal with this issue, al (2016) studied the activity of MeQ (which
many studies have been conducted to develop was isolated from teak heartwood) against
plant-based chemicals as a novel, efficacy two species of subterranean termites,
and safe insecticides to control termites. Coptotermes formosanus and Reticulitermes PC155

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
speratus by using no-choice feeding tests. transmission electron microscopy, dynamic
The results indicated that interactions light scattering, zeta sizer, and Fourier
between MeQ and other components in teak transform infrared spectroscopy. The
wood extracts led to a high feeding deterrent nanocapsules are aimed for use as anti-
effect.10 At high concentrations, MeQ is toxic termite materials.
to termite Reticulitermes flavipes and acts as
a repellent to dry wood termite Cryptotermes 2. Materials and Methods
brevis.10-12 However, most of these studies 2.1 Materials
have focused on the direct application of Ethyl cellulose (EC, 48% ethoxyl),
MeQ to termites. The study on the poly[vinyl alcohol] (PVA, MW=30,000-
encapsulation of MeQ for use as anti-termite 70,000), sodium dodecyl sulfate (SDS, ACS
materials has not been reported. grade), 2-methylanthraquinone (MeQ, HPLC
To overcome the problem of grade), dichloromethane (DCM, ACS grade)
degradation and unpleasant odor of MeQ were used as received. Deionized (DI) water
during the processing of feeding, was applied throughout the work.
encapsulation or embedding of the active 2.2 Preparation of nanocapsules
ingredient into a polymer matrix can be The nanocapsules were prepared by
considered. The polymer matrix protects not miniemulsion process. Essentially, 1.0 g EC
only the active ingredient from the was dissolved in 20 ml DCM under magnetic
environment but also provides biocompatible stirrer. MeQ (MeQ:EC at ratio 1:8 w/w) was
property. Ethyl cellulose (EC) is a derivative added into the solution and continuously
of cellulose, which is the most abundant stirred for 10 min. Then, the solution was
organic polymer. The material is an added into 100 ml aqueous phase containing
important structural component of the different concentrations of PVA or SDS, i.e.,
primary cell wall of green plants. For 0.1, 0.2, and 1.0 w/v, while being
industrial use, this is mainly obtained from ultrasonicated at 40% amplitude for 4 min.
wood pulp and cotton. EC uses in food- After slow evaporation of the organic solvent
packaging applications and as a barrier under the fume hood, nanocapsules were
coating material for controlled release of obtained.
pharmaceutical products. 2.3 Characterizations
In this work, nanocapsules of MeQ Particle size and size distribution of
embedded into the EC matrix are fabricated the nanocapsules were measured by light
by using a facile method based-on scattering technique (Zetasizer; Malvern,
miniemulsion process. By ultrasound Nano ZS). The samples were diluted by DI
treatment, nanodroplet of dichloromethane water and measured thrice. Morphology of
(oil phase) in the presence of MeQ and EC the nanocapsules was observed by using a
are generated in an aqueous continuous phase transmission electron microscope (JEM
containing poly[vinyl alcohol] (PVA) and/or 2100Plus, JOEL). Fourier transform infrared
sodium dodecyl sulfate (SDS) stabilizing spectrometer (Thermo Scientific Nicolet iS5)
agents. The subsequent evaporation of the oil was employed to investigate their chemical
phase results in precipitation of MeQ and EC compositions. All FTIR spectra were
into spherical nanocapsules. The synthesized collected at a spectral resolution of 2 cm-1,
nanocapsules are then characterized by with 32 co-adding scans.
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 By using polymeric PVA as a
3. Results & Discussion stabilizing agent, stable nanocapsules with
3.1 Preparation of nanocapsules monodispersity and an average size of 243,
Nanocapsules of MeQ/EC was 242, and 221 nm were obtained when using
prepared by a simple and efficient method 0.1, 0.2, and 1.0 wt%, respectively. At low
based on the miniemulsion process. By concentrations (0.1 and 0.2 wt.%), the
applying ultrasonication, high-intensity sonic average size of the nanocapsules is not
waves were employed to produce intense significantly different. When the stabilizer
disruptive force to disperse the organic phase concentration was increased to 1.0 wt%, the
and aqueous phase into fine droplets.13 This average size decreased.
leads to a formation of uniform-size The size of the nanocapsules
nanoparticles. stabilized by PVA was larger than those
As concentrations of stabilizing stabilized by SDS. In the miniemulsion
agents, can affect the stability of the initial process, the formation of stable oil droplets
droplets and the final solid particles,14 to dispersed in the water phase requires a
obtain stable nanocapsules with high surface-active agent to reduce the surface
encapsulation efficiency, the effect of energy between the oil and the water phases,
concentrations of stabilizers, e.g., SDS and and hydrophobe to suppress the Ostwald
PVA were examined. The average particle, ripening.16 The presence of DCM and MeQ
size, size distribution, polydispersity index dispersions helps to promote hydrophobic
(PDI), and morphology of the nanocapsules forces of EC chains, thereby increasing the
were characterized, as summarized in Table rigidity of the hydrophobic core composing
1. of MeQ. PVA molecules are adsorbed onto
By using SDS as a stabilizing agent, the particle’s surface in a multilayer structure
the results showed that the average size of all and extend their hydrophobic parts into the
nanocapsules decreased with increasing aqueous phase to stabilize the particles and
stabilizer concentration. It was observed that hence promote an efficient emulsification
at 0.1, 0.2, and 1.0 wt% of the anionic SDS, process.17 In contrast, SDS small molecules
this small stabilizing agent produced stable turn their hydrophobic parts of carbon chains
and monodisperse nanocapsules, with an into the oil droplet and allow the sulfate
average size of 150, 140, and 134 nm, groups to stabilize particles.
respectively. The high and long-term stability Morphology of the resulting
of these anionic nanocapsules is likely due to nanocapsules was further characterized via
high negatively-charged zeta potential value TEM, as displayed in Figure 1.
as a result from the presence of sulfate groups
of the surfactant surrounded the particle’s
surface.15

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 1. Particle size, size distribution and zeta sizer of nanocapsules prepared from different
types and concentrations of stabilizing agents
Average size (nm) Zeta potential
Type Amount (%) PDI
± SD (mV) ± SD
0.1 150 ± 5 0.28 -43.7 ± 2.4
SDS 0.2 140 ± 2 0.18 -44.3 ± 3.0
1.0 134 ± 2 0.13 -54.8 ± 0.6
0.1 243 ± 4 0.17 -
PVA 0.2 242 ± 3 0.15 -
1.0 221 ± 7 0.13 -
SD = standard deviation; PDI = polydispersity index
The presence of MeQ embedded into
the EC matrix by using PVA and/or SDS as
surfactants, with a concentration of 0.1 wt%
was confirmed by FTIR spectra as shown in
Figure 2.
An absorption frequency at 2924 cm-
1
indicates C-H stretching. The strong band of
C=O occurs at 1670 cm-1 and the C=C
stretching bands for aromatic rings occur in
pairs at 1588 cm-1, as indicative of MeQ.18
Moreover, the peak at 1323 cm-1 corresponds
to the O-H group while that at 706 cm-1
corresponds to the C-H bending vibrations of
the aromatic ring.18 These indicate the
presence of MeQ and EC in the
nanocapsules. In addition, based on the
intensity ratio of the bands at 1670/2924, it
can be quantitatively estimated that the
weight ratio between MeQ and EC in the
sample is 1:2 efficiency.
In practical use, the prepared
nanocapsules are aimed for use as anti-
termite feeding materials. With expectation,
Figure 1. TEM images of nanocapsules MeQ is obscured by the natural cellulose
stabilized by 0.1% SDS (A) and 0.1 wt% matrix, which is a preferred food source for
PVA (B). termites. When termites bring the
The nanocapsules prepared by both nanocapsules to their nest, termite mortalities
stabilizing agents displayed spherical and within the nest will be achieved.
monodisperse in size. In the dry state, the size
of the nanocapsules was smaller than as in the 4. Conclusions
hydrodynamic state. This supported the The nanocapsules of MeQ/EC
presence of a multilayer structure of PVA dispersed in the aqueous phase were
molecules on the particle surface. successfully prepared by using a simple and
efficient miniemulsion process. By using low
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
concentration (0.1 wt%) of different types of
stabilizing agents, e.g., anionic SDS and Acknowledgements
steric PVA, nanocapsules with high stability, The financial supports provided by
and monodispersity were produced. The the center Excellence in Materials and
encapsulation efficiency, loading capacity Plasma Technology (CoE M@P Tech), SIIT,
and release behaviors of the active compound Thammasat University are gratefully
from the nanospheres and their anti-termite acknowledged.
and/or anti-rot fungi properties will be further
investigated.

Figure 2. FT-IR spectra: (a) ethyl cellulose, (b) MeQ, (c) nanoparticle with 0.1%PVA and (d)
nanoparticle with 0.1%SDS.

References 5. Bakaruddin, N. H.; Dieng, H.; Sulaiman,

1. Guan, Y.-Q.; Chen, J.; Tang, J.; Yang, S. F.; Ab Majid, A. H. Inf. Process. Agric.
L.; Liu, J.-M. Int. Biodeter. Bioder. 2011, 2018, 5 (3), 298-307.
65 (3), 389-395. 6. Singh, P.; Jain, S.; Bhargava, S.
2. Elango, G.; Abdul Rahuman, A.; Phytochemistry. 1989, 28 (4), 1258-1259.
Kamaraj, C.; Bagavan, A.; Abduz Zahir, 7. Sumthong, P.; Romero-González, R. R.;
A.; Santhoshkumar, T.; Marimuthu, S.; Verpoorte, R. J. Wood. Chem. Technol.
Velayutham, K.; Jayaseelan, C.; Kirthi, 2008, 28 (4), 247-260.
A. V.; Rajakumar, G. Ind. Crops. Prod. 8. Haupt, M.; Leithoff, H.; Meier, D.; Puls,
2012, 36 (1), 524-530. J.; Richter, H. G.; Faix, O. Holz als Roh-
3. Bettiol, W. Outlook. Pest. Manag. 2011, und Werkstoff. 2003, 61 (6), 473-474.
22 (6), 280-283. 9. Lukmandaru, G.; Takahashi, K. Ann. For.
4. Tapondjou, L.; Adler, C.; Bouda, H.; Sci. 2008, 65 (7), 708-708.
Fontem, D. J. Stored. Prod. Res. 2002, 38 10. Ismayati, M.; Nakagawa-Izumi, A.;
(4), 395-402. Kamaluddin, N. N.; Ohi, H. Insects.
2016, 7 (4). PC159

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
11. Da Costa, E.; Rudman, P.; Gay, F. 16. Han, S. W.; Song, H. Y.; Moon, T. W.;
Empire Forestry Review. 1958, 291-298. Choi, S. J. Food Chem. 2018, 242, 91-97.
12. Rudman, P.; Gay, F. J.; Da Costa, E. W. 17. Kaewsaneha, C.; Tangboriboonrat, P.;
B., Sauerländer. 1967. Polpanich, D.; Eissa, M.; Elaissari, A. J.
13. McClements, D. J. Soft Matter. 2011, 7 Colloid. Interf. Sci. 2013, 409, 66-71.
(6), 2297-2316. 18. Allen, N. S.; Hamzah, H.; Edge, M.;
14. Bohrey, S.; Chourasiya, V.; Pandey, A. Liauw, C. M.; Catalina, F.; Edge, R.;
Nano Converg. 2016, 3 (1), 3. Navaratnam, S. J. Photoch. Photobio. A.
15. Shah, V.; Bharatiya, B.; Mishra, M. K.; 2018, 356, 530-544.
Ray, D.; Shah, D. O. J. Mol. 2019, 273,
222-230.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Microwave-assisted preparation of D-lactide
Vavang Paxay1, Khanin Nueangnoraj1, Atisa Petchsuk2, Pakorn Opaprakasit1,
Siwarutt Boonyarattanakalin1*
1
School of Bio-chemical Engineering, Sirindhorn International Institute of Technology, Thammasat University,
Pathum Thani 12120, Thailand
2
National Metal and Material Technology Center 114 Thailand Science Park, Pathum Thani 12120, Thailand
*E-mail: [email protected]

Sustainable development planning points to the necessary replacement of non-

biodegradable plastics with biodegradable polymers. Polylactic acid (PLA) is a prominent
biodegradable polymer made from renewable resources. The ring-opening polymerization of
lactide is the most efficient production method of PLA because it gives high yields and purity.
Lactide is produced by depolymerization of lactic acid oligomers under high temperature and
reduced pressure. In this study, microwave radiation was applied to assist the lactide
production. In contrast to conventional heating, the microwave-assisted depolymerization is a
more energy-efficient method. The microwave-assisted preparation of D-lactide was carried
out by using oligo-D-lactic acid as a reactant, under the reaction temperature of 170-250 °C, 1-
20 kPa in pressure, and the reaction time of 60-180 minutes. The characterizations of the
product were carried out by Fourier Transform Infrared Spectroscopy (FTIR) and High-
Performance Liquid Chromatography (HPLC). The highest yield of D-lactide was 63.7 %
obtained by using 60 g of oligo-D-lactic acid with tin (II) octoate 0.1% at 210 °C, 120 minutes
and 2.3 kPa.

1. Introduction L-lactic acid (PLLA), poly-DL-lactic acid

Recently, plastic disposal is an (PDLLA).2-5
environmental issue that needs to be fixed PLA is produced from lactic acid (LA)
urgently. Biodegradable materials from from the fermentation of carbohydrates by
renewable resources would ideally replace condensation polymerization in many
petroleum-based plastics. Polylactic acid approaches such as azeotropic dehydration
(PLA) is a biodegradable polymer, which is condensation, direct polycondensation, solid-
made from renewable resources. PLA is state polymerization, and ring-opening
biodegradable and biocompatible. Therefore, polymerization.6 Most of PLA production
to replace non-biodegradable polymers in methods focus on the production of PLLA
order to reduce their negative impacts on the and PDLLA, wherein reactants of production
environment, PLA is widely applied in are L-lactide and DL-lactide. This report
several products in medical, packaging, focuses on the production of D-lactide from
agricultural and electronical industries, from oligo-D-lactic acid.
kitchen utensils to artery stent. High molecular weight (Mw) PLA has
The major drawback of PLA is its high high mechanical properties which make it
cost which is almost double of that of appropriate for various applications.9 Ring-
conventional plastics.1 Hence, in order to opening polymerization (ROP) is an
overcome the cost hurdle, the more efficient approach that is widely used in the
technology of PLA production is essential. production of high molecular weight PLA.
There are several different forms of PLA The production is carried out in three stages,
PC161
including poly-D-lactic acid (PDLA), poly- which are polycondensation, depolymeri-

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
zation, and ring-opening polymerization, and can be used for food-grade.9, 10 Lactide
successively.10 ROP is an alternative has three types of stereoisomers, which are
approach of production that can give a high meso-lactide, D-lactide and L-lactide.10
molecular weight of PLA with high yields, Lactide can be purified by distillation,
high purity, and allows for controlling solvent crystallization, and melt
properties of the polymer.3, 11 crystallization. 9

Lactide is generated from oligomers of This study focuses on the

lactic acid (OLA) by depolymerization under development of microwave-assisted
reduced pressure, high temperature, and preparation of D-lactide from oligo-D-lactic
catalysts. The conventional heating methods acid.
have been previously used in lactide
preparation.9 However, conventional heating 2. Materials and Methods
methods have typically shown low 2.1 Materials
production efficiencies because of the high Oligomers of D-lactic acid produced
energy usage over long reaction times. from a starting material-D-lactic acid without
The introduction of microwave a catalyst by using conventional heating
radiation heating has greatly influenced the preparation. Tin (II) octoate, acetonitrile and
efficiency of chemical reactions.12 The direct phosphoric acid were purchased from Sigma-
heat of microwave radiation positively Aldrich.
enhances endothermic chemical reactions by 2.2 Lactide Preparation
shorten reaction time, increase reaction yield, The preparation of lactide was
and allow milder reaction conditions.9 performed by Milestone flexiWAVE
Microwave radiation heating has been used microwave synthesis platform. Oligo-D-
for the preparations of lactide.7, 8, 13 The lactic acid (60 g) and the catalyst with several
microwave-assisted preparations have been quantities were placed in a 100 mL round
optimized with various catalysts, reaction bottom flask equipped to a reflux condenser,
temperatures, reaction pressure, reaction time product vessel, and vacuum system,
and powers of irradiation.7,8, 13 respectively. The vacuum system was
The lactide preparations by the connected with a cold trap. The reaction
microwave-assisted method were more conditions were 170-250 °C, 1-20 kPa, 60-
energy-efficient and required a shorter 180 minutes. Tin (II) octoate was used for the
reaction time. Most of the catalysts for the depolymerization. The characterizations of
lactide preparations are complexes of metals lactide products were done by using FTIR
including tin and zinc. These catalysts are and HPLC.
used in the depolymerization step. 2.3 Lactide Analysis
Tin (II) octoate is one of the most 2.3.1 ATR-FTIR Analysis
efficient catalysts that is used in the Infrared spectroscopy analysis on D-
preparation of lactide, as it increases the rate lactide was performed by Attenuated Total
of reaction and leads to the successful Reflectance-Fourier Transform Infrared
transformation of the reactant at mild Spectroscopy (ATR-FTIR, Nicolet iS5) with
conditions. It should be noted that tin (II) an iD7 ATR accessory and a diamond crystal.
octoate is approved by the U.S. Food and The spectra were recorded at a resolution of
Drug Administration because it is low toxic
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
4 cm-1 with a total of 32 scans. Each sample asymmetric and symmetric of C-O-C in the
measurement was repeated two times. lactonic ring appear at 1,266 cm-1 and 1,093
2.3.2 HPLC Analysis cm-1, respectively. The band of COO ring
The identification and quantitative breathing mode appears at 933 cm-1. The
analyses of D-lactic acid, oligo-D-lactic acid FTIR spectra of pure D-lactide, and product
and D-lactide were done by using a HPLC from experiments No 1, 2, 3 and 6 (Table 1),
(Agilent 1260 Infinity, G1329B, Germany), are shown in Figure 1:
equipped with a Zorbax Eclipse C18 (150
mm × 4.6 mm × 3.5 µm) column. The
analysis was done at 40 °C with a total
retention time of 15 min and a mobile phase
flow rate of 1.0 mL/min. The mobile phase
consisted of 0.015 mol/L orthophosphoric
acid and acetonitrile (88:12 v/v). The injected
sample volume was 5 μL. The UV-detector
was set at a wavelength of 210 nm. The
conditions of HPLC analysis were chosen
based on literature reported elsewhere.4
Figure 1. FTIR Spectrum of standard D-
3. Results and Discussion lactide and products from experiments no. 1,
3.1 Qualitative analysis of crude lactide by 2, 3 and 6 (Table 1).
using the ATR-FITR
The qualitative analysis of the lactide 3.2 Quantitative analysis of crude lactides
products was performed by using an ATR- by using the HPLC
FTIR. The ATR-FTIR spectrum of functional The HPLC chromatogram showing
groups of pure lactide shows the bands at the retention time of each compound is
2,996 cm-1 and 2,935 cm-1 from the shown in Figure 2. The retention times are the
asymmetric and symmetric valence following: D-lactic acid at 1.752 min, low
vibrations of C-H, respectively. The peak at Mw oligo-D-lactic acid at 3.065 min, D-
-1
1,752 cm is from cyclic dilactone C=O. The lactide at 6.680 min, and high Mw oligo-D-
asymmetric and symmetric bending lactic acid at 9.162 min.
vibrations of C-H from CH3 appear at 1,456
cm-1 and 1,355 cm-1, respectively. The
Table 1. Lactide conversion yield of each experiment done by using 60 g of starting material-
oligo-D-lactic acid Mw = 970 g/mol; polydispersity index (PDI)= 1.52.
Exp Mw of PDI of Cat Cat conc. Temp Time Press Crude Lactide
No. OLA OLA (mol %) (°C) (min) (kPa) product (g) yield (%)
(g/mol)
1 970 1.52 Sn(Oct)2 0.1 210 90 2.3 21.46 43.09
2 970 1.52 Sn(Oct)2 0.2 210 90 2.3 16.39 19.42
3 970 1.52 Sn(Oct)2 0.3 210 90 2.3 13.62 24.32
4 970 1.52 Sn(Oct)2 0.4 210 90 2.3 13.49 8.72
5 970 1.52 Sn(Oct)2 0.1 210 30 2.3 16.39 29.55
6 970 1.52 Sn(Oct)2 0.1 210 60 2.3 19.12 41.54
7 970 1.52 Sn(Oct)2 0.1 210 120 2.3 23.39 63.7
8 970 1.52 Sn(Oct)2 0.1 210 150 2.3 20.22 46.72
9 970 1.52 Sn(Oct)2 0.1 210 6h 0.12 8.71 10.69
Note: the experiment no.9 was done by using conventional heating preparation.
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 3.3 Effect of catalyst concentration,
reaction time and comparison of
conventional and microwave heating
preparation
3.3.1 Effect of catalyst concentration

Figure 2. HPLC chromatogram of the

products obtained from experiment no. 9.
The lactide conversion yields were
calculated as follows:
(1)+(2)+(3) Starting material
=
(3) High MW OLA

(1) = Area of LA = 301.37 Figure 3. The catalyst concentration effect

(2) = Area of low Mw OLA = 645.32 on lactide yields by using the oligo-D-lactic
(3) = Area of high Mw OLA = 709.68 acid (60 g) with the tin (II) octoate catalyst
concentrations of 0.1, 0.2, 0.3 and 0.4 % (by
Starting material = 60 g moles) at 210°C, 90 minutes and 2.3 kPa.
(3) x Starting material
The effect of catalyst concentration
High Mw OLA = (1)+(2)+(3) was investigated by carrying out experiments
using tin (II) octoate as a catalyst. The
709.68 𝑥 60
High Mw OLA = 301.37 + 645.32 + 709.68 catalyst concentrations were 0.1, 0.2, 0.3 and
0.4 % (by mole). All experiments were
High Mw OLA = 25.7 g performed using 60 g of oligo-D-lactic acid
Crude product x 100 for 90 minutes and the reaction temperature
Lactide yield (%) = High Mw OLA and pressure were fixed at 210 °C and 2.3
7.59 x 100 kPa, respectively. The lactide conversion
Lactide yield (%) = yields are shown in Figure 4. Using 0.1 % of
25.7

Lactide yield = 29.55 % (experiment no. 5 tin (II) octoate results in the highest lactide
(Table 1)) conversion yield while 0.4 % of tin (II)
octoate leads to the lowest product yield. The
For the experiments carried out using tin (II) octoate at the concentration of 0.1%
microwave heating, the highest lactide significantly generated the lactide
conversion yield at 63.7 % was achieved by composition by backbiting of hydroxyl end
using 60 g of oligo-D-lactic acid with tin (II) of chain.9 Increasing the catalyst
octoate (0.1 %) at 210 °C, 120 min and 2.3 concentration resulted in the reduction of the
kPa. lactide formation, therefore, there were
reactants left after the reaction time was over.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.3.2 Effect of reaction time reaction time of 120 minutes. The
conventional heating conditions yielded only
70.0 10.69 % by using the reaction time of 6 hours.
Since microwave heating preparation
50.0 transmitted more directly into the molecules
Yield (%)

of the starting material, microwave heating

30.0
leads to faster and more efficient heating.12
10.0 Therefore, the reactions heated by
microwave reactions were rapidly completed
-10.0 30 60 90 120 150 at the shorter reaction times. On the other
Reaction time (min) hand, for the reaction heated by the
Figure 4. The reaction time effect on lactide conventional heating, the reactant took
yields by using the oligo-D-lactic acid (60 g) longer to reach the required reaction
with the tin (II) octoate catalyst (0.1%) at temperature which caused the process to have
210°C, 2.3 kPa and the reaction times of 30, a longer reaction time. The product yield
60, 90, 120 and 150 minutes. obtained from the microwave heating
The effect of reaction time on lactide preparation was higher than the conventional
yield was also investigated. The reaction time heating preparation.
was varied from 30, 60, 90, 120 and 150
minutes. All experiments were carried out 4. Conclusion
using 60 g of oligo-D-lactic acid using tin (II)
The catalyst (tin (II) octoate)
octoate (0.1%) as a catalyst and the reaction
temperature and pressure were fixed at 210 concentration of 0.1 % resulted in the highest
°C and 2.3 kPa. The yields of lactide yield of 43.09 % at 210 °C, 90 min and 2.3
increased with increasing reaction time up to kPa. The highest lactide yield obtained was
120 minutes as shown in Figure 5 and 63.7 % at a reaction time of 120 min by using
decreased afterward. The reaction was not 0.1 % tin (II) octoate at 210 °C and 2.3 kPa.
finished at the reaction times of shorter than The product yield obtained was much higher
120 minutes. However, for the reaction time from the microwave heating preparation than
of 150 minutes, the longer vacuum time may the conventional heating preparation and its
remove the lactide product from the product reaction time was shorter than the
vessel. Thus, the highest yield obtained from conventional heating preparation than in
120 minutes. quintuple of that. Therefore, microwave-
3.3.3 Comparison of microwave and assisted preparation is an efficient method.
conventional heating preparation
The comparison of microwave and
Acknowledgements
conventional heating preparation was done in This research was supported by
experiments no.7 and 9 which were the National Metal and Materials Technology
microwave and conventional heating Center (MTEC). We thank Center of
preparation, respectively. These reactions Scientific Equipment for Advanced
were done by using the same conditions of Research, Thammasat University
the reaction (except the pressure shown as in (TUCSEAR) for supporting facilities and
Table 1). equipment.
The microwave heating preparation
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resulted in a product yield of 63.7% at a

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
References 8. Koichi, H.; Karunari, M.; Hitomi, O.
1. Van den Oever, M.; Molenveld, K.; J. Chem. Eng. Japan 2009, 42, 687-690.
van der Zee, M.; Bos, H. T. Wageningen 9. Rafael, A.; Loong- Tak, L.; Susan,
Food Biobased Res. 2017, 26-27. E. M. S.; Hideto, T., Poly(lactic acid)
2. Tsuji, H. Adv. Drug Deliv. Rev. 2016, Synthesis, Structures, Properties, Processing,
107, 97-135. and Applications. John Wiley & Sons 2010,1-
3. Inkinen, S.; Hakkarainen, M.; 16.
Albertsson, A. C.; Sodergard, A. 10. Sungyeap Hong, C. L. Modern Chem.
Biomacromol. 2011, 12 (3), 523-32. Appl. 2014, 02 (04).
4. Zamanova, M. K.; Glotova, V. N.; 11. Balk, M.; Behl, M.; Wischke, C.;
Izhenbina, T. N.; Krutas, D. S.; Novikov, V. Zotzmann, J.; Lendlein, A. Adv. Drug Deliv.
T. Procedia Chem. 2014, 10, 244-251. Rev. 2016, 107, 136-152.
5. Storti, G.; Lattuada, M., Synthesis of 12. Rana, K. K.; Rana, S. OALib 2014, 01
bioresorbable polymers for medical (06), 1-20.
applications. 2017, 153-179. 13. Ying, M. Z.; Peng, w.; Ning, H.; Hai,
6. Muller, J.; Gonzalez-Martinez, C.; F, L. Willey InterScience 2007, 28, 417-421.
Chiralt, A. Materials 2017, 10 (8).
7. Yang, X.-G.; Liu, L.-J. Polym. Bull.
2008, 61 (2), 177-188.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Investigation of gelatin hydrogel gelation for drug release system
Wanlapa Natedungta, Walaiporn Prissanaroon-Ouajai*
Department of Industrial Chemistry, Faculty of Applied Science,
King Mongkut’s University of Technology North Bangkok, Thailand
*E-mail: [email protected]

This research is focused on preparation of glutaraldehyde (GA)–crosslinked gelatin

hydrogel for application in controlled drug release system. Effect of GA concentration and
gelation temperature were investigated. The optimum gelation temperature was found to
be 40 OC. The properties of the gelatin hydrogel depend on the presence of GA quantity.
Increasing GA concentration caused increments in gel fraction, whereas porosity and
swelling percentage decreased. Result obtained from scanning electron microscopy (SEM)
showed that the greater amount of GA led to smaller pore size, hence affecting the
mechanical property of hydrogel. The release of model drug, hydroquinone
monosulfonate, from gelatin hydrogels was studied in pH 7.4 phosphate buffer and pH 4.5
acetate buffer solutions. The result showed that rate of drug release from the hydrogels
was not significantly different for both pH solutions but influenced by GA concentration.
The gelatin hydrogel with a higher crosslinking level resulted in a slow release rate of drug
due to small porous structure of gelatin hydrogel.

1. Introduction Hydrogel is an interesting material for

Drug delivery is necessary to control TDDS. Its porous structure has the ability to
the plasma drug concentration for store and release drugs through the skin layer.
effectiveness in the treatment of patients. In addition, the pore size can be controlled
Transdermal drug delivery system (TDDS) is through crosslinking reactions. Therefore,
one of the effective methods. The advantage this research focuses on preparation of
of TDDS is avoids ‘first-pass’ metabolism of gelatin hydrogel by studying conditions of
drugs, reduces fluctuations in plasma levels preparation, including the effect of
of drugs and easy termination of drug temperature and the concentration of
delivery in case of toxicity.1 The application crosslinking agents. The aim of this research
of gelatin to drug delivery systems or drug is to develop gelatin hydrogel as a material to
release control systems has long been using. control drug release from external conditions
Gelatin microparticle preparation can be to stimulate in the future.
synthesized by controlling particle size
through synthesis via crosslinking reaction. 2. Materials and Methods
As a result, the rate of dissolution of gelatin 2.1 Materials
in the solution is reduced. It can be prepared Gelatin ( Food grade) was purchased
as a material to control the release of long- from J R F&B Co. , Ltd (Thailand).
acting drugs.2 These properties of gelatin Glutaraldehyde (25%) and hydroquinone
particles can be used to control symptoms of monosulfonic acid potassium salt were
certain diseases for a longer time and purchased from Sigma- Aldrich Co. , Ltd
maintain drug concentration for a long (Singapore).
period.3-5 PC167

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2. 2 Effect of temperature on gelatin Where W0 is the weight of hydrogel before
hydrogel preparation extraction and Wi is the weight of hydrogel
Gelatin (Gel) was dissolved at 65 oC after extraction.
with distilled water. The temperature of the 2.5 Gel porosity
solution was reduced to achieve 50 oC and 40 Porosity is one of the important
o
C. Glutaraldehyde (GA), crosslinking agent, factors that will indicate the effectiveness of
was subsequently added into the solution the drug absorbing inside the hydrogel or
with the weight ratio of Gel: GA equal to 10: releasing outside. The dry hydrogel (0.005
0.125 and 10: 0.25. The gelation time was grams) were weighed and soaked in 20 ml of
recorded after the solution form a soft gel ethanol for 24 hours. After that, the hydrogel
structure. was filtered by using vacuum filtration and
2.3 Effect of crosslinking agent on gelatin weighing of the hydrogel after filtering.
hydrogel preparation Porosity of the gel can be evaluated from6
Gelatin was dissolved at 65 oC with (m2 -m1 )
distilled water. The temperature of the Porosity= ρethanol VHG
(3)
solution was reduced to 40 oC, then GA was
added into the solution. The mass ratio of where m1 is mass of dry hydrogel, m2 is mass
Gel: GA were 10: 0.25 (Gel 0.25), 10: 0.50 of hydrogel after immersion and
(Gel 0.50) and 10:1.00 (Gel 1.00).The filtration, ρethanol is the density of ethanol
solution was poured into a silicone mold. The (0.789 g/cm3) and VHG is the volume of the
hydrogel was left in an oven at 55 oC for 4 hydrogel. The hydrogel volume is
hours and washed with distilled water to determined as the dimensional volume.
remove the unreacted of GA. 2.6 Swelling percentage
2.4 Gel fraction percentage Dried hydrogel (1.000 g) was
The quantity of gel is an important immersed in 50 ml distilled water. The
factor that observes the amount of gel swelling behavior of gelatin hydrogel were
insoluble in water. That indicates the measured by immersing the dried hydrogel
efficiency and durability of the hydrogel. The in buffer solutions pH 7.4 and pH 4.5. The
testing procedures were as follows, weight of hydrogel was recorded after
The dry hydrogel (0.005 g) was swollen at 1, 2, 3, 4, 5, 6, 7, 24 and 48 hours.
soaked in 50 ml distilled water and stirred for Swelling percentage of the hydrogel can be
48 hours at room temperature. The wet calculated as7:
Wt -Wo
hydrogel was filtered by vacuum filter and % swelling= W ×100 (4)
o
dried the hydrogel at 60 °C for 24 hours. Gel
fraction percentage was calculated as where Wt is the weight of swelling hydrogel
follows6 at different time and Wo is the initial weight
of dry hydrogel.
W0 -Wi
%sol fraction = ( W0
) ×100 (1) 2.7 Morphological characterization
The morphology of the wet hydrogel
%gel fraction = 100 - %sol fraction (2) was investigated. The hydrogel was cut to
observe cross-sectional structure. The pore
size of the hydrogel was studied under a
scanning electron microscope (FEI Quanta
250 FEG, USA). PC168

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.8 Drug loading efficiency solution for 24 hours before testing. The
Hydroquinone monosulfonate (HQS) hydrogel of both methods was soaked in
was selected as a model drug since it is a phosphate buffer solution pH 7.4 and acetate
negatively charged molecule, as well as buffer solution pH 4.5. The solutions were
dexamethasone phosphate (DEXP), which is tested by shaking at 37 ± 2 ° C. The drug
a drug that is used to treat a variety of release was tested for 48 hours by measuring
diseases such as skin cancer or keloid. every 1 hour in the first 8 hours and
The HQS solution 15% wt of the dry measuring at 24 and 48 hours. In each time of
gel was prepared by using pH 7.4 phosphate sampling, 2 mL phosphate buffer was added
buffer solution as a solvent. The dry hydrogel into the solution. The release of HQS from
(0.5000 g) was soaked in the HQS solution Gel hydrogel was investigated using UV-VIS
for 24 hours. The weight of the swollen spectrophotometer at wavelength 302 nm.8
hydrogel after 24 hours was recorded. Drug
Loading Efficacy (%) was calculated using 3. Results and Discussion
following equation7. At the beginning, the hydrogel was
Wdg prepared by varying GA concentrations and
Drug Loading Efficacy (%) = Wi
×100 (5) gelation time was observed. Gelatin
dissolution was completed at 65 oC. It is
Where Wdg is weight of the HQS within the
difficult to prepare the gelatin hydrogel at this
hydrogel and Wi is weight of the initial HQS
temperature since the gel reaction occurs
in the solution.
very quickly. Therefore, it is necessary to
2.9 Drug release
study the suitable temperature of the gel
The hydrogel which has been
solution before mixing with GA. Table 1
prepared using in-situ drug loading and
shows the gelation time of the gelatin
immersion methods was used to compare the
solution at different temperatures and
drug release efficiency. Gel 0.25 and Gel 1.00
different Gel:GA ratios. It was found that the
were chosen to compare the effect of GA on
amount of GA did not significantly affect
drug release. The in-situ drug loading method
gelation time. However, increase in gelation
was prepared by adding HQS 15%wt of the
time was observed at lower temperature.
gelatin weight during the gelation of the
Therefore, the temperature of 40 oC was
hydrogel. The immersion method was
chosen to study the effect of GA content on
prepared by soaking dry hydrogel in the HQS
the properties of gelatin hydrogel.
Table 1. Gelation time of hydrogel preparation at different temperatures and GA
concentrations.

Sample Weight ratio Gel : GA Gel solution temperature (oC) Gelation time (s)
Gel 0.25 10 : 0.25 60 20
Gel 0.125 10 : 0.125 60 22
Gel 0.25 10 : 0.25 50 26
Gel 0.25 10 : 0.25 40 32

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.1 Appearance of the hydrogel Table 3. Gel fraction percentage and gel
After the gelation completed, clear porosity of gelatin hydrogel.
hydrogel was obtained. The color of the
% Gel % Gel
hydrogel changed according to the amount Sample
fraction porosity
of GA. Table 2 shows the appearance of the Gel 0.25 81.9 ± 6.6 68.5 ± 10.3
hydrogel after removing from the mold. Gel Gel 0.50 94.6 ± 0.3 25.7 ± 12.4
Gel 1.00 98.9 ± 0.5 6.6 ± 4.4
0.25 was light yellow and became darker
brown with increasing the amount of GA.
3.3 Swelling percentage
The gelatin with the most softness was
Result from swelling tests of Gel
resulted from Gel 0.25. Increase in GA
hydrogel in phosphate buffer pH 7.4 and
concentration caused more rigidity. These
acetate buffer pH 4.5 is displayed in Figure
results imply that the crosslinking agent
1. At first 8 hours, the swelling rate increase
affects the physical properties of the
rapidly. Swelling of hydrogel both of buffer
hydrogel. The more GA content is added,
solutions show the similar trend. Therefore,
the more crosslinking level takes place
this implies that the pH does not influence
between the gelatin chains within the
the swelling of the gelatin hydrogel. When
hydrogel, leading to less flexibility of the
comparing the ratio of GA, the greatest
hydrogel.
swelling is Gel 0.25 and %swelling goes
down with higher GA amount. This is due
Table 2. Photo images of Gel hydrogels
to the addition of crosslinking agents,
prepared with difference weight ratio
resulting in a link between the polymer
between Gel and GA for gelation of the
chains. The chains move more difficultly,
hydrogel.
bringing into the reduction of swelling.
Sample Gel 0.25 Gel 0.50 Gel 1.00 3.4 Morphological characterization
Weight SEM micrograph of cross-sectional
ratio Gel : 10 : 0.25 10 : 0.50 10 : 1.00
GA Gel hydrogel is showed in Figure 2. The
inside of Gel hydrogels is close porous
Gel
hydrogel
structure due to crosslinking between
gelatin chain and the GA can create
3.2 Gel fraction percentage and gel porosity. Pore size of Gel hydrogel at
porosity various GA content is observed. An average
Gel fraction percentage and gel pore size of about 14.827 ± 0.1 µm,
porosity of gelatin hydrogel is reported in
Table 3. Increase in gel fraction percentage
was obtained for the hydrogel with high GA 1000 a)
content whereas decrease in gel porosity 800
Gel 0.25
%Swelling

was visible. When increasing the amount of 600

Gel 0.50
crosslinking, the dissolution of the water- 400 Gel 1.00
soluble part of the hydrogel is interrupted, 200
resulting in a higher percentage of gel-
0
forming and keeping the chain closer. 0 10 20 30 40 50 60
time (hr)

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 1200
b)
1000 Gel 0.25 Table 4. Drug loading efficiency (%) of
Gel 0.50 Gel hydrogels at various GA crosslinking
%Swelling

800
Gel 1.00
600 agent content.
400
200
Sample Gel 0.25 Gel 0.50 Gel 1.00
Drug loading
0 55.3 ± 53.4 ± 52.6 ±
0 10 20 30 40 50 60 efficiency
0.4 0.3 0.1
time (hr) (%)
Figure 1. Swelling tests of Gel hydrogel These results can be explained that
crosslink with GA a) in phosphate buffer increasing GA concentration generate tight
solution pH 7.4 and b) in acetate buffer network. Consequently, hydrogel with
solution pH 4.5. lower GA concentration is be able to fill up
more drug into the porous. However, this
9.54 ± 0.1 µm and 7.676 ± 0.3 µm result method contains 55% of drug into the
from Gel 0.25, Gel 0.50 and Gel 1.00, hydrogel. To enhance effective of drug
respectively. Adding amount of GA loading, the HQS is incorporated by in-situ
conduct small pore size of Gel hydrogel method. This procedure dissolves the drug
corresponding to decreasing of gel swollen during the gelation. It can be assumed that
in previous results. the in-situ method incorporates 100% of
a) b) drugs into the hydrogel.
3.6 Drug release
Drug release profile of Gel hydrogel
crosslink with GA is presented in Figure 3.
Both Gel 0.25 and Gel 1.00 show a similar
release trendy. HQS is released rapidly at
c)
first hour and then slow release rate is
observed. At different pH solution testing
does not have a significant effect on drug
release profile. Considering the effect of
crosslinking concentration on the drug
release, Gel 1.00 show less cumulative
release percentage than Gel 0.25 for both
Figure 2. SEM micrograph of a) Gel 0.25 pH solutions. This suggesting that the
b) Gel 0.50 and c) Gel 1.00 magnification release of drug is difficult from small
x5000. porous of Gel 1.00. Moreover, the results
3.5 Drug loading efficiency exhibit that Gel 1.00 can release the drug
Firstly, immersion method is a for more stable concentration.
technique to diffuse HQS through swelling
behavior of hydrogel. Drug loading
efficiency (%) of Gel hydrogels is
investigated as shown in Table 4. The
hydrogel that higher amount of GA give
slighter drug loading efficiency. PC171

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 160 a)
% Cumulative release

140
120 References
100 1. Kumar, R.; Philip, A. Trop. J. Pharm.
80
60 Res. 2007, 6, 633-644.
Gel 0.25
40 2. Cortesi, R.; Espositoa, E.; Ostia, M.;
20 Gel 1.00
0 Squarzonia, E.; Davisb, S.S.;
0 100 200 300 Nastruzzia, C. Eur. J. Pharm.
Time (min)
Biopharm. 1999, 47,153–160.
160
3. Vandelli, M. A.; Rivasi, F.; Guerra, P.;
b)
% Cumulative release

140 Forni, F.; Arletti, R. Int. J. Pharm.

Gel 0.25
120
100 Gel 1.00 2001, 215, 175–184.
80 4. Gunji, S.; Obama, K.; Matsui, M.;
60 Tabata, Y.; Sakai, Y. J. Surg. 2013, 154,
40
20 991-999.
0 5. Drew, V. J.; Huang, H. Y.; Tsai, Z. H.;
0 100 200 300
Time (min)
Tseng, C. L. J. Polym. Res. 2017, 188,
1-10.
6. Ranjha, N. M.; Ayub, G.; Naseem, S.;
Figure 3. Drug release profile of Gel Ansari, M. T. J Mater Sci: Mater Med.
hydrogel crosslink with GA a) in phosphate 2010, 21, 2805–2816
buffer solution pH 7.4 and b) in acetate 7. OOi, S. Y.; Ahmad, I.; Amin, M. C. I.
buffer solution pH 4.5. M. Ind. Crop. Prod. 2016, 93, 227-234.
8. Wilke, T.; Schneider, M.;
4. Conclusion Kleinermanns, K. Ojpc. 2013, 3, 97-
The cross-linking reaction between 102.
Gel and GA is an important role of
controlling the drug release behavior. Gel
1.00 provides the smallest pore size to
regulate the release rate constant. Therefore
it is suitable for further application as a drug
control release material.

Acknowledgements
This research is supported by
Research fund from Faculty of Applied
Science, King Mongkut's University of
Technology North Bangkok, Thailand.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Characterization of immunoliposomes targeting CD4+ T lymphocytes
Suthasinee Meeroekyai1,2, Thanapak Jaimalai1,2, Nuttee Suree2,3, Panchika Prangkio2,3*
1
Department of Biotechnology, Graduate School, Chiang Mai University, Chiang Mai, 50200, Thailand
2
Division of Biochemistry and Biochemical Technology, Department of Chemistry,
Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand
3
Center of Excellence in Materials Science and Technology,
Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
*E-mail: [email protected]

Drug delivery targeting CD4+ T lymphocytes can be useful for treatment of many
immune-mediated diseases including HIV/AIDS. In this study, we focus on developing
liposomal drug delivery system for improving specific targeting, maintaining drug stability
while minimizing adverse effect of the drug. Liposome was conjugated with CD4 monoclonal
antibody (mAb) as referred to as immunoliposomes in order to direct to the target site through
antigen-antibody recognition. The immunoliposomes were prepared from soyPC and
cholesterol using various total lipid amounts. To evaluate the stability of liposomes, size and
surface charge were characterized using dynamic light scattering (DLS) and zeta potential
measurement, respectively. The results revealed that the mean diameter of liposomes was in
the range of 100-300 nm and the zeta potential of -5 to -20 mV which were stable up to 12
weeks. In addition, attachment of polyethylene glycol (PEG) could promote liposomal cellular
uptake and enhance stability of liposomes due to the increase in hydrophilicity and electrostatic
interaction. Cellular uptake by J-Lat Clone 10.6 cells, CD4+ T lymphocytes was evaluated
using flow cytometry. Our findings showed that immunoliposome composed of 20 mg of
soyPC containing CD4 mAb and PEG was suitable for cellular uptake and could be potentially
used as drug carrier targeting CD4+ T lymphocytes.

1. Introduction effects. Liposome (LPs) is one of the

At present, the conventional promising drug carriers used for drug
treatments of several immune-related delivery. LPs contain bilayers of
diseases are still not effective due to some phospholipid molecules formed in a closed
limitations e.g. toxicity, low stability and vesicle filled with aqueous solution,
insufficient drug accumulation to target providing similar structure to that of
sites.1-3 Failure of the immune system can biological membranes.2,3 Moreover, LPs
suppress prevention and the control of surface can be modified with various types of
pathogens which can result in immune ligands to enable specific functions of the
disorders including autoimmune diseases, LPs. For example, LPs PEG to protect the
lymphopenia, and an acquired immune LPs from blood protein adsorption.3
deficiency syndrome or AIDS.4,5 Currently, PEGylation can inhibit the rapid clearance of
38 million people are living with HIV while the LPs by monocytes/macrophages.
there is no cure for HIV.6 HIV can silently Additionally, monoclonal antibody (mAb)
persist in latent form in resting CD4+ T cells, can be attached to LPs surface forming
which do not respond to the treatments. immunoliposome (imLPs) to provide
Therefore, drug delivery system with specific specificity to target site.1,3 In this study, both
targeting to the cells needs to be designed to LPs and imLPs were prepared with different
overcome limitations and unwanted side amounts of soyPC to investigate the efficacy PC173

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 1. Schematic illustration of functionalization of LPs. The imLPs was created by
attaching mAb to LPs surface through avidin-biotin linkage.

of cellular uptake. PEGylation of the carriers mAb), neutrAvidin-biotin binding protein

can promote hydrophilicity and enhance the (neutrAvidin) were purchased from Thermo
cellular uptake. The size and surface charge of Fisher Scientific, USA.
both LPs and imLPs were constantly 2.2 Preparation of immunoliposomes
characterized for 12 weeks to evaluate the Thin-film hydration method was used
stability of the nanoparticles. Due to the to prepare LPs with soyPC:chol:biotin-PE
different characteristics of LPs and imLPs (10:1:0.01 mol), PEG-PE (2.5 or 5% mol),
which influenced cellular uptake efficacy, and fluorescently labeled PE (FITC-PE). The
physicochemical properties of the carriers and lipid mixture was dissolved in chloroform and
cellular uptake by targeted cells were evaporated using rotary evaporator. After
evaluated simultaneously in this study.2,7 This rehydrating the lipid film with 10 mM
work presented a promising approach for HEPES, pH 7.4, LPs suspension was
developing a liposomal drug delivery system incubated at 37ºC for 2 h. The LPs were
for targeting CD4+ T cells which are extruded through 100 nm polycarbonate
considered the main target of latent HIV membrane. NeutrAvidin with 1:1 mol ratio to
infection or some other immune-related the amount of biotin-PE containing in LPs
diseases. was then incubated for 30 min followed by
centrifugation with centrifugal filter (Amicon
2. Materials and Methods Ultra-4 10K, Merck, Germany) at 5000×g for
2.1 Materials 15 min. The neutrAvidin-conjugated LPs
Soy phosphatidylcholine (soyPC), were then incubated with 1% biotinylated
biotiny-lated phosphatidylethanolamine anti-CD4 mAb for 30 min followed by
(biotin-PE), 1,2-dioleoyl-sn-glycero-3-phos- centrifugation to discard the unconjugated
phoethanola-mine-N-(carboxyfluorecein) components (9390×g for 15 min). The
(FITC-PE) and 1,2-disteroyl-sn-glycero-3- functionalization of LPs with anti-CD4 mAb
phosphoethanola-mine-N-[methoxy- was illustrated in Figure 1.
(polyethyleneglycol)2000] (PEG-PE) were 2.3 Characterization of immunoliposomes
purchased from Avanti Polar Lipids, USA. LPs and imLPs suspension were
Cholesterol (chol), 4-(2-hydro-xyethyl)- diluted with DI water and determined for their
piperazine-1-ethanesulfonic acid (HEPES), size and zeta potentials using zetasizer Nano
PC174
CD4 monoclonal antibody-biotin (anti-CD4 ZS (Malvern Instruments, UK) at 25°C. For

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
morphology analysis, the samples were 3. Results & Discussion
visualized by using transmission electron
3.1 Preparation and characterization of
microscope (JEM-2011, JEOL, Japan).
liposomes
Briefly, a drop of the specimen was placed on
In this work, LPs were prepared from
copper grid and allowed to dry. Then, 2%
soyPC: chol:biotin-PE with 10:1:0.01 mol
phosphotungstic acid solution was dropped
ratio varying amounts of soyPC from 10 mg
onto a grid and dried under vacuum
to 40 mg followed by functionalizing with
desiccator. The imaging was operated at 200
anti-CD4 mAb (as referred as to imLPs) to
kV.
obtain sufficient amount of liposomes to be
2.4 Cell culture
taken up by cells. The images obtained from
J-Lat full length clone 10.6 (J-Lat
transmission electron microscope showed that
10.6) which is a human T lymphocyte with
both LPs and imLPs exhibited a spherical
CD4 expression was obtained from the NIH
shape with different textures on the surface
AIDS Reagent Program.8 The cell culture was
(see Figure 2). In this study, the size of LPs
maintained in RPMI-1640 culture medium
and imLPs were approximately 100 nm and
supplemented with 10% fetal bovine serum
250 nm in diameter respectively which were
and 1% penicillin-streptomycin at 37°C in 5%
optimal for long-circulating carriers with
CO2 incubator.
specific targeting.2
2.5 Flow cytometric analysis
3.2 Cellular uptake of immunoliposomes
To examine liposomal cellular uptake,
To achieve the optimal cellular
the cells were seeded into 96-well plate (105
uptake, LPs composition is one of the crucial
cells/well). Then, LPs or imLPs were mixed
keys of consideration as a drug carrier
with the cells and incubated at 37ºC in 5%
because it can affect the spontaneous
CO2 incubator for 24 h. After the exposure,
curvature and change the elastic parameters of
the cells were collected by centrifugation and
LPs when fusing with cell membrane.9,10 The
fixed with 4% para-formaldehyde. The
cellular uptake by J-Lat 10.6 which contains
cellular uptake was evaluated using flow
CD4 antigen was evaluated using flow
cytometry (CyAnTM ADP, Beckman
cytometry as shown in the scatter plots in
Coulter, USA).
Figure 3A. The number displayed in each
2.6 Fluorescence microscopic analysis
rectangle represents the percentage of
The high-content analysis system
liposomal cellular uptake. Over 25% of
microscope (imageXpress Micro4, Molecular
population of cells could take up the
devices, USA) was used to confirm cellular
fluorescently-FITC labeled LPs, while the
uptake. The remaining cells from flow
cells treated with buffer showed negligible
cytometry were collected by centrifugation.
cellular uptake.
The cell pellets were rehydrated with
phosphate buffered saline (Gibco-Invitrogen,
UK) then the solution was transferred to new
96-well plate. The cellular uptake was
visualized under the fluorescent microscope
with 40× amplification.

PC175

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 2. Morphology of (A) LPs and (B)
imLPs. TEM images were visualized with
40000× and 15000× amplification,
respectively and operated at 200 kV.
Figure 3B showed that the cellular
uptake of both LPs and imLPs increased over
time with increasing amount of lipids used for
LPs preparation. After 24-h incubation, the
cellular uptake was higher when compared to
1-h incubation for both LPs and imLPs Figure 3. Determination of liposomal cellular
containing anti-CD4 mAb. In general, non- uptake. (A) Flow cytometric scatter plots of J-
functionalized LPs has higher cellular uptake Lat 10.6 cells after treatment with buffer or
than imLPs, suggesting that the LPs. The cell population and the number
functionalization of LPs with mAb may slow displayed in the rectangle specifies the
down the diffusion process of the LPs. Our cellular uptake percentage of FITC-labeled
findings showed that 20 mg of soyPC LPs at 24 h-incubation. (B) Cellular uptake of
provided high cellular uptake of LPs (>25%) both LPs and imLPs with varying amounts of
after 24 h which was significantly higher than soyPC at 1-h and 24-h incubation. The
at 1 h of incubation, whereas 10 mg of soyPC cellular uptake of LPs prepared from 20 mg of
could produce insufficient amount of LPs and soyPC increased significantly after 24-h
imLPs, resulting in low cellular uptake. The incubation as compared to that of 1-h
cellular uptake was highest for the particles incubation.
prepared from 40 mg, but was not
significantly different between 1 h and 24 h In this study, 20 mg of soyPC was
possibly because the cellular uptake was sufficient for LPs/imLPs preparation and
quickly saturated after 1-h incubation. High showed the marked difference of cellular
concentration of lipids could also result in uptake between LPs and imLPs. Additionally,
lipid aggregation and short-term storage. cellular uptake of both LPs and imLPs by J-
However, the cellular uptake of imLPs was Lat 10.6 cells were confirmed by fluorescence
generally lower than LPs due to the presence microscopy as demonstrated in Figure 4.
of the anti-CD4 mAb on imLPs surface Although J-Lat 10.6 cells seemed to take up
resulting in a different mechanism of cellular LPs easily, the LPs without mAb could not be
uptake. specifically directed to their targeted cells
especially in the presence of other groups of
cells due to the lack of specificity.3 Moreover,
LPs could be eliminated more rapidly from PC176

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
blood circulation. The recognition of cellular uptake using flow cytometry. Figure
nanoparticles to biological sites is an 5 demonstrated that the cellular uptake of
important key of consideration. Therefore, imLPs increased with increasing amount of
imLPs which contains anti-CD4 mAb could PEG in imLPs preparation. The cellular
provide a specific targeting for drug delivery uptake of imLPs with 2.5% and 5%
and accumulate into target site especially the PEGylation enhanced to approximately 15-
circulating cells as CD4+ T lymphocytes.1,3 In 20% when compared to non-PEGylated LPs.
order to verify the specificity of imLPs to Attachment of PEG to the imLPs could alter
CD4+ T cells, the cellular uptake by additional physicochemical properties of imLPs due to
cell types, with and without CD4 antigen will the hydrophilic characteristic of PEG which
be compared, which is beyond the scope of affects several phenomena including
this study. hydration process, imLPs-cell interaction,
surface characteristics and stability of the
particles.11,12 PEGylation may promote the
interaction of water and imLPs surface,
facilitating the release of cargos from imLPs.
Thus, attachment of PEG to imLPs can
enhance cellular uptake and could be
beneficial for a development of drug delivery
system targeting CD4+ T cells.

Figure 4. Fluorescence microscopic images

of cells upon uptake of LPs and imLPs. J-Lat
10.6 cells were treated with fluorescently-
labeled LPs or imLPs for 24 h. The cellular
uptake of LPs was higher for fluorescently-
labeled cells than imLPs.

3.3 Effect of PEGylation on cellular uptake

As previously reported, PEG could be
Figure 5. Effect of PEGylation with imLPs
used to provide an additional surface
on cellular uptake. Scatter plots showed
hydration layer for nanoparticles such as
populations of J-Lat 10.6 cells which take up
imLPs to create a protective barrier and
FITC-labeled imLPs in the absence and
prolong circulation time of the particles.3,10 In
presence of PEG. The attachment of PEG to
this work, PEGylation was achieved by using
imLPs enhanced the cellular uptake of imLPs.
imLPs composed of PEG-conjugated PE. The
imLPs with 2.5% and 5% PEG were treated 3.4 Evaluation of liposome stability
with the cells for 24 h before examined for PC177

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
To evaluate stability of both LPs and imLPs, remained at 100-200 nm in diameter over
the particle size and zeta potential of LPs/ time, and their zeta potentials were
imLPs in all conditions were monitored up to significantly reduced providing a negative
12 weeks when the samples were kept at 4°C. shift. Our findings suggested that the stability
Surface characteristics of the carrier with high of PEGylated imLPs was enhanced, since
stability should be relatively constant during PEG provides the hydrophilic characteristics
the storage period. Figure 6 revealed that the of imLPs which allow efficient
LPs remained in a size of ~100 nm in diameter functionalization of LPs with the mAb. Thus,
for 12 weeks, regardless of PEGylation, the attachment of PEG into imLPs provides
whereas the size of imLPs (no PEG) was benefits over the non-PEGylated LPs as a
observed to be 300 nm and tended to increase targeted drug delivery system.
overtime. This is possibly due to low zeta
potential which promotes a high tendency of 4. Conclusion
imLPs for aggregation and adherence to the This work presents a liposomal
other components. delivery system with specific targeting to
CD4+ T lymphocytes. The imLPs was mainly
prepared from soyPC and cholesterol with
FITC-conjugated lipids as a tracker of cellular
uptake. The conjugation of anti-CD4 mAb
was achieved via biotin-avidin linkage to
provide specific targeting CD4+ T cells.
Attachment of PEG to imLPs could enhance
the cellular uptake of J-Lat 10.6 by ~15-20%
as compared to non-PEGylated imLPs. The
presence of PEG on imLPs also promoted
stability of the particles, due to the
hydrophilicity of PEG. Overall, we
demonstrated that anti-CD4 imLPs composed
of 20 mg of soyPC with 2.5-5% PEGylated
could be used as a nanocarrier which can be
used as a platform for delivering therapeutic
Figure 6. Size and zeta potential drugs to CD4+ T lymphocytes as the main
characterization over the storage time. (A) target for latent HIV therapy.
Size and (B) zeta potential of both LPs and
imLPs were measured over time. LPs and Acknowledgements
imLPs were represented in dashed line and This work was partially supported by
solid line, respectively. Center of Excellence in Materials Science and
Although this size of imLPs was in an Technology, Chiang Mai University, Ministry
acceptable range of nanocarriers used for of Science and Technology to P.P. (Grant:
biomedical applications, especially drug SCH-NR2015-102), National Research
delivery (50-500 nm in diameter)12, the Council of Thailand to N.S. and P.P. (Grant:
stability of the imLPs needed to be optimized. 2556NRCT51390 and 2558NRCT 350269).
In contrast to non-PEGylated imLPs, the size S.M. was supported by Dr. Bruno
Werdelmann foundation for graduate study. PC178
of imLPs with 2.5% or 5% PEGylations

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
We would like to acknowledge Department of 6. World Health Organization. Global Health
Chemistry and Medical Science Research Observatory (GHO) data-HIV/AIDS.
Equipment Center, Faculty of Medicine, https:// www.who.int/gho/hiv/en/
Chiang Mai University for all research (accessed Jan 11, 2020).
facilities. 7. Batrakova, E. V.; Gendelman, H. E.;
Kabanov, A. V. Expert Opin. Drug Del.
References 2011, 8(4), 415-433.
8. Jordan, A.; Bisgrove, D.; Verdin, E.
1. Su, Y.; Xie, Z.; Kim, G. B.; Dong, C.;
EMBO J. 2003, 22 (8), 1868–1877.
Yang, J. ACS Biomater. Sci. Eng. 2015,
9. Koller, D.; Lohner, K. Biochim. Biophys.
1(4), 201-217.
Acta- Biomembr. 2014, 1838 (9), 2250–
2. Danaei, M.; Dehghankhold, M.; Ataei, S.;
2259.
Hasanzadeh Davarani, F.; Javanmard, R.;
10.Nele, V.; Holme, M. N.; Kauscher, U.;
Dokhani, A.; Khorasani, S.; Mozafari, M.
Thomas, M. R.; Doutch, J. J.; Stevens, M.
R. Pharmaceutics 2018, 10 (2), 1–17.
M. Langmuir 2019, 35 (18), 6064–6074.
3. Sercombe, L.; Veerati, T.; Moheimani, F.;
11.Dan, N. Biochim. Biophys. Acta-
Wu, S.Y.; Sood, A. K.; Hua, S. Pharmacol.
Biomembr. 2002, 1564 (2), 343–348.
2015, 6, 1–13.
12.Lombardo, D.; Calandra, P.; Barreca, D.;
4. Schulze-Koops, H. Arthritis Res. Ther.
Magazù, S.; Kiselev, M. A. Nanomaterials
2004, 6 (4), 178–180.
2016, 6 (7), 125.
5. Sai YRKM, A. D. J. Clin. Cell. Immunol.
2011, 02 (03), 1–7.

PC179

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Effect of rheological properties in relation to fabrication conditions of
medical-grade poly(L-lactide-co-glycolide) for use as
resorbable bone fixation devices
Paveena Tikakosol1, Jutamas Kongsuk2, Sumontha Ramangkoon2, Aphinan Saengsrichan2,
Robert Molloy2,3, Asira Fuongfuchat4, Winita Punyodom1,2,3*
1
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand
2
Bioplastics Production Laboratory for Medical Applications, Faculty of Science, Chiang Mai University,
Chiang Mai, Thailand
3
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand
4
National Metal and Materials Technology Center, National Science and Technology Development Agency,
Pathumthani 12120, Thailand
*E-mail: [email protected]

Nowadays, resorbable polymer plates and screws can be used as alternatives to metal
bone fixation devices in orthopedic surgery. One of the most promising materials is poly(L-
lactide-co-glycolide) (PLG) due to its biocompatibility and the ability to control its
biodegradation rate through its copolymer composition. However, PLG’s main drawback is its
low melt strength which negatively influences its ease of fabrication. A key to moderating the
effect of PLG’s low melt strength during the fabrication process is an understanding of its melt
rheology. In this study, medical-grade PLG 80:20 (mole %) was synthesized according to
ASTM F1925-17 specifications with weight-average molecular weights (Mw) ranging from
90,000 to 400,000 Da. All of the samples had similar thermal properties with glass transition
temperatures (Tg) and melting temperatures (Tm) in the ranges of 42-51 °C and 148 -157 °C,
respectively. The results of oscillatory testing at 170 °C indicated that the PLG melt exhibited
a liquid-like state characteristic of a viscoelastic material with a linear plateau region. Values
of complex viscosity obtained through steady shear testing were shown to be dependent on
both copolymer composition (L:G ratio) and molecular weight. Therefore, depending on their
particular microstructures, PLG melts can be expected to respond differently upon the
application of steady and dynamic shear forces.

1. Introduction operation.2,3 Recent studies have shown that

Regeneration of bone fracture is a biodegradable bone pates and screws can
clinical challenge that requires orthopedic overcome the limitations of metal.4 In this
surgery to restore the fractured bone to its study, medical-grade poly(L-lactide-co-
original condition.1 In the first period, bone glycolide) 80:20 (mole %) has been
fracture treatment with the use of orthopedic synthesized by ring-opening polymerization
plates and screws made of metal such as (ROP) and characterized by ASTM F1925-17
stainless steel, titanium because of their (Standard Specification for Semi-Crystalline
strength. However, metallic devices have Poly(lactide) Polymer and Copolymer Resins
fundamental problems is stress shielding of for Surgical Implants). Thermal and
the underlying bone that effects on facial rheological properties have been studied to
growth. Therefore, the metallic fixation understand the melting properties and to
device needs to be removed in a second determine fabrication conditions.
PC180

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2. Materials and Methods calorimetry (DSC) using a Mettler Toledo
2.1. Polymer Synthesis and DSC1 stare system instrument. The
Characterizations temperature at which the weight of the
Medical-grade poly(L-lactide-co- polymer is reduced by 5% was determined by
glycolide) 80:20 (mole %) was synthesized a Perkin Elmer TGA 7 Thermogravimetric
by ROP of L-lactide (L) and glycolide (G) at Analyzer.
a polymerization temperature of 140°C for 72 2.2. Melt Rheological Evaluation of the
hrs as shown in Figure 1. Tin(II) n-butoxide5 PLG Copolymer
was used as initiator in varied concentration: Rheological characterization was
0.125, 0.100, 0.075 mole% to obtained carried out using a parallel-plate geometry
PLG1, PLG2, and PLG3. To prove that the stress-controlled rotational rheometer
polymers are medical-grade polymer for (Bohlin Gemini HRnano, Malvern Instruments
surgical implants, they were characterized Ltd., UK) using smooth aluminum parallel
according to ASTM F1925-17. plates with a diameter of 25 mm and a final
gap of 0.5 mm as shown in Figure 2.
a)

Figure 1. Synthesis route of the PLG

copolymer.
Total Residual Monomer and solvent b)
residuals were detected by gas
chromatography Agilent Technologies 6890
with BD-17 MS (30 m x 0.25 mm) column.
Determined the Residual Water by Karl
Fischer Titrator from Mettler Toledo. Heavy Figure 2. Bohlin Gemini HRnano Rotational
metals were analyzed by inductively coupled Rheometer apparatus. a) parallel plate
plasma technique. Polymer composition and geometry and b) the gap between the plates.
monomer sequencing were characterized by Before testing, the PLG was
a combination of 400 MHz 1H-NMR compressed into a plate of thickness 0.1 mm
spectroscopy using a Bruker DPX-400 NMR at 180 °C and cut to 25 x 25 mm2 dimension.
spectrometer (Bruker, Switzerland). An oscillation mode at 1 Hz frequency was
Molecular weight and dispersity were used to study the stability of the raw materials
characterized by Gel Permeation at 170 °C. Stress sweeps were performed to
Chromatography (GPC). Intrinsic viscosity, define the region of linear viscoelasticity.
[ ], was determined by dilute-solution The frequency dependence of storage (G’)
viscometry at a single concentration of 0.1% and loss (G”) moduli and complex viscosity
(w/v) in chloroform (CHCl3) as solvent at 30 (*) of the PLG were analyzed at a strain of
± 0.1 °C using a Ubbelohde-type viscometer 5%. The changes in rheological properties
in conjunction with a Schott-Gerate AVS300 during increasing temperature from 170 to
Automatic Viscosity Measuring System. 230 °C were evaluated at a heating rate of 10
Temperature transitions and crystallinity °C/min.
were determined by differential scanning PC181

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 1. Physical/chemical property requirements for virgin semi-crystalline poly(L-lactide-
co-glycolide) copolymer resins for surgical implants.
Specification ASTM F1925-17 PLG1 PLG2 PLG3
Residual < 2.0 % 0.74 % 0.60 % 1.29 %
Monomer

Residual Solvent < 1000 ppm < 1000 ppm < 1000 ppm < 1000 ppm
Residual Water ≤ 0.5 % 0.44 % 0.32 % 0.23 %
(Optional)
Heavy Metals ≤ 10 ppm < 1 ppm < 1 ppm < 1 ppm
Residual Catalyst ≤ 150 ppm 75 ppm 73 ppm 74 ppm
(Optional)

Copolymer Ratio ±3% 1.88 % 2.00% 0.12%

(molar ratio) of target (78.5 : 21.5) (78.4 : 21.6) (80.1 : 19.9)
Specific Rotation 125° to 145° 139° ± 0.24 143° ± 3.83 143° ± 1.73

To investigate the flow behaviour of PLG samples met the ASTM F1925-17
the PLG copolymers at a wide range of property requirements. Therefore, they can
shear rates, shear viscosity () as a function be used as surgical implants. The number-
of shear rate was carried out by applying a average molecular weight (Mn), the weight-
shear rate varying from 1 to 100 s-1. average molecular weight (Mw), dispersity
Table 2. Molecular weight, dispersity and and inherent viscosity at 30 ± 0.1 °C of the
inherent viscosity of poly(L-lactide-co- PLG copolymers are shown in Table 2,
glycolide). while their thermal properties are shown in
Properties PLG1 PLG2 PLG3 Table 3.
Mn (Dalton) 50,000 66,800 260,000 Table 3. Thermal properties of poly(L-
lactide-co-glycolide)
Thermal
Mw (Dalton) 94,000 128,000 442,000 PLG1 PLG2 PLG3
properties
Glass transition
Dispersity 1.88 1.92 1.70 temperature at 41.8 °C 47.4 °C 47.2 °C
1st run
Inherent 1.1 ± 0.11 1.6 ± 0.16 3.5 ± 0.12 Glass transition
viscosity, temperature at 48.6 °C 50.1 °C 51.2 °C
dl/g 2nd run
(at 30 °C) Melting
temperature at N/A N/A N/A
3. Results & Discussion 1st run
Melting
3.1. Polymer Synthesis and 155.5 156.6 147.7
temperature at
°C °C °C
Characterizations 2nd run
The property requirements 5% weight loss 284.6 273.5 287.6
according to ASTM F1925-17 of medical- temperature °C °C °C
grade poly(L-lactide-co-glycolide) (PLG),
are detailed in Table 1. From the results, all PC182

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
3.2. Melt Rheological Evaluation of the that the PLG is a viscous fluid in the studied
PLG Copolymers  range. The *
3.2.1 Dynamic Testing
Stress Sweep a)
Usually, the rheological properties
of a linear viscoelastic polymer are
independent of strain up to a critical strain
level (C). Above this critical value, the
storage modulus (G’) decreases with the
applied strain indicating the nonlinear
viscoelastic behavior of the polymer.
Consequently, measuring the strain
b)
amplitude dependence of the storage and
loss moduli (G”) usually is the first
experiment tested in order to determine the
linear viscoelastic region of the sample.
Figure 3 shows the strain amplitude
dependence of G’ and G” of the PLG at 170
°C with a frequency of 1 Hz by a stress
sweep experiment. At this temperature, the
value of G” was higher than that of G’ c)
indicating that the PLG was predominantly
viscous at this temperature. On the other
hand, G’ curve showed a linear plateau
region for the experiment strain range. In
the linear viscoelasticity limit where the
melt was strain-independent, the behavior
of copolymer melt was a combination of
irreversible viscous flow associated with Figure 3. Strain dependence of storage (G’,
the polymer chain slippage and reversible ) and loss (G”, ) moduli of the PLG with
elastic deformation associated to molecular a frequency of 1 Hz at 170oC for the first
entanglement and other regular structures. run. Arrows indicate positions of C. a)
Therefore, the linear viscoelastic property PLG1, b) PLG2, and c) PLG3.
of the PLG melt was conducted at a strain
of 5% for the following dynamic curve of PLG shows the Newtonian or
measurements. linear viscosity region at the experiment
Frequency Sweep frequency. Generally, in the terminal
The frequency dependence of region, the curves of G’ and G” of typical
storage (G’) and loss (G”) moduli and polymer melts are shown the power-law
complex viscosity (*) of the PLG at a relationship to the , i.e., (G’)  2 and (G”)
strain of 5% at an isothermal temperature of  . The PLG melts at 170 °C showed the
170 °C are shown in Figure 4. The results frequency-dependent behavior and the
evaluated the terminal region that G” higher slope of log G’ and log G” versus log  was
than G’ in the entire  range and indicating smaller than 2 and 1, respectively.
PC183

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Temperature Sweep properties. When opening the rheometer
The changes in rheological after finishing the measurement, the
properties such as storage moduli (G’), loss copolymer became more yellow and less
moduli (G”) and loss factor (tan) were viscous. Moreover, the complex viscosity
evaluated during of PLG decreases with increasing
temperature due to thermal degradation at
a)
high temperatures.
0.9
1.5
a)

2

b)
0.9

1.8 b)

2

c)
0.9
1.6

c)

2

Figure 4. Frequency dependence of storage

(G’, ) and loss (G”, ) moduli and
complex viscosity (*, ) of PLC at strain
5% for an isothermal temperature of 170oC. Figure 5. Temperature dependence of
a) PLG1, b) PLG2, and c) PLG3. storage (G’, ) and loss (G”, ) moduli
increasing temperature from 170 to 230 °C and tan () of the PLG at a strain of 5%
at a heating rate of 10 °C/min, as shown in and a frequency of 1 Hz. a) PLG1, b) PLG2,
Figure 5. Throughout the temperature and c) PLG3.
range, PLG melt exhibited a liquid-like 3.2.2 Steady Shear Testing
state characteristic of the highly viscous In polymer processing by injection
behavior of viscoelastic materials. For molding, polymers must have an
PLG1-3, the value of tan was higher than appropriate shear viscosity so that they can
one demonstrating its low elastic be fabricated into products with accurate PC184

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
dimensions. Therefore, the polymer’s flow a linear plateau region. Values of complex
properties at different shear rates must be viscosity obtained through steady shear
studied in order to obtain shear viscosity, testing were shown to be dependent on both
which is a function of shear rate. Changes copolymer composition (L:G ratio) and
in melt viscosity for the PLG copolymers at molecular weight. Thus, it can be
different molecular weights are shown in concluded that PLG can be fabricated by
Figure 6. The flow behavior of PLG1 was injection molding at 170 °C.
in the Newtonian plateau region where the
viscosity is independent of shear rate, while Acknowledgements
the shear viscosities of PLG2 and PLG3 This work has been supported by
decreased at a shear rate higher than about the Biodiversity-Based Economy
60 s-1 and 40 s-1. PLG has a shear viscosity Development Office (BEDO). The first-
() at 170 °C dependent upon its molecular named author (PT) would also like to thank
weight. PLG1 had the lowest molecular the Science Achievement Scholarship of
weight and showed the lowest shear Thailand for financial support.
viscosity. In contrast, PLG3 exhibited the
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3. Hughes, T. B. Clin. Orthop. Relat.
Res. 2006, 445, 169–174.
4. Prabhu, B.; Karau, A.; Wood, A.;
Dadsetan, M.; Liedtke, H.; DeWitt,
Figure 6. Shear viscosity () as a function T. Bioresorbable Materials for
of shear rate of the PLC copolymers at 170 Orthopedic Applications (Lactide
°C. and Glycolide Based). In
Orthopedic Biomaterials; Li, B;
4. Conclusions Webster,T., Ed.; Springer: Cham,
Medical-grade PLG 80:20 (mole %) 2014; pp 287–339.
synthezised according to ASTM F1925-17 5. Meepowpan, P.; Punyodom, W.;
specifications exhibited a liquid-like state Molloy, R. U.S. Patent No. US
9,637,507 B2, 2013, 757–760.
characteristic of a viscoelastic material with

PC185

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Investigation of xylitol and sorbitol derivatives on mechanical and thermal
properties of polypropylene fibers
Thanrada Santisumranvilai, Thunyaporn Phutthisa, Supatra Pratumshat*
Department of chemistry, Faculty of science, Naresuan University, Phitsanulok 65000
*E-mail: [email protected]

The effect of xylitol and sorbitol derivatives which have different substitution group
positions (e.g. ortho, meta, and para position) and types of halogen substitutions (e.g. fluoro,
bromo, chloro) on crystallization temperature, melting temperature and percentage of
crystallinity of polypropylene (PP) were studied. Thermal properties of PP blended with these
derivatives were studied by differential scanning calorimeters ( DSC) . These materials
functioned as a nucleating agent in PP matrix. The nucleating agent was mixed with PP using
two roll mill machine and then melt spinning into fiber. It was found that the crystallization
temperature of 0. 5% wt para- chloro dibenzylidene xylitol ( p- Cl- DBX) is higher than the
crystallization of neat PP about 10 °C. The amount of p-Cl-DBX that was greater than 1%wt,
did not affect the crystallization temperature of PP. The melting temperature and percentage of
crystallinity of PP did not change when these additives were added. Morphologies of xylitol
and sorbitol derivatives in organic solvents showed fibril morphology with diameters ranging
from 50 to 140 nm. The effect of these derivatives on tensile properties of PP fibers was also
studied.

organic solvents and polymers, to produce

1. Introduction organogels.2 Several DBS have been studied
Polypropylene (PP) is a semi- as organogels to improve mechanical
crystalline polymer that is different in properties, transparency and crystallization
stereospecificity and comonomer content. It temperature. Mahaffey3 studied a polyolefin
is commercially produced in isotactic, plastic dispersed with additives to improve
syndiotactic and atactic forms with varying mechanical properties and transparency
characteristics. Nagarajan et al.4 investigated
degree of tacticity, the isotactic form being
the effect of nucleating agents such as DBS,
the most common. PP is widely used in many
pine crystal 1500, sodium and potassium
applications due to its excellent balance of benzoates in isotactic polypropylene. It was
physical properties and low cost. The found that DBS act as a nucleator even at low
property profile of PP is strongly influenced concentration as 0.014%wt and the
by the level of crystallinity that is achieved nucleation efficiency of DBS is concentration
when the polymer crystallizes from the melt. dependent. The crystallization temperature of
The modulus (stiffness) and strength of the isotactic polypropylene is linearly
final part is depending on the percent proportional to the DBS concentration.
crystallinity, and higher crystallinity leads to Shepard et al.5 examined the thermal and
higher stiffness and strength.1 mechanical properties, as well as
1,3:2,4-dibenzylidene sorbitol (DBS) morphological characteristics, of isotactic
is a butterfly-shaped amphiphile derived polypropylene (iPP) copolymer with 3 wt%
from the sugar alcohol D-glucitol. It is known ethylene upon addition of less than 1 wt% of
as a gelator. It can self-organize to form a 3D 1,3:2,4-di-p-methylbenzylidene sorbitol
network, stabilized by hydrogen bonds at (MDBS). The addition of MDBS at different
relatively low concentrations in a variety of concentrations is also found to promote PC186

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
increase in optical clarity, yield strength, has been studied to compare with previous
tensile strength, and ultimate elongation of study.
modified copolymer formulations. Lipp et al.
6
investigated the role of 1,3:2,4-di(3,4- 2. Materials and Methods
methylbenzylidene) sorbitol (DMDBS) in 2.1 Materials
inducing oriented crystallization during the
melt spinning of PP fiber. The results show a Polypropylene used in this work is
higher tensile modulus at 0.4%DMDBS, isotactic polypropylene (iPP) (Mophen
likely due to better orientation of the PP HP400H) from Basell Polyolefins. The melt
crystals along the fiber direction flow index and density are 2 g/10 min (230
Sutthatang et al. 7 studied the effect of C/2.16 kg) and 0.9 g/cm3, respectively. DBS
halogenated sorbitol derivatives using as derivatives were prepared by the reaction
nucleating agent and their effect on between D-sorbitol and halogenated aromatic
orientation of polypropylene fiber. It was aldehyde in cyclohexane using acid catalyst.
found that p-Cl-DBS reveal the most For chloro derivative, different positions of
effective for nucleating agent and elastic substituent (ortho, meta and para) were also
synthesised. The procedure for sorbitol
modulus. Yamasaki et al. 8 have proposed
derivatives synthesis was shown in Scheme
that the 6-OH group plays a crucial role in the
1. Meanwhile, DBX derivatives were
ability of DBS to self-organise and ultimately synthesized in the same way but xylitol was
form a network structure. They have used. DBS and DBX derivatives were
demonstrated that the 5-methoxy derivative characterized by FTIR, NMR and DSC
in which the pendant hydroxy (5-OH) group techniques. The percentage yield of products
is replaced with a methoxy group, can induce are about 36-54 % were reported by
gelation while the 6-methoxy DBS derivative Sutthatang.11
with terminal hydroxyl (6-OH) group
substituted cannot. However, Watase et al.9
have revealed that the formation of a ground
state dimer between two benzylidene
attributing to  electron overlap between
adjacent phenyl rings. This suggested that
DBS molecules stack neatly on top of each
Scheme 1. Synthesis of sorbitol and xylitol
other. Wilder et al.10 have used molecular
derivatives
mechanics and molecular dynamics
2.2 Gel formation and fibril morphology
simulations to elucidate the equilibrium
Physical gel of DBX and DBS
structure of DBS and the molecular
derivatives were prepared by dissolving in
interactions that govern self-assembly. They
tetradecane at elevated temperature and
have proposed that the mechanism of
cooled down to room temperature. Scanning
nanofibrillar network formation involving
electron microscopy (SEM),(Leo1455VP)
more than one type of physical interaction,
and Transmission electron microscopy
i.e. the forming of hydrogen bonds and 
(TEM, Philllips Tecnai12) were used to
interactions. In this work, the effect of DBX
investigate the fibril network of these
with various substituent groups and positions
derivatives. For SEM technique, a drop of
on thermal and mechanical of polypropylene
solution was placed on nylon membrane
filters 0.2 μm and dried at ambience PC187

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
temperature for one week. Samples for TEM 2.5 Mechanical testing
analysis were prepared by solution drop- Mechanical properties were tested by
casting onto a carbon coated copper grid and tensile tester (WDW-5E) with load 100 N and
examined under instrument operating at an cross head speed 50 mm/min. The specimen
accelerating voltage of 80 kV. gauge length of fiber was 20 mm. At least 10
2.2 Melt blending specimens were tested for each sample.
DBX and DBS derivatives and iPP Tensile strength, Modulus and Elongation at
were melt-blended using two-roll mill break will be reported.
(Pirom-olarn, 110-1E) at 140 °C for 5 min.
The compounds were then compressed with 3. Results & Discussion
hot press mold into film thickness of 2 mm 3.1 Effect of DBX and DBS Derivatives on
using mold temperature at 175 °C for 5 min. Crystallization and Melting Temperature
The compounds were cut into small pieces of iPP
for fiber formation.
2. 3 Crystallization and melting
temperature of iPP, iPP/DBX, iPP/DBS by
DSC technique
10 to 15 mg of fiber in aluminum pan
was heated from 25 C to 180 C with heating
rate of 10 C/min, and then cooled down from
180 C to 25 C with cooling rate 5 C/min,
and reheated again with heating rate of 10 Figure 2. Cooling thermogram of iPP and
C/min. iPP with different amounts of p-Cl-DBX.
2.4 Fiber preparation
The process used a mini-extruder DSC thermograms shown in Figure 2
(Randcastle RCP-0625) equipped with a fiber reveal that the addition of 0.5% wt of p-Cl-
line having a single hole spinneret (Figure 1). DBX increase the crystallization temperature
An aluminum tube was connected with the of iPP. At concentration higher than 0.5%
die to retain a temperature inside during the wt, it is likely that the crystallization
process. The temperature profiles were fixed temperature of iPP contained p-Cl-DBX
at 120, 175, 185, and 190 C for feed zone, remain constant as shown in Table 1. Table 1
compression zone, metering zone, and die, shows the effect of substitution group of F-
respectively. iPP and iPP compound pellets DBX, Br-DBX, Cl-DBX on the
were fed into the hopper of mini-extruder to crystallization temperature of iPP. It was
melt the pellet. The molten polymer was found that p-Br-DBS shows a bit higher in the
extruded through the spinneret was pulled by
crystallization temperature of p- F-DBX and
slow set of rotating godets, immediately
p-Cl-DBX. However, small amount of these
cooled in air and subsequently cooled in
water. DBX derivatives can act as a nucleating agent
for iPP. The effect of substitution position of
Cl-DBX on the crystallization temperature of
iPP revealed that m-Cl-DBX and p-Cl-DBX
show more effective in term of increasing the
crystallization temperature of iPP. When the
Figure 1. schematic of fiber preparation same amount of p-Cl-DBX and p-Cl-DBS PC188

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
added, p-Cl-DBS show more effective 3.2 Fibril Morphology
increasing in the crystallization temperature Figure 3 shows SEM and TEM
of iPP by 15 C. micrographs of extracted of DBX and DBS
Table 1. Crystallization temperature of iPP, derivatives which were dissolved in
iPP/DBX and iPP/DBS derivatives. tetradecane. It can be seen that all derivatives
are in the form of fibril bundle and twisted in
Crystallization temperature low molecular weight solvent. Diameter and
Sample (C) length of these fibrils are shown in Table 3.
Onset Peak Different substituent Different positions of
iPP 121.30 116.97 groups substituent group
iPP/0.2%p-Cl-DBX 120.53 113.91 0.05% p-F-DBX 10000x 0.1% o-Cl-DBX 10000x
iPP/0.5%p-Cl-DBX 131.69 125.79
iPP/1%p-Cl-DBX 132.41 126.39
iPP/3%p-Cl-DBX 131.49 127.01

iPP/0.5%p-F-DBX 131.91 124.47

iPP/0.5%p-Cl-DBX 131.69 125.79
iPP/0.5%p-Br-DBX 133.18 127.72 0.05% p-Cl-DBX 5000x 0.1% m-Cl-DBX 3000x

iPP/0.5%o-Cl-DBX 118.32 112.51

iPP/0.5%m-Cl- 126.59 120.52
DBX
iPP/0.5%p-Cl-DBX 131.69 125.79
iPP/0.5%p-Cl-DBS 136.42 131.61
0.05% p-Cl-DBX 5000x
Table 2. Melting temperature and % 0.05% p-Br-DBX 10000x
crystallinity of iPP, iPP/ DBX and iPP/ DBS
derivatives.
Melting temperature %Xc
Sample (C)
Onset Peak
iPP 154.15 163.53 46.33 0.05% p-Cl-
iPP/0.5%p-F- 153.07 164.25 43.23 0.05% p-Cl-DBS(TEM)
DBS10000x(SEM)
DBX
iPP/0.5%p-Cl- 150.70 166.27 46.24
DBX
iPP/0.5%p-Br- 150.73 166.91 45.88
DBX
iPP/0.5%o-Cl- 149.19 159.17 45.47
DBX
iPP/0.5%m-Cl- 136.83 160.43 46.60
DBX Figure 3. SEM and TEM micrographs of
iPP/0.5%p-Cl- 148.10 166.96 51.02
DBS
DBX and DBS derivatives.
Melting temperature of iPP did not
change when these derivatives were added
with respect to the effect of p- Cl- DBX. The
addition of 0. 5 % wt of p- Cl- DBS slightly
increased the degree of crystallinity of iPP.
Meanwhile, the additions of most derivatives
are not effective on the degree of crystallinity
of iPP fiber.
PC189

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 3. Diameter and length of DBX and elastic modulus of iPP fiber by 93%, while
DBS derivatives were observed by SEM tensile strength and percentage of elongation
technique of iPP fiber containing these derivatives were
Diameter Length not much different except for 3%wt.
Sample
(nm) (m)
Different substituent groups show slightly
0.05%wt p-F-
50-300 9 increase in tensile strength when compare to
DBX
0.05%wt p-Cl-
150-210  14
iPP while ortho and meta position show a
DBX decreasing in tensile strength which might be
0.05%wt p-Br-
100-140  50 related to the different sizes of fibril.
DBX
0.1%wt o-Cl- Table 4. Mechanical properties for iPP,
130-220  12
DBX iPP/DBX and iPP/DBS derivatives.
0.1%wt m-Cl-
280-400  20
DBX Tensile
0.05%wt p-Cl- Elongation Modulus
16-80 11
9 strength
DBS
Sample MPa % MPa
In case of low concentration, i. e. Me S.D Mean S.D. Me S.D
0. 05% wt of o-Cl-DBX and m-Cl-DBX, the an . an .
fibril network could not be observed. While
iPP 27.4 2.24 1198.8 111 2.29 0.21
p- Cl- DBX and p- Cl- DBS could reveal the
7 1
fibril structure even at low concentration.
Therefore, the concentrations of o- Cl- DBX iPP/0.2% 29.4 3.41 1251.6 120.7 2.35 0.35
p-Cl- 4 2
and m- Cl- DBX were increased up to
DBX
0. 1% wt. The fibril network of o- Cl- DBX iPP/0.5% 28.0 1.74 631.54 231.7 4.43 1.93
and m- Cl- DBX can be revealed and their p-Cl- 2
diameters are similar to those of p-Cl-DBX. DBX
iPP/1% 26.6 2.75 1137.9 173.1 1.99 0.19
SEM micrographs of gel extracted p-Cl- 5 4
from organic solvent revealed the fibril DBX
network of chloro and bromo substitutes iPP/3% 8.68 1.75 264.69 138.1 3.03 0.24
which their diameters are in the range of 100- p-Cl-
DBX
210 nm and length higher than 14 m.While iPP/0.5% 30.7 3.15 1343.2 160.1 2.29 0.14
ortho and meta chloro substitute show bigger p-F-DBX 9 2
diameter than para position. This diameter
iPP/0.5% 28.0 1.74 631.54 231.7 4.43 1.93
range of p-Cl-DBS is similar to the p-Cl- 2
morphology of DBS in polymers by using DBX
TEM discovered by Wilder et al.12-13 It was iPP/0.5% 25.5 2.44 669.62 2669 3.81 0.91
p-Br- 1
found that the DBS molecule can form highly
DBX
connected networks, with nanofibrils iPP/0.5% 11.5 4.85 1311.3 47.1 0.88 0.41
measure about 10 to 70 nm in diameter and o-Cl- 8 9
length are up to 500 nm. DBX
iPP/0.5% 8.46 3.47 1106.0 245.4 0.76 0.12
3.3 Mechanical properties m-Cl- 3
Mechanical properties of iPP fiber, DBX
iPP/DBX and iPP/DBS derivatives were iPP/0.5% 33.6 2.72 2847.8 307.4 1.18 0.08
summarized in Table 4. It was found that p-Cl- 3 8 0
DBS PC190
adding 0.5%wt of p-Cl-DBX increase the

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
4. Conclusion G. and Spontak R. J. J. Polym Sci B Polym.
DBX and DBS derivatives can act as Phys., 1997, 35, 2617-2628.
nucleating agent for iPP. The crystallization 6. Lipp J. , Shuster M. , Feldman G. and
temperature of iPP increase by 10-15 C Cohen Y., Macromolecules, 2008, 41 , 136-
compared to neat iPP for 0.5 %wt of p-Cl- 140.
7. Sutthatang, T, Wichai,U Wangsoub S. ,
DBX and p-Cl-DBS. In contrast, different
JMMM, 2013,1 , 1-8 .
types and amount of these derivatives in iPP
8. Yamasaki S. , Ohashi Y. , Tsutsumi
did not affect to the melting temperature of
H. ,Tsujii K. , Bull. Chem. Soc. Jpn. , 1995,
iPP. All DBX and DBS derivatives are in the
68,146-151.
form of very long fibril in low molecular
9. Watase M. , Nakatani Y. , Itagoki H. ,
weight solvent which their diameters are in
J.Phys.Chem.B, 1999, 103, 2366-2373.
the range of 16-400 nm.
10. Wilder E. A. , Spontak J, Hall C. K. ,
Molecular Physics, 2003, 101( 19) , 3017-
Acknowledgements
3027
SP thanks Faculty of Science
11.Sutthatang, T. Effect of Sorbitol
Naresuan University for financial support.
Derivatves on Mechanical Properties and
We also thank Assoc. Prof. Taweechai
Morphology of Polypropylene Fiber M. Sc.
Amornsakchai, Mahidol University for
Thesis, Naresuan University,
instrument supporting for fiber preparation.
Phitsanulok,Thailand, 2012.
12. Wilder E. A., Hall C. K., Khan S. A. and
References
Spontak R. J. Langmuir, 2003, 19, No. 15,
1. www. mayzo. com/ pdf/ Beta- Nucleation-
Article- Plastic- Additives- Compound. pdf, 6004-6013.
2007 (accessed May 22, 2011). 13. Wilder E. A., Braunfeld M. B., Jinnai H.,
2. Merurio D. J. and Spontak R. J, J. Phys. Hall C. K., Agard D. A. and Spontak R. J. J.
Chem. B. 2001, 105 , 2091-1098. Phy. Chem. B, 2003, 107, No. 42, 11633-
3. Mahaffy R. L. and Inman Jr., SC. United 11642.
States Patent 4371645, July 29, 1981.
4. Nagarajan K., Levon K. and. Myerson A.
S, J. Them. Anal. Cal. 59, 2000, 497-508.
5. Shepard T. A., Delsorbo C. R., Louth R.
M., Walborn J. L., Norman D. A, Harvey N.

PC191

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Effect of rheological properties on the melt extrusion of poly(L-lactide-co-ε-
caprolactone) monofilament absorbable surgical sutures
Kittisak Yarungsee1, Montira Sriyai2, Jutamas Kongsuk2, Robert Molloy2,3, Asira
Fuongfuchat4, Winita Punyodom1,2,3*
1
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
2
Bioplastics Production Laboratory for Medical Applications, Faculty of Science, Chiang Mai University,
Chiang Mai 50200, Thailand
3
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
4
National Metal and Materials Technology Center, National Science and Technology Development Agency,
Pathumthani 12120, Thailand
*E-mail: [email protected]

In the production of medical devices intended to be used in the human body, polymers
must be of medical-grade and should not contain any stabilizers, which makes processing more
challenging. The melt extrusion of high molecular weight polymers can lead to problems
arising from high melt viscosity and long residence times which can in turn lead to serious
thermal degradation of the polymer. Our aim in this work is to understand and compare the
melt behaviour of medical-grade poly(L-lactide-co-ε-caprolactone) (PLC) in an extrusion
process using a single-screw extruder. Rheology measurements are widely used to define the
processing window without requiring a large amount of material. This is especially useful for
expensive medical-grade polymers. The rheological properties of the PLC melt were studied
in both oscillatory and steady shear testing modes in order to suggest how temperature or shear
rate can be tuned to tailor the melt behaviour for melt extrusion. The combination of
temperature and shear rate in an extruder is needed to modulate the polymer’s melt behaviour
and achieve good material properties by determining the polymer’s “processing window”. The
results indicated that the PLC copolymer in the melt state is pseudoplastic due to the linearity
of shear viscosity at low shear rate. This suggests that the copolymer melt may contain some
ordered microstructures such as small crystalline domains of poly(L-lactide) which remained
intact at high strain deformation.

1. Introduction Biodegradation proceeds via simple

Synthetic biodegradable polyesters hydrolysis (random chain scission) leading
such as polyglycolide (PG), polylactide to progressively lower molecular weight
(PL), poly(ε-caprolactone) (PCL), fragments which are then removed from the
polydioxanone (PDO) and their co- or implant site by the body’s own biological
terpolymers have been widely used in mechanisms.
medical applications such as absorbable In this research work, attention has
sutures and nerve guides, orthopedics, drug been focused on absorbable surgical sutures
delivery systems, and scaffolds for tissue which can be classified into two main
engineering.1-8 Copolymers of L-lactide groups, namely: monofilaments and
(LL) and ε-caprolactone (CL) are known to multifilaments. Monofilament sutures have
be both biocompatible and biodegradable in a smooth surface and therefore show less
the human body and therefore are widely tendency to harbor bacteria - major
used in biomedical applications. advantages in minimizing tissue drag and PC192

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
tissue reaction respectively. However, behavior is related to specific molecular
compared with multifilaments, they are structures and the molecular weight
relatively stiff and not so easy to handle. An distribution. In the fabrication of polymeric
appropriate balance of mechanical objects, most of the shaping is carried out in
properties is therefore essential for their use the molten state, as it is an important part of
in this type of application. For example, the the physical property development. Melt
tensile strength of the fiber must be processing involves interplay between fluid
sufficiently high while still maintaining mechanics and heat transfer in rheological
sufficient flexibility for handling purposes. complex liquids, and taken as a whole, it is
At the same time, the rate of biodegradation a relevant example of the importance of
(hydrolysis) must be appropriate to the time coupled transport processes. The
required for absorption. The rationale for viscoelastic character of polymer melts
the choice of LL and CL as the both reflects the entangled microstructure and
monomers is based upon these stringent plays an important role in property
property requirements. LL is the main development and in flow stability.
crystallizable component which determines Since rheological behavior is
the tensile strength while CL increases strongly influenced by the material’s
chain flexibility and thermal stability, structure and the interfacial characteristics,
thereby lowering the fiber stiffness and investigation of polymer rheology helps to
widening the melt processing window. By resolve processing problems such as slow
varying the monomer composition, polymer production rates, dimensional instability,
properties can be tailored to meet specific and poor mechanical properties. Moreover,
demands. However, such property control rheological studies are also employed for
can only be achieved by (a) controlling the the analysis of parameters such as
polymer’s chemical microstructure during molecular structures and chain
synthesis and then (b) by controlling the entanglements.13
polymer’s matrix morphology during fiber This research work has focused on
processing.9-11 investigating the melt behavior of a
Processing of polymer materials has medical-grade poly(L-lactide-co-ε-
a large influence on the resulting caprolactone) (PLC) copolymer for
mechanical and optical properties of the monofilament surgical suture production by
end-product. The combination of studying its rheological properties in the
temperature and shear rate in an extruder melt state in order to gain an understanding
needed to modulate the melt behavior of the of its processability. As a result, the
polymer to achieve desirable material copolymer’s chemical micro-structure and
properties is known as a “processing matrix morphology can be improved and
window”. Determining a defined controlled in order to meet the stringent
processing window is an empirical process property requirements of the application.
requiring a large quantity of materials that
may be expensive for certain medical grade 2. Materials and Methods
polymers. Therefore, rheology has been 2.1 Materials
used extensively to understand the flow L-lactide monomer was synthesized
behavior of polymers in different from L-lactic acid (Carlo Erba, Italy, 88%),
processing techniques such as extrusion and purified by repeated recrystallization and
additive manufacturing without requiring a dried for 24 hours under reduced pressure
large amount of material.12 Rheological (130 torr) at 55°C prior to its use in PC193

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
copolymerization. ε-caprolactone (Acros
Organics, Belgium, 99% ) monomer was
purified by fractional distillation under
reduced pressure. Tin (II) n-butoxide, Sn(n-
OBu)2, initiator was synthesized following
the method described in the US Patent Figure 1. The chemical structure of PLC.
9637507B2. A thermal stabilizer, triphenyl 2.3 Rheological measurements
phosphine (TPP) T-1136 supplied by The PLC pellets were melted at 180
o
Sigma®, was added to the reaction flask in C to the square plate 2.5×2.5 cm in a
order to evaluate its effect on the final thickness of 0.1 cm. Rheological behavior
properties of the monofilament fiber. of the PLC copolymer was investigated
2.2 Synthesis and Characterization of using a stress-controlled rotational
PLC rheometer (Bohlin Gemini HRnano, Malvern
Medical-grade poly(L-lactide-co-- Instruments Ltd. , UK) shown in Figure 2.
caprolactone), PLC, 70:30 mole% was The sample was heated at 180 oC in lower
synthesized by ring-opening plate of rheometer and pressed with the 25
polymerization (ROP) of LL and CL. The mm diameter plate to achieve a final gap of
initiator and thermal stabilizer were added 0. 5 mm. Dynamic strain sweeps were
to the reaction flask under dry nitrogen in a performed at various strains of 0.01-100%,
controlled atmosphere glove box at room and elastic moduli (G), viscous moduli
temperature. The reaction was heated at 160 (G) and complex viscosities (η*) were
o
C for 2 days and decreased to 140 oC, achieved. The frequency sweep test was
continued heat for 2 days. The PLC performed by varying a frequency range of
copolymer was cut, grinded and purified by 0.1-100 rad/s, the strain was fixed at 5%.
vacuum-dried at 30 oC, 55 oC and 65 oC for The temperature sweep test was
18 hours, 4 hours and 2 hours, respectively. investigated by setting the range of
The structures and properties of temperature from 170 oC to 200 oC. Steady
PLC copolymer were characterized shear testing was measured at constant of
according to ASTM F1925-17. Polymer temperature at 180 oC and various shear rate
composition and monomer sequencing were of 0.001 to 100 s-1 to specify the linearity of
characterized by a 500 MHz Bruker NEOTM melted PLC.
1
H-NMR spectrometer. Intrinsic viscosity,
[], was determined by dilute-solution
viscometry at a concentration of 0.1% (w/v)
in chloroform at 30 C using a Ubbelohde-
type viscometer in conjunction with a (b)
Schott-Gerate AVS300 Automatic
Viscosity Measuring System. Temperature
transitions and crystallinity were
determined by differential scanning (a) (c)
calorimetry (DSC) using a Perkin-Elmer
Figure 2. (a) Bohlin Gemini HRnano
DSC7 instrument with Pyris software.
Rotational Rheometer apparatus, (b)
polymer melted on lower plate and (c) PLC
sample plate. PC194

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 1. Physical/chemical property requirements of semi-crystalline poly(L-lactide-co--
caprolactone) copolymer resins for use as surgical implants
Specification ASTM F1925-17 PLC PLC with TPP
Residual Monomer < 2.0 % 0.69% Total 1.40% Total
(max 0.01% LL, 0.68% CL) (max 0.11%LL, 1.29%CL)
Residual Solvent < 1000 ppm 1 ppm 1 ppm
Heavy Metals ≤ 10 ppm 1 ppm 1 ppm
Residual Catalyst ≤ 150 ppm 126 ppm 86 ppm
(Optional)
Residual Water ≤ 0.5 % 0.12 % 0.08 %
(Optional)
Copolymer Ratio ± 3 % of target 0.57 % 2.14 %
(69.6:30.4)
(molar ratio) (71.5:28.5)
Specific Rotation 113° to120° 117° ± 0.26 116° ± 0.44

3. Results and discussion 3.2.2 Frequency sweep

3.1 Synthesis and Characterization of The elastic property of polymer can
PLC be investigated by the frequency sweep.
The structure and properties of the The range of frequency used in this research
medical-grade PLC according to ASTM is 0.1-100 Hz. The measurement was
F1925-17 are shown in Table 1. shown in Figure 4. The cross-section of G
From the characterization and
and G of PLC at frequency 80.36 Hz
property results of the PLC copolymers,
synthesized both with and without TPP, it appear in graph but the cross-section of G
was found that both copolymers were in and G of PLC with TPP disappear.
accordance with the requirements of ASTM Therefore, the transition of viscous liquid to
F1925-17. All of the variables; residual elastic solid of PLC can be happened before
monomer, solvent, heavy metals, catalyst, PLC with TPP. 3.2.3 Temperature sweep
residual water were within the permitted From the result of differential
limits, as were the copolymer compositions scanning calorimetry, both PLC and PLC
(70:30 mole ratio). with TPP had melting temperatures (Tm,
3.2 Rheological measurements end) of 157.0 oC. Temperature sweep
The rheological measurements from measurements were performed over the
4 methods show the properties of both temperature range of 170-200 oC, as
copolymers in the melt state. shown in Figure 5.
3.2.2 Strain sweep
The strain sweep plots of G (a), G
(b) and η* (c) of PLC and PLC with TPP in
melt state are shown in Figure 3. PLC has a
higher value of G, G and η* than PLC
with TPP but the stability is inverse,
observable from the linearity of elastic
modulus. Since, the substitution of TPP can
be replace by PLC, this process leads to be
chain extension of PLC by TPP. All values
have a linear of range 0.1 – 12.4 % strain;
hence we used a fixed 5 % strain to control PC195
the other sweep tests.

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 1.00E+04 (a) 1.00E+05 (b)
PLC 1.00E+04
1.00E+03 PLC
1.00E+03
1.00E+02
PLC
G'

G''
1.00E+02 PLC
with
1.00E+01 with
TPP
1.00E+01 TPP

1.00E+00 1.00E+00
1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E-01 1.00E+00 1.00E+01 1.00E+02
%Strain %Strain

1.00E+05
(c)
1.00E+04
PLC
1.00E+03
η*

1.00E+02 PLC
with
1.00E+01 TPP
1.00E+00
1.00E-01 1.00E+00 1.00E+01 1.00E+02
%Strain

Figure 3. The plot of elastic modulus (G) (a), viscous modulus (G) (b) and complex viscosity
(η*) (c) of PLC and PLC with TPP in melt state.

1.00E+05
1.00E+06
(a) 1.00E+04 (b)
1.00E+05 G' G'
G' and G" (Pa), Tan delta

G' and G" (Pa), Tan delta

1.00E+03
1.00E+04
1.00E+02 G''
1.00E+03
G'' 1.00E+01
1.00E+02
1.00E+00 Tan
1.00E+01 delta
1.00E-01
1.00E+00 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02
1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02
frequency (Hz)
frequency (Hz)

Figure 4. The relationships between elastic modulus (G), viscous modulus (G) and complex
viscosity (η*) of (a) PLC and (b) PLC with TPP by varying the range of frequency.

1.00E+05
1.00E+05
(a) (b)
1.00E+04
1.00E+04 PLC
PLC
1.00E+03
1.00E+03
PLC
G'
G"

with PLC
1.00E+02 1.00E+02
TPP with
TPP
1.00E+01 1.00E+01

1.00E+00 1.00E+00
170.00 180.00 190.00 200.00 170.00 180.00 190.00 200.00
Temperature (oC) Temperature (oC)

Figure 5. Plots of (a) elastic modulus (G) and (b) viscous modulus (G) by given temperature
of PLC and PLC with TPP.
PC196

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Both copolymers have a low stability this research work will lead to the fabrication
at increasing temperature. The values of G of absorbable surgical suture and improve the
and G decrease with temperature. properties of absorbable surgical sutures.
Accordingly, the melt extrusion at rather high
temperature than Tm can affect the degradation Acknowledgements
of the copolymer. This work has been supported by
3.2.4 Steady shear viscosity Chiang Mai University. Kittisak Yarungsee
The shear viscosity of polymer can be would also like to express his sincere thanks
measured by the resistance of melt flow. The to the Science Achievement Scholarship of
response of shear viscosity by giving shear Thailand, SAST, for providing financial
rate was shown in Figure 6. In the beginning support.
of shear input, the graph of viscosity is quite
stable. This linearity show the toleration with References
shear force, shear viscosity independent of 1. Ayyoob, M.; Lee, D.H.; Kim, J.H.; Nam,
shear rate. The viscous fluid behaves as a S.W.; Kim, Y.J. Fiber Polym., 18, 407
Newtonian fluid. (2017).
2. Weir, N.A.; Buchanan, F.J.; Orr, J.F.;
1.00E+03 Farrar, D.F.; Boyd, A. Biomaterials 2004,
25, 3939.
PLC 3. Azimi, B.; Nourpanah, P.; Rabiee, M.;
Shear viscosity (η,Pas)

1.00E+02
Arbab, S. J. Eng. Fiber Fabr. 2014, 9, 74.
4. Abhari, R.E.; Mouthuy, P.-A.; Zargar, N.;
1.00E+01 PLC Brown, C.; Carr, A. J. Mech. Behav.
with
TPP
Biomed. Mater. 2017, 67, 127.
5. Tomihata, K.; Suzuki, M.; Oka, T.; Ikada,
1.00E+00
1.00E-03 1.00E-01 1.00E+01
Y. Polym. Degrad. Stabil. 1998, 59, 13.
Shear Rate (1/s)
6. Baimark, Y.; Molloy, R.; Molloy, N.;
Siripitayananon, J.; Punyodom, W.;
Figure 6. The variation of shear viscosity Sriyai, M. J. Mater. Sci.- Mater. M. 2005,
compared to shear rate of both copolymers. 16, 699.
7. Ruengdechawiwat, S.; Siripitayananon, J.;
4. Conclusions Molloy, R.; Somsunan, R.; Topham, P.D.;
The synthesis of PLC and PLC with Tighe, B.J. J. Mater. Sci.- Mater. M. 2016,
TPP are effective in physical/chemical 65, 277.
properties. The compositions of both 8. Siripitayananon, J.; Molloy, R.; Bunkirn,
copolymers were not significantly different. S.; Kleawkla, A.; Panjakha, R.;
The addition of the TPP thermal stabilizer had Chooprayoon, P. Int. Polym. Proc. 2008,
2, 1
only a slight effect on the copolymer’s
9. Choi, E.-J.; Park, J.-K.; Chang, H.-N. J.
rheological properties. However, it was Polym. Sci. Polym. Phys. 1994, 32, 2481.
significant to note that the PLC copolymer 10. Grijpma, D. W.; Pennings, A. J. Polym.
synthesized with TPP had values of elastic Bull. 1991, 25, 335.
modulus, viscous modulus and complex 11. Hiljanen-Vainio, V.; Karjalainen, T.;
viscosity less than the PLC without TPP from Seppälä, J. J. Appl. Polym. Sci. 1996, 59,
all methods. The addition of TPP could also 1281.
increase the length of the linear region of 12. Ahlinder, A.; Fuoco, T.; Finne-Wistrand,
thermal stability. Ultimately, it is hoped that A. Polym. Test. 2018, 72, 214. PC197
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
13. Sadiku-Agboola, O.; Sadiku, E. R.;
Adegbola, A. T.; Biotidara, V. Mater. Sci.
Appl. 2011, 2, 30.

PC198
© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Synthesis and characterization of hydrophobic cellulose from Khoi fiber
Worranun Wongchompoo1, Radchada Buntem2*
Department of Chemistry, Faculty of Science, Silpakorn University, Nakhon Pathom 73000, Thailand
*E-mail: [email protected], [email protected]

Cellulose can be easily hydrophobized using trimethylsilyl groups. The modified

cellulose is being used for drug delivery and microencapsulation. In this research, khoi fiber
was used as a source of cellulose fiber. Khoi bark was refluxed with 4 % (w/v) NaOH solution
to remove lignin and hemicellulose. The completeness of lignin removal was monitored by IR
spectroscopy. 1.0 g of extracted cellulose was soaked in water and N,N-dimethylacetamide
(DMA) respectively. The soaked cellulose was dissolved in dimethylacetamide/LiCl and
reacted with hexamethyldisilazane (HMDS) yielding trimethylsilylcellulose (K_TMSC). The
IR spectrum shows the presence of -Si(CH3)3 groups: Si-O at 1046 cm-1, C-Si at 1252, 842 and
749 cm-1. The 1H-NMR result confirms the presence of -Si(CH3)3 groups at  0 ppm and
pyranose ring protons in the range of 3-4 ppm. SEM image of K_TMSC shows the fibrous
characteristics of cellulose while the EDX shows the presence of Si. The degree of substitution
(DS) values calculated from FT-IR and EDX data are 1.56 and 1.02 respectively. TGA results
show the higher stability of cellulose in K_TMSC as compared with that of khoi fiber after
alkali treatment

1. Introduction historical-related fiber. In this research,

cellulose was extracted from khoi bark by
Cellulose, a natural long chain
an alkaline method. The modification
polymer, has versatile uses in many
process was performed on treated khoi and
industries such as paper,1 textiles2 and
commercial celluloses using hexamethyl-
foods.3 Cellulose is an abundant,
disilazane (HMDS) to yield trimethylsilyl-
biodegradable and easily modified
substituted cellulose (TMSC).
biomaterial. Having a large number of
reactive hydroxyl groups, cellulose can be
2. Materials and Methods
functionalized via esterification4,
2.1 Materials
etherification,5 nitration,6 oxidation7 and
Khoi bark (K) was cut from Streblus
silylation.8 Among these, silylation is used
asper Lour. Commercial cellulose (C) DS-
to hydrophobize the cellulose surface. The
0 was obtained from Fluka. All chemicals
hydrophobic cellulose has been used in
were obtained from Fluka and used as
various applications like pharmaceuticals,9
received. All solvents were of analytical
foods10 and coating.11 Many cellulose
grade.
precursors from different plant fibers have
2.2 Cellulose extraction
been attempted for hydrophobized
Cellulose extraction was performed
process.12,13 In the past, khoi fiber from the
by reacting khoi bark with 4% (w/v) NaOH
bark of Streblus asper Lour. was processed
solution under reflux. The extraction
for making khoi paper used in Thai
process was repeated several times until all
manuscripts. A few studies were performed
lignin was removed. The extracted
on khoi fiber14,15 and no chemical
cellulose was neutralized by 1 M HCl,
modification has been done on this Thai
PC199

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
subsequently washed several times with 3. Results & Discussion
water and oven-dried to yield K_1. 3.1 Cellulose extraction and synthesis of
2.3 Synthesis of trimethylsilyl cellulose trimethylsilyl cellulose.
The synthesis of trimethylsilyl Lignin and hemicellulose in khoi (K)
cellulose was followed from a previous were successfully removed via the
publication.12 1.0 g of K_1 or commercial hydrolysis of the ester bond15 using NaOH
cellulose (C) was soaked with deionized solution. ATR-FTIR spectra of K and K_1
water at 4°C for 24 hours and filtered. The are presented in Figure 1 (a) and (b)
fiber was then swelled in a 100 mL of N,N- respectively. The carbonyl vibration in
dimethylacetamide (DMA) for 1 hour and lignin at 1733 cm-1 is not observed in the
filtered. In a separate flask, 150 mL of spectrum of K_1.
DMA were heated under nitrogen to 110°C
for 15 minutes. The DMA was further (a)
heated to 165°C at which temperature the
treated fiber was added. After 1 hour the (b)
temperature was decrease to 100 °C and 15
(c)
g of LiCl was then added and stirred until
dissolved. The solution was cooled to room
temperature and then the clear yellow (d)
solution was heated to 80°C and 20 mL of
hexamethyldisilazane (HMDS) were added
dropwise. The mixture was maintained at
this temperature for 4 hours to obtain Figure 1. IR spectra of (a) K (b) K1 (c)
yellow gel. The gel was filtered and washed K_TMSC (d) C_TMSC.
by methanol and left to dry in a desiccator Table 1. Modes of vibration in cellulose
to yield trimethylsilylcellulose (K_TMSC samples.
or C_TMSC).
2.4 Spectroscopic measurement Wave number (cm-1)
The cellulose samples were Mode of Vibration K
K_1 K_TMSC
C_TMS
analyzed using Spectrum 100 FT-IR C
spectrophotometer (Perkin Elmer). 1H- (O-H) 3336 3337 3490 3484
(C-H) 2918 2916 2959 2958
NMR of TMSC was measured by a Nuclear
(C=O) 1733 - - -
Magnetic Resonance Spectrometer, Bruker (O-H) 1619 1635 1624 1631
300 MHz (Avance III HD) using CDCl3 as 1424, 1429, 1415, 1415,
a solvent and a standard. The surface (C-H) 1367, 1371, 1373, 1373,
morphology and elemental composition 1316 1335 1311 1313
were studied by a TESCAN MIRA 3 (C-O-C)
1158 1160 1159 1160
(pyranose ring)
scanning electron microscope associated
(C-O) (2º
with EDAX microprobe (element). The 1103 1104 1124 1121
alcohol)
thermal stability was measured using Pyris (Si-O) - - 1046 1061
1 Thermogravimetric analyzer (Perkin (Si-CH3) - - 1252, 1251,
Elmer) 842, 841,
749 751

PC200

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 To synthesize TMSC, the crucial
(a)
step is to dissolve the cellulose. The strong
hydrogen bonds between the cellulose
polymeric chains are destroyed (a) by
−
DMA/LiCl. The Cl anions replace the
OH···O hydrogen bonds with the formation
of OH···Cl− links16 Li+ cations bind
strongly with the carbonyl oxygen of
DMAc molecules to form a Li+(DMAc)x
(b)
complex which can further stabilize the
OH···Cl− and help disperse the cellulose
chain.17 The dispersed cellulose is then
readily reacted with HMDS to form TMSC
as the following details:18

Figure 3. 1H-NMR spectrum of (a)

K_TMSC (b) C_TMSC.
K_1, K_TMSC and C_TMSC were
analyzed by SEM-EDX technique. The
SEM image of K_1 shows clearly the
microfibril structure as seen in Figure 4(a).
The fibrous characteristics of cellulose
were still observed in K_TMSC (Figure
4(b)) but none was observed in C_TMSC
(Figure 4(c)). This indicates the incomplete
Figure 2. Reaction mechanism of cellulose conversion of K_TMSC as compared with
and HMDS C_TMSC. The elemental analysis of
K_TMSC and C_TMSC shows the
The K_TMSC and C_TMSC were
presence of Si as seen in Figure 5.
characterized by ATR-FTIR, 1H-NMR and
SEM-EDX. The IR data was presented in (a) (b)
Figure 1c and d and Table 1. The
characteristic Si-CH3 vibrations of
K_TMSC were observed at 1252, 842, 749
while those of C_TMSC are observed at
1251, 842, 751 cm-1. The Si-O stretching of
(c)
K_TMSC and C_TMSC appeared at 1046
and 1061 cm-1. The 1H-NMR spectrum in
Figure 3 showed the presence of -Si(CH3)3
groups at 0.08 (K_TMSC) and 0.12 ppm
(C_TMSC) and pyranose ring protons in
the range of 2.94-4.37 (K_TMSC) and
Figure 4. SEM image of (a) K_1 (b)
2.94-4.65 ppm (C_TMSC).19
K_TMSC (c) C_TMSC. PC201

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Table 2. Decomposition of cellulose
(a) (b) sample.
Sample Decompo Temperature (°C) % weight
-sition step loss
Start Final Tp* Each Total
step
K_1 1st 48.8 187.6 85.0 2.8 86.9
2nd 187.6 435.4 361.0 58.7
3rd 435.4 693.9 494.8 24.8
Average atomic % (±SD) (n=3)
Sample 4th 693.9 775.2 716.6 0.7
C O Si
C 1st 49.1 214.9 92.7 2.0 92.0
69.83 25.57 4.60
K_TMSC 2nd 214.9 405.7 353.0 90.0
(±2.54) (±1.77) (±0.84)
59.94 31.07 8.99 K_TMSC 1st 48.8 431.7 390.1 87.0 87.0
C_TMSC C_TMSC 1st 48.4 203.8 107.8 1.2 96.0
(±0.54) (±0.48) (±0.31)
Figure 5. SEM-EDX data of (a) K_TMSC 2nd 203.8 431.9 389.7 94.8
Tp* = Peak temperature the temperature at the maximum
(b) C_TMSC. decomposition

Degree of substitution (DS)

(a) (b)
Degree of substitution of K_TMSC
was calculated using IR, NMR and EDX
data. For the IR data, the DS value can be
calculated by using the following formula21
A
4.05  OH
A CH
(c) (d) DS 
1.37

AOH = peak area (absorbance mode) of the (O-H)

ACH = peak area (absorbance mode) of the (C-H)
while the DS value from 1H-NMR data was
Figure 6. TGA spectrum of (a) K_1 (b) determined using equation below :22
K_TMSC (c) C (d) C_TMSC.
7 A (a)
DS = 
The K_1, C, K_TMSC and 9 A (b  c)
C_TMSC were analyzed by TGA
technique. The higher decomposition A(a) = peak area of proton a
temperature of K_TMSC as compared with A(b+c) = peak area of proton b and c
K_1 indicates the higher stability of
modified cellulose. The same trend was The equation for calculating DS value from
observed in the case of C_TMSC and C EDX data is as below :23
samples as the data in Table 2. The silyl
5  Si%
groups help protect the cellulose20 so that DS 
the thermal stability of both K_TMSC and O%
C_TMSC is increased. All DS values are summarized in Table 3.
Among the three techniques, NMR PC202

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
provides better DS values due to the greater 2. Alam, M. N.; Christopher L. P.
homogeneity of the analyzed sample. In the Carbohyd. Polym. 2017, 173, 253-258.
case of C_TMSC, the DS values obtained 3. Mu, R.; Hong, X.; Ni, Y.; Li, Y.; Pang,
from these three techniques are larger than J.; Wang, Qi.; Xiao, J.; Zheng, Y.
two. This indicates that more than half of Trends. Food. Sci. Tech. 2019, 93, 136–
the hydroxyl groups of cellulose are 144.
4. Keyrilainen, P. W.; Ropponen, J.
substituted by trimethylsilyl groups. While
Heliyon. 2019, 5, e02898.
in the case of K_TMSC, the DS values from
5. Li, W.; Xu, Z.; Wang, Z.; Liu, X.; Li,
ATR-FTIR and SEM-EDX data are less C.; Ruan, F. Int. J. Adhes. Adhes. 2018,
than two. 1H-NMR data showed very low 84, 101-107.
signal of pyranose ring protons in the range 6. Nikolskya, S. N.; Zlenkoab, D. V.;
of 2.94-4.37 so the actual DS value could Melnikova, V. P.; Stovbuna S. V.
not be calculated. The low DS value of Carbohyd. Polym. 2018, 204, 232-237.
K_TMSC may come from the residual 7. Siró, I.; Plackett, D. Cellulose. 2010,
lignin in K_1. Lignin removal24 by reacting 17, 459–494.
the K_1 with oxidizing agent like hydrogen 8. Hubbe, M.A.; Rojas, O. J.; Lucia, L. A.;
peroxide may help improve the DS value of Sain, M. Bioresources. 2008, 3, 929-
the K_TMSC. 980.
9. Bruschi, M. L.; Cardoso, M. L. C.;
Table 3. DS values of TMSC calculated by Lucchesi, M. B.; Gremia˜o, M. P. D.
three different techniques. Int. J. Pharmaceut. 2003, 264, 45–55.
10. Wojtowicz, E.; Zawirska-Wojtasiak,
DS value
Technique R.; Adamiec, J.; Wa˛sowicz, E.;
K_TMSC C_TMSC
Przygon´ ski, K.; Remiszewski, M. J.
ATR-FTIR 1.56 2.26
1
H-NMR - 2.49
Food Sci. 2010, 75, S441–S445.
EDX 1.02 1.39 11. Sunanda, R.; Lindong, Z.; Jung, W. K.;
Hyun, C. K.; Jaehwan, K. Prog. Org.
Coat. 2020, 140, 105500.
4. Conclusion
12. Wongchompoo, W.; Kanthamoon, T.;
The alkali treatment of khoi fiber
Buntem, R. KEM. 2019, 804, 121-127.
using 4%(w/v) NaOH was successfully 13. Zhang, X.; Liu, M.; Wang, H.; Yan, N.;
remove lignin and hemicellulose. The Cai, Z.; Yu, Y. Carbohyd. Polym. 2019,
extracted cellulose was subsequently 208, 232-240.
silylated to form hydrophobic trimethylsilyl 14. Boonpitaksakul, W.; Chitbanyong, K.;
cellulose. This modified khoi cellulose is Puangsin, B.; Pisutpiched, S.;
higher in thermal sensitivity as compared Khantayanuwong, S. Bioresources.
with khoi after alkali treatment. 2019, 14, 6411-6420.
15. Rueangyodjantana, J.; Buntem, R.
Acknowledgements Veridian E-J. 2017, 4, 50-59.
Many thanks to Department of 16. McCormick, C. L.; Callais, P. A.
Chemistry, Faculty of Science, Silpakorn Polymer. 1987, 28, 2317-2323.
17. Zhang, C.; Liu, R.; Xiang, J.; Kang, H.;
University.
Liu, Z.; Huang, Y. J. Phys. Chem. B.
2014, 18, 9507−9514.
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1. Chutrtong, J.; Chutrtong, W. Procedia Dubois, P.; Dellacherie, E.; Six, J. L.
Manufacturing. 2019, 32, 969-974. Polymer. 2002, 43, 1735-1743. PC203

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19. Livazovic, S.; Li, Z.; Behzad, A. R.; 22. Puspasari, T.; Pradeep, N.; Peinemann,
Peinemann, K.V.; Nunes, S. P. J. K.V. J. Membr. Sci. 2015, 491, 132-
Membr. Sci. 2015, 490, 282–293. 137.
20. Petzold, K.; Koschella, A.; Klemm, D.; 23. He, A.; Liu, D.; Tian, H.; Jin, Y.;
Heublein, B. Cellulose. 2003, 10, 251– Cheng, Q.; Song, J. Cellulose Chem.
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Macromol. Chem. Phys. 1999, 200, 2017, 2, 100-110.
693-697.

PC204

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Evaluation of non-thermal atmospheric pressure plasma pretreatment on
microwave-assisted hydrolysis of cellulose and sugarcane bagasse
Panithinat Suwannanon, Rachnarin Nitisoravut, Siwarutt Boonyarattanakalin*
School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology,
Thammasat University, Pathumthani 12120, Thailand
*E-mail: [email protected]

Depolymerization of cellulose is a critical step for sustainable production of chemicals

and fuels from lignocellulosic biomass. However, cellulose contains highly crystalline parts
which obstruct the access of reactants and catalysts. Several pretreatments had been studied to
decrease crystallinity in order to improve the hydrolysis of cellulose. Non-thermal atmospheric
plasma for biomass pretreatment is relatively new and investigated in only a few studies. Non-
thermal atmospheric pressure plasma (NTAP) is advantageous due to low energy consumption
and solvent-free. In this study, cellulose and sugarcane bagasse powder were selected as
biomass sources. The samples were pretreated under the dielectric barrier discharge (DBD)
plasma reactor with the frequency and voltage of 5.5 kHz and 6 kV, respectively. The
pretreatment time of 30 to 180 minutes was investigated. The experiments showed that the
longer pretreatment time significantly lowered the crystallinity of the samples. Microwave
irradiation was employed to assist the hydrolysis reaction because it features a faster, uniform
and more efficient heating. Dilute hydrochloric with a concentration of 1 M was used as a
catalyst. The reaction parameter especially the operating temperatures was investigated, the
optimum temperature of 150 °C gave the maximum glucose yield. The glucose released from
the hydrolysis of the samples was quantified by high performance liquid chromatography
(HPLC). A higher glucose released from the pretreated samples confirmed the success of
NTAP pretreatment technique.

1. Introduction polymers namely cellulose, hemicellulose

Biomass currently has become and lignin. In particular, cellulose is
attractive feedstock for fuel and chemical composed of glucose monomer units that can
productions because it is renewable and be converted into various fuels and
carbon-rich material. Moreover, the use of chemicals, such as, 5-hydroxymethylfurfural
biomass, particularly, wastes from (HMF), levulinic acid, ethylene glycol,
agricultural and industrial segments does not ethanol, liquid alkanes, and many others.
compete with the food supply. Unfortunately, due to the highly
In Thailand, sugarcane, rice, and crystalline structure of cellulose, it is
palm oil are among the top agricultural recalcitrant to enzymatic and chemical
products. Their residues are generally transformations. In order to achieve efficient
eliminated by burning at the harvesting fields depolymerization of cellulose, any
leading to air pollutions. To reduce pretreatment techniques were developed to
environmental problems, therefore, it is reduce its crystallinity and induce partial
better to converse those residues into depolymerization.1 However, the
valuable chemicals. conventional chemical pretreatments using
Biomass is a lignocellulosic material enzyme, acid or alkaline may generate
containing three major carbohydrate dangerous chemical wastes leading to PC205

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
negative environmental impacts and high These drawbacks prevent the
operation costs.2 Moreover, the products applications of conventional technologies for
from the traditional methods contain large-scale production with competitive
undesired compounds, such as organic acids prices.
and aldehydes from side-reactions.3

Figure 1. Illustration of the DBD plasma reactor

Recently, non-thermal atmospheric To investigate chemical accessibility

plasma (NTAP) pretreatment of of biomass after the exposure to NTAP, the
lignocellulose has been developed to dilute acid hydrolysis was conducted as it
overcome the presence of toxic chemicals uses simple chemicals with short reaction
from conventional treatments.1 NTAP was time but requires high temperatures because
reported as a physical treatment for the partial the conductive and convective heating
depolymerization of cellulose without the possess are slow.6 Therefore, microwave
presence of neither solvent nor catalyst. irradiation was employed as it potentially
Plasma also promotes a chemical treatment provides fast, uniform and efficient heating
using the reactive species, such as singlet together with synergic effects on several
delta oxygen, radicals, HNO2 and NO2. These reactions.7
reactive species were capable of rapidly Herein, the NTAP pretreatments on
breaking C‒C bonds, creating additional cellulose and sugarcane bagasse were studied
functional groups such as carbonyls in the in order to understand how the hydrolysis of
biomass via oxidation processes.4 cellulosic samples into soluble glucose could
In addition, O3 produced from the air be improved by varying the pretreatment
or pure oxygen in the plasma was predicted to time. The aim of this experiment was to
oxidatively degrade unsaturated organic decrease the crystallinity of the cellulose
compounds in lignin, while it affected samples to achieve better depolymerization.
carbohydrates only to a minor extent. The The efficiency of the NTAP pretreatment for
removal of lignin would be beneficial to different pretreatment conditions was
subsequent enzymatic hydrolysis and evaluated by chemical composition
fermentation.5 PC206

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
analysis after pretreatment and after with 32 scans at a resolution of 4 cm-1 in
microwave-assisted dilute acid hydrolysis. absorbance mode. The energy change of
dehydration measured by differential
2. Materials and Methods scanning calorimetry (DSC, Mettler Toledo
2.1 Materials DSC1) was used to determine crystallinity8 of
Cellulose powder purchased from pretreated biomass as the following equation;
Sigma-Aldrich. Sugarcane bagasse was dried ∆𝐻0 − ∆𝐻𝑠
%𝐶𝑟𝑦𝑡𝑎𝑙𝑙𝑖𝑛𝑖𝑡𝑦 = × 100%
in an oven at 105 °C then grounded and ∆𝐻0
sieved, the powder was kept in a desiccator at Where; ∆𝐻0 =energy required to dehydrate
room temperature. completely amorphous cellulose (anhydrous
2.2 Plasma pretreatment deacetylation of cellulose triacetate)
2 g of biomass powder was placed ∆𝐻𝑠 =energy required to dehydrate a sample.
between the dielectric barriers discharge For DSC, 15 mg of sample was scanned over
(DBD) plasma reactor with the frequency and the temperature range of 50 to 400°C with a
voltage of 5.5kHz and 6 kV, respectively. The heating rate of 40°Cmin-1. The integration of
instrument set up is illustrated in Figure 1. each DSC curve was performed between
2.3 Microwave-Assisted dilute acid Tmax-60°C to Tmax+60°C where Tmax was
hydrolysis nearly 130°C.
100 mg of biomass was hydrolyzed by The liquid solutions were analyzed by
1 mL of 1 M diluted hydrochloric and heated high performance liquid chromatography
by microwave reactor (CEM, Discover SP (HPLC) equipped with a refractive index (RI)
909155, USA). The reactor parameter set up detector and a UV detector. The
was pressure = 290 psi, power = 150 watts concentrations of saccharides were measured
and ramping time = 5 min. The reaction by an RI detector and a carbohydrate column
temperature was 150 °C. The reaction time (Transgenomic CARBOSEP CHO682,
was fixed at 15 min. Afterward, the reaction LEAD column, CHO-99-9854, USA) using
was terminated by adding 9 mL of DI water H2O with the flow rate of 0.4 mL min-1 as the
to the hydrolysate. The dilute hydrolysate mobile phase. The column temperature was
was stirred 1 hour to dissolve soluble maintained at 80 °C and the injection volume
components. The insoluble component was was 20 µL.
filtered through Whatman filtering paper Alternatively, HMF was measured by
No.1. the UV detector at 280 nm along with a
2.3 Analysis of samples Luna® 10 µm C18 100 Å, LC Column (250
The pretreated biomass powder was x 4.6 mm) column using a solution of
dried and kept in a desiccator with CH3OH: H2O = 10:90 (v/v) with the flow rate
CaSO4·H2O as an absorber prior analysis. of 1 mL min-1 as the mobile phase. the
The changes in the constituent injection volume was 5 µL.
characteristics of non-pretreated and
pretreated biomass particles were measured 3. Results & Discussion
by an attenuated total reflectance - Fourier Cellulose powder was used as a model
transforms infrared spectroscopy (ATR- compound in order to investigate the effect of
FTIR, Nucolet iS5) with an iD7 ATR NTAP pretreatment on the hydrolysis, then
accessory with a diamond crystal. The FTIR sugarcane bagasse was evaluated as an
spectra were recorded from 400 to 4000 cm-1 abundantly available biomass. The PC207

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
investigation on NTAP pretreatment mainly noticeably lower than the non-pretreated
focused on the effect of the duration of sample. It is believed that the lignin content
pretreatment which was varied from 30 to 180 in the sample was altered leading to the
min. delignification of samples as found in a
previous study.2
Carbonyl groups (∼1,700 cm–1)
would be expected in cellulose and xylan if
they were oxidized by O3.5 However, there
was no peak observed at this wavelength for
both pretreated cellulose and sugarcane
bagasse since the oxidation might not occur.
The broad absorption in the range 3000 to
3600 cm−1 can be described to the stretching
of H-bonded –OH groups. The intramolecular
Figure 2. FTIR spectra of non-pretreated hydrogen bonding of O(3)H···O(5) in
(dash line) and 180min-pretreated cellulose cellulose is generally shown at 3375-3340
(solid line) cm-1.10 The peak intensity of the pretreated
cellulose at 3331 cm-1 was lower than the
non-pretreated cellulose which suggests a
weaker intramolecular hydrogen bonding of
cellulose after the pretreatment. However, the
peak of the non-pretreated and the pretreated
sugarcane bagasse at this range were
identical. It was assumed that the
pretreatment might not be sufficiently strong
to pass through surrounded complex
matrixes, such as lignin and hemicellulose,
thereafter, cellulose was slightly affected by
Figure 3. FTIR spectra of non-pretreated
the plasma.
(dash line) and 180min-pretreated sugarcane
Regarding the crystallinity as shown
bagasse (solid line)
in Table 1. The longer exposure time of the
FTIR spectra disclose the changes in
plasma pretreatment, the lower crystallinity
the structure of non-pretreated and NTAP-
was seen in the result. For cellulose, the
pretreated cellulose and sugarcane bagasse as
crystallinity was significantly dropped since
shown in Figures 2 and 3 respectively. The C-
the first 30 min, then slightly decreased after
O-C stretch of the β-1,4-glycosidic linkage in
60 min until 180 min. The maximum
cellulose is indicated at 1160 and 900 cm-1.9
difference between the crystallinity of non-
The peak intensity at these wavelengths was
pretreated and pretreated cellulose was
slightly reduced after NTAP pretreatment for
approximately 12%, while sugarcane bagasse
both cellulose and sugarcane bagasse.
was 7%. NTAP had less effect on the
The wavelength of 1030 cm-1 is
crystallinity of sugarcane bagasse compared
associated with C-H in guaiacyl which is one
to cellulose as it was assumed that the crystal
of the aromatic units in lignin.5 The intensity
regions mainly contain in cellulose.
of this peak after the pretreatment was
Sugarcane bagasse, composing of 30-40% PC208

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
cellulose, has originally less crystalline parts gave the highest glucose yield which
than pure cellulose. Thus, sugarcane may be accounted for ~8% higher than the C0.
less affected by NTAP. For the hydrolysis of sugarcane
Due to the positive effects on the bagasse, in a similar fashion as the cellulose,
reduction of crystallinity in cellulose and an increase of pretreatment time resulted in a
sugarcane bagasse, the hydrolysis reactions higher glucose yield. The pretreatment time
were performed to confirm that the pretreated bagasse, in a similar fashion as the cellulose,
samples were less recalcitrant, leading to an increase of pretreatment time resulted in a
easier depolymerization. Since glucose is a higher glucose yield. The pretreatment time
major constituent of cellulose, it was of 180 min (SBG180) gave the highest
expected to obtain a higher glucose glucose yield which accounted for ~8%
concentration from the pretreated sample higher than the non-pretreated sugarcane
after the hydrolysis step. bagasse (SBG0).
A set of experiments was performed In addition, glucose could undergo
to investigate the effect of reaction dehydration to form HMF. Although, HMF is
temperatures. Figure 1 exhibits preliminary a versatile compound but also an inhibitor in
screening of temperature parameters (100, the fermentation process. Since NTAP
130, 150, 170, and 200 °C) on the conversion pretreatment from this study did not show a
of native cellulose into glucose. The reaction significant improvement in HMF production,
temperature of 150°C was the most suitable therefore, this technique may be compatible
reaction temperature for the conversion of with the fermentation of derived glucose from
cellulose into glucose. Therefore, the reaction biomass for biofuels production.
temperature of 150 °C was used for the entire
hydrolysis experiment.
In addition, glucose could undergo
dehydration to form HMF. Although, HMF is
a versatile compound but also an inhibitor in
the fermentation process. Since NTAP
pretreatment from this study did not show a
significant improvement in HMF production,
therefore, this technique may be compatible
with the fermentation of derived glucose from
biomass for biofuels production.
Figure 4. Preliminary screening of
For the hydrolysis of cellulose, an
temperature parameter (100,130,150,170,
increase of pretreatment time resulted in a
and 200°C) on the conversion of native
higher glucose yield (Table 1). Although, the
cellulose into glucose using 1M HCl, 15min.
crystallinity of 30-min-pretreated cellulose
(C30) was relatively lower than non-
pretreated cellulose (C0), however, the
glucose yields from C0 and C30 were similar.
The pretreatment time of 120 min (C120)

PC209

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 1. The results of crystallinity and hydrolysate products of cellulose and sugarcane
bagasse pretreated by NTAP.
Pretreatment Time
Material Sample Name %Crystallinity %Glucose %HMF
(min)
C0 0 62.18±1.21 17.97±0.70 0.93±0.15
C30 30 52.80±0.28 18.34±0.58 1.15±0.35
Cellulose C60 60 46.85±2.42 25.42±0.18 1.20±0.13
C120 120 46.52±0.28 26.54±1.43 1.17±0.01
C180 180 49.47±1.06 26.25±0.78 1.20±0.02
SBG0 0 53.43±0.65 8.86±0.71 0.31±0.04
SBG30 30 52.25±0.40 13.90±0.12 0.38±0.01
Sugarcane
SBG60 60 50.86±0.71 14.79±0.41 0.42±0.00
Bagasse
SBG120 120 46.77±0.60 16.00±0.38 0.41±0.01
SBG180 180 45.31±0.43 16.64±0.13 0.55±0.00

Acknowledgments
This work was supported by the 4. Vanneste, J.; Ennaert, T.; Vanhulsel,
Thailand Research Fund (RSA6280106). We A.; Sels, B. ChemSusChem 2017, 10 (1), 14-
thank Center of Scientific Equipment for 31.
Advanced Research, Thammasat University 5. Schultz-Jensen, N.; Leipold, F.;
(TUCSEAR) for supporting facilities and Bindslev, H.; Thomsen, A. B. Appl. Biochem.
equipment. Mr. Suwannanon is a JGSEE Biotechnol. 2011, 163 (4), 558-572.
6. Lee, Y.; Iyer, P.; Torget, R. W., Dilute-
scholarship recipient.
acid hydrolysis of lignocellulosic biomass. In
Recent progress in bioconversion of
References lignocellulosics, Springer: 1999; pp 93-115.
1. Benoit, M.; Rodrigues, A.; Vigier, K. 7. Surati, M. A.; Jauhari, S.; Desai, K.
D. O.; Fourré, E.; Barrault, J.; Tatibouët, J.-M.; Arch. Appl. Sci. Res. 2012, 4 (1), 645-661.
Jérôme, F. Green Chem. 2012, 14 (8), 2212- 8. Bertran, M. S.; Dale, B. E. J. Appl.
2215. Polym. Sci. 1986, 32 (3), 4241-4253.
2. Souza-Corrêa, J.; Oliveira, C.; Wolf, 9. Kshirsagar, S. D.; Waghmare, P. R.;
L.; Nascimento, V.; Rocha, G.; Amorim, J. Loni, P. C.; Patil, S. A.; Govindwar, S. P. RSC
Appl. Biochem. Biotechnol. 2013, 171 (1), 104- Adv. 2015, 5 (58), 46525-46533.
116. 10. Oh, S. Y.; Yoo, D. I.; Shin, Y.; Seo, G.,
3. Song, C.-L.; Zhang, Z.-T.; Chen, W.- Carbohydr. Res. 2005, 340 (3), 417-428.
Y.; Liu, C. IEEE Trans. Plasma Sci. 2009, 37
(9), 1817-1824.

PC210

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Hydrogel composite of bacterial cellulose and polyacrylamide
for application in drug delivery
Walaiporn Prissanaroon-Ouajai*, Wanida Phungpai, Palida Hanprasert
Department of Industrial Chemistry, Faculty of Applied Science,
King Mongkut’s University of Technology North Bangkok, Thailand
*E-mail: [email protected]

Polyacrylamide (PAM) hydrogels have been used as one of the novel soft materials in
drug delivery applications. This research focused on the development of PAM hydrogel with
improved mechanical properties by incorporating of bacterial cellulose (BC) from Nata de coco
in the hydrogel. The influence of the different BC amounts on the hydrogels properties was
also investigated in order to assess their potential applications in matrices for advanced
controlled drug release systems. The properties of the PAM/BC hydrogel composites were
determined by the analysis of the swelling ratio, gel fraction, porosity and mechanical
properties. The results indicated the BC amounts played an important role in the enhancement
of chemical crosslinking process of PAM hydrogel. The high BC content incorporated in the
hydrogel resulted in the decreases in swelling performance and porosity. Mechanical properties
of the PAM/BC hydrogel composites were also improved with the high BC content. The
PAM/BC hydrogel composites showed a slow rate of releasing benzoic acid, model drug,
offering their great potentials in application of controlled drug delivery.

1. Introduction fibers of BC can form a physically entangled

Hydrogels are hydrophilic three- network with other polymer chains. Different
dimensional networks with excellent water from polymeric hydrogels, the hydrogen
swelling capacity.1 Polyacrylamide (PAM) bonding between water molecules and BC is
hydrogels are the most common synthetic mostly on the fiber surface, large amounts of
hydrogels. These hydrogels undergo large free water are filling the voids in between BC
volume transition on swelling but they lack fibers, so the water in a cellulose-containing
hydrolytic stability. PAM hydrogel is non- hydrogel can be squeezed out easily. Great
toxic and stable. They have been extensively physical properties of BC including high
studied as novel soft material for bio- average molecular weight and crystallinity
application. The good biocompatibility of are the main advantages in this work.
hydrogels originates from their higher water In this work, BC was selected as a
content, but it is also a limitation to the reinforcing material of the PAM hydrogel.
mechanical properties, leading to the limited The properties of the PAM/BC hydrogel
application.2 Bacterial cellulose (BC) composites including swelling ratio, gel
hydrogel is one of the most common natural fraction, porosity and mechanical properties
cellulose. The diameter of BC fibers is 20– were investigated. Releasing performance of
100 nm. Bacterial cellulose has high water benzoic acid, a model drug, was also studied.
retention due its hydrophilicity and high
surface area to mass ratio. It also has great 2. Materials and Methods
mechanical strength, exhibits high 2.1 Materials
crystallinity, and is relatively inexpensive to Acrylacmide (AAm), N,N-methyl-
produce.3 The long and refined nanoscale enbisacrylamide (MBA) and N,N,N,N- PC211

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
tetramethylethylenediamine (TEMED) were To prepare PAM/BC hydrogels, the
purchased from Sigma-Aldrich and used solution of BC in the mixed solvent was
without purification. Ammonium persulfate added into the monomer solution prior to
(APS), urea and sodium hydroxide (NaOH) initiating with APS. The BC content was
were obtained from Ajax Finechem. Nata de varied from 0.5, 1.0, 2.0%wt/v and the
coco was purchased as food-grade from the PAM/BC hydrogels were hereafter referred
local food industry in the form of cubes. as PAM/BC-0.5, PAM/BC-1.0 and
2.2 Preparation of bacterial cellulose PAM/BC-2.0, respectively
Nata de coco was washed and soaked 2.4 Characterization of PAM and
in distilled water for 15 days until the pH was PAM/BC hydrogels
around pH 5-7. Nata de coco was blended in
2.4.1 Fourier transform infrared (FT-IR)
a blender, poured into trays and dried up in
spectroscopy
the oven at 60°C for 1 week. The cellulose Chemical structure of the synthesized
sheets were then dried and blended with a hydrogels was investigated by using FT-IR
blender before they were subjected to spectrophotometer, (Perkin Elmer, Spectrum
grinding to produce a puffy celluloses 2000). The FT-IR spectrum was recorded
powder. over the range of 400-4000 cm-1 by KBr
2.3 Preparation of PAM and PAM/BC pellet method.
hydrogels
PAM hydrogels were prepared by 2.4.2 Scanning electron microscopy (SEM)
free-radical copolymerization of acrylamide Surface morphology of the hydrogel
with N,N-methylenebisacry-lamide (MBA) was examined by SEM. Freeze-dried swollen
as chemical cross-linker. A mixed solvent of hydrogels were fixed on a scanning electron
urea/NaOH used in this work was prepared microscope sample holder with a double
by mixing equal volume of urea (4%w/v) and sided adhesive tape and coated with a layer of
NaOH (8%w/v). For a typical PAM hydrogel gold of 150 Å for 2 min using a sputter coater
synthesis, AAm (0.6 mol) and MBA (10 in a vacuum of 3x10-1 atm of argon gas. The
mmol) were mixed in a dry 50 mL filter flask sample was then examined using a scanning
to which 20 mL mixed solvent of urea/NaOH electron microscope (JEOL JSM-6610LV).
was added. The monomer solution was gently 2.4.3 Mechanical property
swirled with a magnetic bar on a stirring plate The tensile strength of hydrogels was
until all reactants were completely dissolved. examined by ASTM D 638-03. The stress
Subsequently, APS (1 mmol) and TEMED (1 and strain (%) at break of hydrogels were
mmol) were added to initiate polymerization, measured using rectangular specimens with
and the solution was swirled gently five or six the size of 24x100mm. The stress was
times by hand to mix all reactants and poured calculated based on the cross-section area of
into a polypropylene petri dish. The solution each sample and the strain based on its
was polymerized at room temperature for 2 h. relative elongation in percentage from its
The synthesized gel was immersed in the original length.
mixed solvent of urea/NaOH for five days, 2.5 Property assessment of PAM and
with water changes three times a day to PAM/BC hydrogels
remove any unreacted monomers. 2.5.1 Gel fraction
PC212

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The gel content was evaluated by Franz-Diffusion cell, consisting of two
measuring its insoluble part in dried sample compartments: a donor compartment, which
after immersion in DI water for 16 h. The gel was exposed to an ambient condition, and a
fraction was calculated as Eq. 1, using the receptor component which was filled with
initial weight of the dry gel (W0) and the phosphate buffer solutions of pH 7.4 and
weight of the extracted dry gel (Wi). maintained at 37 °C. The BA-loaded
hydrogels were placed on top of a nylon net
 Wi 
%GF     100
 (1) above the receptor compartment. A sample of
W
 0  4 mL was withdrawn at various time intervals
and simultaneously replaced with an equal
2.5.2 Gel porosity volume of the fresh buffer solution. The drug
For porosity measurement, the amount in the withdrawn solution sample
solvent replacement method was used. Dried was determined by UV/Visible spectrophoto-
hydrogels were immersed in absolute ethanol meter at the wavelength of 296 nm. The drug
overnight and weighed after that the excess release was determined by:
ethanol on the surface was blotted. The M 
Drug release(%)   t   100 (4)
porosity was calculated from Eq. 2:
m2  m1  Mo 
Porosity  (2)
 ethanolVHG where M0 and Mt are the amount of the loaded
and released at time t.
where, m1 and m2 are the mass of hydrogel
before and after the immersion in absolute 3. Results and Discussion
ethanol, respectively; ρ is the density of
absolute ethanol and V is the volume of the 3.1 Characteristics and mechanical
hydrogel. properties of PAM and PAM/BC
hydrogels
2.5.3 Degree of swelling A comparison of the FTIR spectra
Reverse osmosis water was used for was made between PAM hydrogel, BC and
the investigation of swelling properties of the PAM/BC hydrogels with different BC
hydrogels at room temperature. At a given contents as shown in Fig. 1. PAM hydrogel
time, each specimen was removed from the showed a broad and strong absorption peak at
water to be sieved where it was carefully 3435 cm-1, attributed to the NH2 stretching of
wiped by filter paper and then weighed. The the PAM structure. A broad band in the range
swelling percentage of hydrogels was of 2860-2930 cm-1 was assigned to the
calculated based on Eq. (3) stretching of -CH2 group. The bands at 1638
 W  Wd  cm-1 and 1537 cm-1 were attributed to the
%Swelling   s   100 (3)
stretching of C=O and N-H from amidic
 Wd 
groups in PAM hydrogel.4
where, Ws and Wd correspond to the weights
of the swollen gels and dry gel, respectively.
2.6 Drug release performance
Benzoic acid (BA) was selected as a
model drug for this work. Drug release
profile was studied by using a modified PC213

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 5–20 m in diameter. Adding BC into PAM
hydrogel caused interpenetrating networks as
observed in Figure 2b-d. However, the pore
size of the hydrogel was also influenced by
the BC content, showing that the pore size of
the hydrogels decreased from the loose cross-
linked hydrogel of PAM/BC-0.5 to densely
cross-linked hydrogel of PAM/BC-2.0.
Averaged pore sizes were found to be 13 m,
Figure 1. FTIR spectra of the PAM, BC and 12 m and 6 m for PAM/BC with 0.5, 1.0
PAM/BC. and 2.0 %wt/v BC, respectively.
FTIR spectrum of BC exhibited O-H Table 1 presents the mechanical
stretching at 3350 cm-1 and other fingerprints, properties of PAM and PAM/BC hydrogels.
confirming the purity of the cellulose Comparing to the PAM hydrogel, the
produced as reported elsewhere.5 For the PAM/BC hydrogels showed an increase in
PAM/BC hydrogels, the broad absorption tensile stress at break (B). The influence of
band observed at 3438 cm−1 was due to the BC in tensile properties is attributed to the
overlap of the O-H stretching of BC and the fact that BC is nanofibers, acting as
N-H stretching of PAM. The strong reinforced materials for the PAM hydrogel.
absorption band observed at 2925 cm−1 was The results shown in Table 1 also indicates
also attributed to the overlapping of C-H that PAM hydrogel may be stretched around
stretching of BC and PAM 170% of its original length before breaking,
unlike the PAM/BC hydrogels which showed
less stretching. This result corresponded to
(a) (b) smaller pore size, hence greater network
density of the hydrogel after incorporating of
BC as discussed in SEM images previously.
Table 1. Mechanical properties of PAM and
PAM/BC hydrogels with different BC
(c) (d) contents.
Hydrogel B (kPa) B (%)
PAM 0.3 170
PAM-BC-0.5 0.7 152
PAM-BC-1.0 4.8 127
PAM-BC-2.0 7.2 105

Figure 2. SEM images of (a) PAM, (b) 3.2 Physical properties of PAM and
PAM/BC-0.5, (c) PAM/BC-1.0 and (d) PAM/BC hydrogels
PAM/BC-2.0. Gel fractions and gel porosity are
SEM micrograph of PAM hydrogel presented in Table 2. Gel fraction of PAM
(Figure 2a) presents a porous microstructure hydrogel was found to be 85.0%.
with dispersed pores. The pores had an Incorporation of BC into the PAM hydrogel
approximately irregular shape, varying from slightly increased gel fraction and decreased PC214

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
gel porosity, suggesting the BC plays a role 3.3 Release of benzoic acid from the
in the crosslinking process. hydrogels
Table 2. Gel fractions and gel porosity of The release profiles of the benzoic
PAM and PAM/BC hydrogels with different acid (BA) model drug from PAM, PAM/BC-
BC contents. 0.5, PAM/BC-1.0 and PAM/BC-2.0 are
Hydrogels Gel fraction(%) Gel porosity presented in Fig. 4. It was visible that the BA
PAM 85.0  3.9 0.11  0.03 molecules are gradually released from the
PAM/BC-0.5 86.4  7.7 0.17  0.08 hydrogels up to 8 hours until the amount of
PAM/BC-1.0 90.5  6.4 0.14  0.07 the released BA reached equilibrium.
PAM/BC-2.0 91.4  4.3 0.07  0.01 For all the hydrogels, a linear
relationship of the cumulative release of BA
Figure 3 shows the degree of swelling with release time was observed over the first
for the PAM and PAM/BC hydrogel with 8 hours. As seen in Fig. 4, the cumulative
different BC contents. The results showed release at the equilibrium state of BA from
that the degree of swelling decreased with the PAM hydrogel was found to be 76%. The
increasing BC content in the hydrogels. cumulative release decreases to 64%, 50%
Incorporation of BC in the hydrogel and 28% after incorporating of 0.5%, 1.0%
enhanced crosslinking and reduced space and 2.0% BC, respectively in the PAM
between the PAM polymer chains, producing hydrogel. This is because of the decrease in
a dense network. Apart of AAm, the pore size in the PAM/BC hydrogels, as
solubilized BC could also be initiated by APS mentioned earlier.
to generate the active sites of hydroxyl 90
radicals. The hydroxyl radicals on BC 80 PAM
Cummulative release (%)

subsequently induced more crosslinking 70 PAM/BC-0.5

between the PAM polymer chains.6 These 60
results agreed with the SEM images of the 50
hydrogel shown in Fig. 2. Smaller pore sizes 40
PAM/BC-1.0
were observed for the PAM/BC hydrogel. 30
The higher the content of BC gives smaller 20 PAM/BC-2.0
pore size. 10
0
35000 0 5 10 15 20 25
PAM Release time (hr)
30000
25000 Figure 4. Release profiles of BA from PAM
% Swelling

20000 and PAM hydrogel with different BC

PAM/BC-0.5
15000
contents.
10000 PAM/BC-1.0 4. Conclusion
5000 PAM/BC-2.0 We reported the characteristics and
0 drug release performance of a developed
0 2 4 6 8 hydrogel designed for application as
Swelling time (hr) transdermal drug delivery system. BC was
selected as a reinforced material to improve
Figure 3. Degree of swelling for the PAM the mechanical properties of the PAM
and PAM/BC hydrogels with different BC hydrogel. The effect of BC contents on the
contents. hydrogel properties, mechanical properties PC215

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
and release behavior were investigated, References
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and leading to smaller pore size and 2013, 29, 861-870.
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swelling degrees of the PAM/BC hydrogels Sirivat, A. Materials, 2013, 6, 4787-4800
were dependent upon the BC content due to 3. Silva, N; Rodrigues, A.; Almeida, I.;
the fact that crosslinking reduces the access
Costa, P; Rosado, C., Carbohydr. Polym.,
of water into the PAM network. Releasing
2014, 106, 264–269.
profile of BA from the hydrogel network
showed the linear relationship with time, 4. Jayaramudu, T.; Ko, H.U.; Kim, H.C.;
indicating a great potential in controlled drug Kim, J.W.; Kim, J. Materials, 2019, 12, 1-
release application. 14.
5. Fuller, M.E.; Andaya, C.; McClay, K., J.
Acknowledgement Microbiol. Meth., 2018, 144, 145-151.
The authors would like to acknowledge 6. Pandey, M.; Amin C.I.M.; Ahmad, N.;
the Faculty of Applied Science, King Abeer, M.M. Int. J. Polym. Sci., 2013, 5,
Mongkut’s University of Technology North 1-10.
Bangkok for their financial assistance and
support (Contract no. 6041102).

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Effect of temperature on the cellulosic products from sulfuric-acid-treated
pineapple leaf fiber
Gisma Coraima Asmarani1, Umphan Ngoensawat1, Attasith Parnsubsakul1,2,
Sanong Ekgasit1,2*
1
Sensor Research Unit (SRU), Department of Chemistry, Faculty of Science, Chulalongkorn University,
254 Phayathai Road, Pathumwan, Bangkok 10330, Thailand
2
Research Network NANOTEC-CU on Advanced Structural and Functional Nanomaterials, Faculty of Science,
Chulalongkorn University, Bangkok 10330, Thailand
*E-mail: [email protected]

Pineapple leaf fiber (PALF) is an agricultural residue that is available abundantly as a

renewable resource with high cellulose content. Sulfuric acid (SA) treatment is commonly used
for producing cellulosic products. This work investigated the effect of temperature on cellulosic
products from PALF via SA treatment. SA at low temperature (-20 ºC) broke down the H-
bonding that led to the production of regenerated amorphous cellulose (RAC). On the other
hand, SA at high temperature (50 ºC) hydrolyzed cellulose by breaking β-1,4-glycosidic
linkage that led to nanocrystalline cellulose (NCC). FTIR spectra showed changes in chemical
bonding of RAC comparing to that NCC: O-H stretching corresponding to inter-molecular H-
bonding between O(6)H⋯O’(3) (3285 cm-1) and intra-molecular H-bonding of O(3)H⋯O(5)
(3331 cm-1) disappeared, transformed to weak H-bonding (3490 cm-1); CH2 scissoring of C(6)
or crystalline absorption band (1427 cm-1) decreased while C-O-C valence vibration
representing amorphous region (897 cm-1) increased. Cellulosic products also showed different
optical phenomena under cross-polarized light, attributing to their crystalline or amorphous
structures. This work not only provided an understanding of the effect on temperature on SA
treatment of PALF but also suggested economical means for obtaining cellulosic products of
various forms.

1. Introduction advantages such as biodegradability,

Nowadays, sustainable concern has biocompatibility, non-toxic, and good
raised great attention, which motivates thermal stability that make cellulose an
people to maximize the utility of renewable attractive “green” material. Cellulose was
resources and minimize the production of widely used in the textile industry, sensing,
industrial residues. Cellulose is the most composite material, and biomedical
2
abundant natural polymer that can be derived applications.
from agricultural products and residues. Pineapple is one of the most favorite
Cellulose consists of linear tropical fruit that widely cultivated. In
homopolysaccharide composed of Thailand, due to its popularity for food and
unbranched glucose units linked by β-1,4- beverage consumption, pineapple contributes
glycosidic linkages. Cellulose has strong to approximately 1.93 million tons of
intra- and inter-molecular H-bonding from agricultural residue annually. Pineapple
glucose unit that carries three hydroxyl leaves are the major residue of pineapple
groups, causing it remains insoluble in most plants (1.86 million tons of leaves with 1.79
solvents.1 Cellulose possesses significant million tons of pineapple production).3 PC217

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Pineapple leaf fiber (PALF) has high (NaOH) and sulfuric acid (H2SO4 95-97%
cellulose content (74%) that can be a great w/w) were purchased from Merck Ltd.,
resource for cellulosic products such as Thailand. Hydrogen peroxide (H2O2 50%
nanocrystalline (NCC), microcrystalline, w/w) was purchased from Solvay Peroxythai
(MCC), and regenerated amorphous cellulose Ltd., Thailand. Kim-Tech wiper was
(RAC).4 The advancing applications can be purchased from Kimberly-Clark Ltd.,
applied using these cellulosic products, Thailand. Deionized (DI) water was used as
which make them more valuable. NCC can the solvent.
be used for drug carriers, nanodevices, and 2.2 Purification
sensing.5 MCC can be used for commercial 2.2.1 Alkali treatment
starting material to make NCC. Meanwhile, PALF (50 g) was cut into 10 cm
RAC can be used for hybrid material and lengths. The cut-PALF was boiled in 4% w/v
water in oil emulsions stabilizer.6, 7 NaOH (500 mL) for 2 h under mechanical
Despite the high potential of PALF stirring. The alkali-treated PALF was washed
usage, there is no company playing the role with DI water to obtain a neutral pH.
of processing pineapple residue into a 2.2.2 Bleaching treatment
valuable product. Moreover, there is a lack of The mixture solution of 50% w/w
knowledge from farmers about processing H2O2 (25 mL) and 0.1% w/v NaOH (500 mL)
the pineapple residue. As a result, burning was prepared. The alkali-treated PALF was
becomes a preferable choice for farmers to immersed and boiled in the mixture solution
eliminate pineapple residue. Comprehensive for 1 h under mechanical stirring. The
works must be done to create value from bleached-PALF was washed with DI water to
pineapple leaves by turning them into obtain a neutral pH. Then, it was kept in the
cellulosic products. refrigerator for further usages.
Sulfuric acid (SA) treatment is a 2.3 Preparation of cellulosic products
method generally used to produce NCC or The bleached-PALF (1 g) was treated
RAC. Interestingly, the temperature with H2SO4 (10 mL) with continuous stirring
condition of treatment affects the obtained in different conditions as follows: 25% and
product. Huang et al. (2016) obtained 50% (w/w) H2SO4 solution. Each
cellulose solution from spruce cellulose after concentration was treated at -20 ºC, 30 ºC,
SA treatment at low temperature (-20 ºC), and 50 ºC for 2 h. The reactions were
which formed RAC after they regenerated it terminated by adding an excess (10-fold) of
with a coagulation bath.8 Santos et al. (2013) cold DI water. The acidic solution was
obtained NCC from PALF after SA treatment removed by washing the precipitate with DI
at high temperature (45 ºC).9 In this research, water and centrifuged it several times (6000
we plan to observe the effect of temperature rpm for 15 min in one cycle of
on PALF for producing cellulosic products centrifugation). Then, the precipitate was
via SA treatment. collected after reached a neutral pH. The
cellulosic products were labeled
2. Materials and Methods “Temperature-PALFSA concentration”. For
2.1 Materials example, “-20PALF25” means the PALF in
PALF was obtained from local 25% w/w H2SO4 and -20º C condition.
farmers in Thailand. Sodium hydroxide
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
2.4 Characterizations
2.4.1 Fourier transform infrared (FTIR) Raw PALF from local farmers could
spectroscopy not be used directly for producing cellulosic
The raw PALF, alkali treated-PALF, products due to the impurity of PALF. The
bleached-PALF were dried using an oven at impurity of PALF consists of non-cellulosic
100 ºC. All cellulosic products were air-dried components, lignin. The lignin acted as
on a glass slide in the form of a thin film. A natural protection obstructing acid access by
piece of Kim-Tech wiper was directly put on making the PALF stiff and also bundling
the FTIR spectrometer. FTIR spectra of the together. The lignin and other non-cellulosic
raw PALF, alkali treated-PALF, bleached- components made the brown color on the
PALF, Kim-Tech, and all cellulosic products PALF, shown in Figure 1.
were collected using ATR Nicolet iD7 FT-IR First, alkali treatment was performed
spectrometer. The FTIR spectra were effectively using sodium hydroxide to
recorded over the range of 4000−400 cm−1 remove the impurities such as lignin,
with 16 co-addition scans. hemicellulose, pectin, and protein. As shown
2.4.2 Optical microscopy (OM) in Figure 2, as the impurities were removed,
Morphology images of the raw fibril started to appear. The color of the PALF
PALF, alkali treated-PALF, bleached-PALF, after alkali treatment became lighter due to
and all cellulosic products were captured the elimination of non-cellulosic
using an optical microscope (OM) of Axio components. However, most parts of PALF
Scope Carl Zeiss with magnification 50X, still bundled together because lignin could
100X, 200X, 500X, 1000X by putting the not wholly remove after alkali treatment.
sample on the glass slide. Bleaching treatment using H2O2 was
2.4.3 Birefringence analysis applied to remove the lignin residue. It
Each cellulosic product at the same happened in alkali condition (pH 10-12). The
concentration (0.1 g/mL) was placed in the bleaching treatment changed the brownish
glass bottle. These bottles were placed in a PALF into white PALF, indicating that lignin
cross-polarized attachment and photographed was removed and caused the separation of the
by a camera phone. fibril that once bundled together by lignin and
hemicellulose.
3. Results & Discussion
3.1 Purification of PALF in chemical
treatments

Figure 1. OM images of raw PALF with (A)

impurities and (B) brown stain.
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 PALF after chemical treatments. In FTIR
spectra, the first observation was at O-H
region (3700-3000 cm-1) and C-H region
(2900-2800 cm-1). The chemical treatments
have aggravated the intra- and inter-
molecular H-bonding in the PALF proven by
more prominent peak at 3427 cm-1, 3331 cm-
1
, and 3285 cm-1 corresponding to the intra-
molecular H-bonding of O(6)H⋯O(2),
O(3)H⋯O(5) and inter-molecular H-bonding
O(6)H⋯O’(3), respectively.10
The presence of lignin and
hemicellulose in raw PALF have shown in
several bands at range of 1800-800 cm-1. The
Figure 2. OM images of (A) raw PALF, (B) peak at 1731 cm-1 of the acetyl and uronic
alkali-treated PALF, (C) bleached-PALF, ester groups of the hemicellulose or the ester
and (D) images of (d1) raw PALF, (d2) linkage from carboxyl groups of the ferulic
alkali-treated PALF, (d3) bleached-PALF. and p-coumaric acids of lignin has decreased
The FTIR spectra (Figure 3) of the dramatically after alkali treatment and
raw PALF, alkali-treated PALF, and completely disappeared at bleached-PALF
bleached-PALF have taken to prove that the spectrum. Peaks at 1600 cm-1 and 1511 cm-1
chemical treatments successfully removed were attributed to the stretching of aromatic
the impurities from PALF. rings of lignin. Peak at 1243 cm-1
corresponded to C=O stretching also
disappeared after chemical treatments.11 The
spectrum of bleached-PALF was compared
with the Kim-Tech spectrum. The spectra of
both samples suggested that the chemical
treatments have successfully removed the
impurities from raw PALF and reached the
same purity as that of Kim-Tech.
3.2 Effect of concentration and
temperature in the sulfuric acid treatment
In this research, we have observed the
effect of temperature (-20, 30, and 50 ºC) on
the sulfuric acid treatment toward PALF and
the obtained products.
Figure 3. FTIR spectra of (a) Kim-Tech, (b) OM images have been taken to
bleached-PALF, (c) alkali-treated PALF, and analyze the morphology of each cellulosic
(d) raw PALF. product. According to Figure 4, -20PALF25,
30PALF25, and 50PALF25 showing the same
Kim-Tech, a commercial pure shape which was rod-like shape. -20PALF25,
cellulose for scientific wiping was used as a 30PALF25, 50PALF25 have length of ~89.2,
standard to compare with the spectra of the PC220

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
122.0, and 62.5 μm, respectively. The length has gel-like feature due to swelling and
of those cellulosic products has belonged to regenerating process of sulfuric acid
the microcrystalline category. The different treatment at low temperature (-20 ºC).
temperatures of those samples have affected Acid broke down the intra- and inter-
the size of the MCC they obtained. molecular H-bonding, making cellulose
dissolved into a transparent solution. After
that, the transparent solution regenerated in a
random manner into the insoluble gel-like
particle called regenerated amorphous
cellulose (RAC) after washed with DI water.
The transformation was captured in Figure 6.

Figure 4. OM images of (A) bleached-PALF,

(B) -20PALF25, (C) 30PALF25, and (D) Figure 6. (A) Transparent solution
50PALF25. transformed into (B) RAC.
On the other hand, the 30PALF50
appeared the same shape with the previous
25% w/w H2SO4 samples as an MCC, with
length ~70.1 μm. At this condition, acid
partially hydrolyzed cellulose by breaking
the β-1,4-glycosidic. But the temperature
wasn’t enough to help the acid hydrolyzed
the cellulose into NCC.
Meanwhile, the 50PALF50 was
assumed as NCC due to physical
characteristics such as homogeneous and
well-dispersed in the water. The OM images
Figure 5. OM images of (A) bleached-PALF, couldn’t capture the morphology of this
(B) -20PALF50, (C) 30PALF50, and (D) sample because of OM limitation wouldn’t
50PALF50. be able to see the material under 1 μm. To
prove our assumption, we used another
This result has triggered our interest
technique that was cross-polarizer. The flow
to study the effect of temperature in a higher
birefringence phenomena could be seen in
concentration of sulfuric acid. We have tried
50PALF50 under cross-polarizer, which
to use 50% w/w H2SO4. The results were
proved that 50PALF50 was NCC (Figure 7).
fascinating. Based on Figure 5, the
Just like MCC, the acid hydrolyzed cellulose
morphology of each cellulosic product
by breaking the β-1,4-glycosidic. But,
showing different shapes. The -20PALF50 PC221

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
because the condition happened at 50 ºC, the molecular H-bonding, except for -20PALF50.
acid was capable of aggressively hydrolyzed This sample showed the characteristic of
the cellulose into NCC. amorphous cellulose, which had a band at
3490 cm-1 correspondings to weak H-
bonding transforming from the loss of intra-
and inter-molecular H-bonding bands at 3331
and 3285 cm-1 which resulted in boarded of
the O-H region.12 Also, the peak at 1427 cm-
1
correspondings to CH2 scissoring of C(6)
or crystalline absorption band decreased
significantly, while the band correspondings
to the C-O-C valence vibration or amorphous
band (897 cm-1) increased significantly.11
FTIR can be a firm proof to conclude that we
obtained RAC in 50% w/w H2SO4 at -20 ºC.
The similar patterns of spectra from
bleached-PALF, -20PALF25, 30PALF25,
50PALF25, 30PALF50, and 50PALF50
explained that the hydrolysis reaction would
Figure 7. (A) Water, (B) -20PALF50, (C)
only cut off the cellulose chain by breaking
30PALF50, and (D) 50PALF50 under cross-
β-1,4-glycosidic linkage but not change any
polarizer.
chemical functional group on the cellulose.
4. Conclusion
Combining the results of OM, FTIR,
and cross-polarizer, we can draw a solid
conclusion that different temperatures on the
sulfuric acid treatment will affect the
obtained products if the sulfuric acid
concentration is adequate. Using low
concentration such as 25% w/w H2SO4 will
obtain MCC in every temperature meanwhile
using high concentration such as 50% w/w
H2SO4 will obtain different cellulosic
products at different temperatures which are
RAC, MCC, and NCC at -20, 30, and 50 ºC,
respectively.
Figure 8. FTIR spectra of cellulosic
products. Acknowledgements
FTIR spectra were taken to analyze This work has been partially
the chemical changes of the cellulosic supported by National Nanotechnology
products (Figure 8). At O-H region (3700- Center (NANOTEC), NSTDA, Ministry of
3000 cm-1), all the spectra have similar in Science and Technology, Thailand, through
patterns representing of intra- and inter- its Research Network NANOTEC (RNN)
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program. Gisma Coraima Asmarani is an 6. Chang, C.; Peng, J.; Zhang, L.; Pang, D.-
ASEAN scholarship student at W., J. Mater. Chem. 2009, 19, 7771-7776.
Chulalongkorn University, Thailand. 7. Jia, X.; Chen, Y.; Shi, C.; Ye, Y.; Wang,
P.; Zeng, X.; Wu, T., J. Agric. Food
Chem., 2013, 61, 12405-14.
References 8. Huang, W.; Wang, Y.; Zhang, L.; Chen,
1. Nuruddin, M.; Hosur, M.; Uddin, M. J.; L., Cellulose 2016, 23, 3463-3473.
Baah, D.; Jeelani, S., J. Appl. Polym. Sci. 9. Santos, R. M. d.; Flauzino Neto, W. P.;
2016, 133, 42990. Silvério, H. A.; Martins, D. F.; Dantas, N.
2. Singhsa, P.; Narain, R.; Manuspiya, H., O.; Pasquini, D., Ind. Crop. Prod. 2013,
ACS Appl. Nano Mater. 2017, 1, 209-221. 50, 707-714.
3. Jirapornvaree, I.; Suppadit, T.; Popan, A., 10. Fareez, I. M.; Ibrahim, N. A.; Wan
Int. J. Recycl. Org. Waste in Agricult. Yaacob, W. M. H.; Mamat Razali, N. A.;
2017, 6, 345-350. Jasni, A. H.; Abdul Aziz, F., Cellulose
4. Maniruzzaman, M.; Rahman, M. A.; 2018, 25 , 4407-4421.
Gafur, M. A.; Fabritius, H.; Raabe, D., J. 11. Lionetto, F.; Del Sole, R.; Cannoletta, D.;
Compos. Mater. 2011, 46, 79-90. Vasapollo, G.; Maffezzoli, A., Materials
5. Thomas, B.; Raj, M. C.; B, A. K.; H, R. 2012, 5, 1910-1922.
M.; Joy, J.; Moores, A.; Drisko, G. L.; 12. Leng, E.; Zhang, Y.; Peng, Y.; Gong, X.;
Sanchez, C., Chem. Rev. 2018, 118, Mao, M.; Li, X.; Yu, Y., Fuel 2018, 216,
11575-11625. 313-321.

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 Using portable type and conveyor belt system type VIS-NIR spectrometer
to predict the CIE L*a*b* color value
Watcharakorn Moolsri1, Sarawut Phupaichitkun2*
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakhon Pathom 73000, Thailand
E-mail: [email protected]

This research is to apply the portable Vis-NIR spectrometer (multispectrometer, Tec 5

AG, Germany, 305-1140 nm) and conveyor belt system spectrometer (LineScan Vis-NIR,
Silpakorn University, 400-1000 nm) for predicting the color of sample based on CIE L*a*b*
standard. CIE L*a*b* value and spectra of color, thickness, and roughness of various types of
plastic, comprising PET, HDPE, PP, PS, and PVC, were evaluated via the ColourFlex EZ
(HunterLab, USA) in the spectra range of 400-700 nm. These color values and spectra were
statistically analysed using the Partial Lease Square (PLS) method on MATLAB for calculating
loading matrix and constant value (B0). The prediction values of L*a*b* show R2 is equal to
0.9932 compared with the measured values. The ColourFlex EZ has a standard light source
and excellent measured condition therefore the spectra could be obtained without additional
treatment. On the other hand, the spectra measured by portable spectrometer and conveyor belt
systems have light interfering from surrounding, shape and thickness of samples during
measurement. For this reason, both Vis-NIR spectrometers spectra must be subjected to
treatment in order to produce R2 value higher than 0.9.

1. Introduction based on the different method or the

In industry, the colors were used for opponent theory of color vision. L*
clarifying the quality of products such as represented lightness from black to white (0-
food, pharmaceutical, textile and plastic 100), a* represented red (positive value) to
industries. The color values are the optical green color (negative value) and b*
property relining on the light sources, object represented yellow color (positive value) to
characteristic and detector sensitivity ranges. blue (negative value). Therefore the L*a*b*
For example, together cones and rods cell on value could provide all shade and tone
fovea in human eye, detected colors for instead of lightness, hue and chroma3. Using
millennia.1 These color values have been spectrophotometer in the range 400-700 nm,
systematically standardized by the the color meter determines the L*a*b* value
Commission International de l’Eclairage of a certain object area in a specific
(CIE) to communicate conveniently and environment such as a close chamber.
correctly. Normally, The XYZ color system In this research, the spectra of a single
was used2. The XYZ values are based on point were measured out of the chamber by
three positive primary color values, X is using a portable spectrophotometer.
represented red, Y is represented green and Z Furthermore, representing the real-time color
is represented blue, as known as the RGB measuring on the conveyor in the sorting line,
system. Other colors of the XYZ system were the spectra are measured by adapting the
mixture values of hue, chroma (saturation) visible-near infrared (VIS-NIR) line scan
and indirect lightness. In 1964, CIE system from previous work.4 Spectrum
developed the L*a*b* color system, which would be treated and apply the statistic PC224

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
algorithm to get the model which transfers Germany) in 305-1140 nm wavelength and
the spectra to L*a*b* value for evaluating the using spectrometer for conveyor belt system
possibility to evaluate the color value real- (LineScan Vis-NIR, Silpakorn University,
time on the conveyor. 400-1100 nm).
2.5 Correlation of color and spectra
2. Materials and Methods analysis
2.1 Materials The partial least square (PLS)
Five polymer types were used for correlation analysis was applied for obtaining
preparing the plastic samples: poly(ethylene regression model between spectra and
terephthalate) (PET, SA135T, Thai PET L*a*b* value measured from ColourFlex EZ.
Resin Co., Ltd, Bangkok, Thailand), high Applying the PLS algorithm with spectra
density polyethylene (HDPE, HD60005, PTT from each equipment, the transfer model will
global chemical public., Ltd, Rayong, be found and able to evaluate the precision of
Thailand), polypropylene (PP, 2300K, IRPC the model.
public Co., Ltd, Rayong, Thailand),
polystyrene (PS, GP150, IRPC public Co., 3. Results & Discussion
Ltd, Rayong, Thailand) and compounded 3.1 Spectra and affecting parameter
poly(vinyl chloride) (PVC, R9173022 04134, Regarding all techniques measured
Thai plastics and chemicals PCL., Rayong, the deflection light from the surface of the
Bangkok). The colored polymer (red, green objects, the thickness and surface roughness
and blue) from Salee color public Co., Ltd, of objects effect to intensity of the spectrum.
(Samut Prakan, Thailand) was used in this Especially the virgin color samples which
study. more transparent than color samples, the
2.2 Preparation of plastic samples spectra will have interfered with the
Polymer pellets or compounded background of the sample chamber or the
polymers were compressed at Silpakorn color of background made spectra lower
University, Nakhon Pathom, Thailand) with intensity. The results were numerous and the
different thickness (1, 3 and 5 mm). The same had the same tendency, would like to
compressed sheets were cut into 15×15 mm2. instance HDPE samples. (Fig.1) Spectra of
The samples with 3 mm thickness were virgin HDPE measured with ColourFlex EZ
surface abrasion into two roughness level.4 shown in Figure 2a. 1 mm and 3 mm
2.3 Color measurement thickness samples present the same intensity
CIE L*a*b* color values and spectra of spectra due to both samples are
of samples in 400-700 nm wavelengths were transparence. The intensity of the sample
measured using reflective mode with deflection decreased when the thickness of
ColourFlex EZ spectrophotometer (from the measured samples increased without
HunterLab, USA). The measurement based background. The measured spectra of
on CIE standard illuminant D65 and 10 ColourFlex EZ had not affected the light
observers.5 reflection of the background therefore
2.4 Spectroscopic measurement increased spectra intensity while thickness
Spectra of plastic samples were increased. For multispectrometer, 3 mm
measured using a portable Vis-NIR samples would have the highest intensity
spectrometer (multispectrometer, Tec 5 AG,
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Figure 2. Effect of different thicknesses of a)
ColourFlex EZ, b) multispectrometer and c)
Linescan.
because it had the fit distance between the
light source and background close enough to
detected background reflection light while
Figure 1. The examples of HDPE measured the distance of 1 mm samples measured was
spectrum of a) ColourFlex EZ, b) too close the background than that resulting
multispectrometer (white background), c). in less the effect of the background reflection.
And in 5 mm samples, the effect of the
background reflection was reduced with the
thickness of samples which decreased bounce
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
off the intensity of the light source. (Figure
2b) For Linescan, detector and light source
was stationary. In this degree, the thickness
of the samples decreased the light bounce off
affection that resulting in the sample
thickness and detected light intensity
inversely. (Figure 2c) The roughness affected
light scattering directly causing an increase in
the spectra intensity. (Figure 3)
3.2 Color and spectra correlation
To evaluate the correlation between
CIE L*a*b value and spectra, using the
statistic method. In this study, PLS 6 was
applied to the spectrum which CIE L*a*b*
was Y-value. The results were R-square or
regression coefficient, which affected the
accuracy of the CIE L*a*b* value prediction.
Figure 4 shows Colourflex EZ CIE L*a*b*
values (calibration) versus predication
L*a*b* values (validation) of each
spectrometers. When compared calibration
value with the validation value, the R-square
reaches to 0.9932 for ColourFlex EZ and less
than 0.9 for multispectrometer that required
the pre-treatment method for smoothing and
cut off unconcerned variant. The maximum
of R-square was 0.9401 with normalization,
filtered by Savitzky Golay and baseline
normalization, respectively. Wherewith R-
square less than 0.95, the predicted value was
quite different from the measured value. For
these reasons, the spectra were measured by Figure 3. Effect of different roughness of a)
changing the background from white to ColourFlex EZ, b) multispectrometer and c)
black. The R-square was 0.9665 with Linescan.
normalization and baseline normalization,
respectively. The black background could absorb
transmitted light. Hence, background
changing, it was a reduced background
reflection effect. Linescan was disturbed with
surrounding light and measured with white
background, therefore the maximum R-
square was 0.9121 with spectrum averaged
and Multiplicative scatter correction (MSC)
method. PC227

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Figure 4. The maximum R-square of regression mode with PLS of ColorFlex EZ, White
background multispectrometer (treatmented), Black background multispectrometer
(treatmented) and Linescane (treatmented).

4. Conclusion would like to thank you department of Food

The CIE L*a*b value could Technology, Silpakorn University for
measure by 400-1000 nm spectroscopy ColourFlex EZ and multispectrometer .
cooperate with statistical analysis on PLS
with calibration value from ColourFlex EZ. References
The possibility to create a model for CIE 1. Pease, P. L., Color vision. In
L*a*b* measurement of multispectrometer Borish's Clinical Refraction, Elsevier:
is positive, but Linescan must be improved 2006; pp 289-355.
for cut off noise from interference light 2. Charvat, R. A., Coloring of plastics:
(increased light source intensity) and Fundamentals. John Wiley & Sons: 2005;
reflected light from the background Vol. 35.
3. Gilchrist, A.; Nobbs, J.,
(changing color of the conveyor).
Colorimetry, theory. Encyclopedia of
Spectroscopy and Spectrometry, 3rd ed.
Acknowledgements USA: Elsevier. https://doi.
This research was fund by org/10.1016/B978-0-12-803224-4.00124-2
department of Materials Science and 2017.
Engineering, Silpakorn University. Authors PC228

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
4. Intajak, J.; Phupaichitkun, S., different spectrometers for assessing
Sorting post-consumer polymer on soluble solids content of pears on-line by
conveyor belt using NIR spectroscopy. Vis/NIR spectroscopy. IFAC Proceedings
Silpakorn University, 2019. Volumes 2010, 43 (26), 230-234.
5. HunterLab, ColorFlex EZ user´ s
manual. Hunter Associates Laboratory:
2013.
6. Tong, S.; Huirong, X.; Yibin, Y.;
Kondo, N.; Ogawa, Y., Comparison of

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Novel bio-based rubber oil from epoxidized and acetylated cashew nutshell
liquid
Idris Kalkan, Watthana Klairutsamme, Ittipol Jangchud*
Department of Chemistry, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang,
Bangkok 10520, Thailand
*E-mail: [email protected]

In this work, epoxidation and acetylation of Cashew nutshell liquids (CNSLs), a bio-
based additive derived from agricultural waste, was carried out. Cardanol, one of main
components of CNSLs, was used as model compound for modification. Epoxidized cardanol
(EC) was carried out via peracetic acid formed in-situ, in the presence of ion-exchange resin as
catalyst. Acetylated cardanol (AC) was achieved by solvent free mechanism and zinc oxide as
catalyst. EC and AC were characterized by FTIR and 1HNMR tests. Vanished peaks for
unsaturated alkyl chain and appeared peaks for epoxy groups proved conversion of
unsaturation into epoxy groups during epoxidation. The presence of peaks for C=O group and
disappearance of peaks for OH group confirmed acetylation. Modified oils as rubber processing
oil in CR/NR (50:50) blend were comparatively studied with commercial petroleum-based oil.
Rubber samples were tested for Mooney viscosity, cure characteristics, mechanical and
physical properties. Rubber samples with AC showed unchanged cure characteristics, but
improvement in heat deterioration. Rubber samples with EC revealed better properties, such
as, %elongation, hardness, modulus and heat deterioration, but longer cure time compared to
rubbers with commercial petroleum-based oil. In conclusion, the modified oils have high
potentials to be used commercially in rubber industry.

1. Introduction precious cashew nut, the plant provides a

Forecasted depletion within next few byproduct liquid called Cashew Shell Nut
decades and hazardous effects of fossil fuels Liquid (CNSL), which is a non-edible
have made people look for renewable mixture of oils and one of the most promising
resources. There have been numerous studies renewable bio-based resources, inside soft
and researches on finding alternatives to honeycomb structure of cashew nutshell.
petroleum products in different areas, in Making up around 25% of overall cashew nut
order to help protect nature, as well as, weight, CNSL has a very high potential of
diminish and eventually end the dependence being resource to many applications as
on the crude oil and the other fossil alternative to petroleum products. With the
resources.1,2 phenolic ring and unsaturated alkyl side
Bio-renewable resources and the chain in its chemical structure, CNSL gives
usage of agricultural wastes or byproducts as many other application possibilities than only
resource has gained a great importance due to being used as wood coating right after
the limited amounts of fossil fuel reservoirs, extracting from nutshell or being burnt for
environmental problems as a result of fossil heat within the nutshell.1,3
fuel usage and financial concerns.1,2 CNSL consists of four liquids or oils,
Although native to Brazil, cashew nut which, in common, have a phenolic aromatic
tree may grow in Asia Pacific region and in ring and a fifteen-carbon unsaturated side
Thailand. Being highly valuable owing to the chain at beta position. PC230

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 huge negative consequences on fossil fuel
reserves and environment. Being a bio
renewable resource and a very strong
candidate to replace petroleum, CNSL and its
modified forms by epoxidation and
acetylation will be used as processing oil for
NR/CR (50:50) rubber blend compounding
and will be compared with a petroleum based
commercial oil.
Figure 1. Components of CNSL: a)
2. Materials and Methods
Anacardic acid, b) cardanol, c) cardol and d)
2.1 Materials
2-methyl cardol.2
Cardanol was purchased from Vertex
Unsaturation level of side alkyl chain Chemicals (Thailand). Glacial acetic acid,
varies as saturated (5-8%), monoene (48- hydrogen peroxide (40% w/w) and toluene
49%), diene (16-17%) and triene (29-30%).1- were supplied from Carlo Erba (France).
3 Acetyl chloride (98% w/w) and amberlite IR
Table 1. Unheated and heated CNSL 120H ion exchange resin were purchased
Compositions. from Acros Organics (France) and zinc oxide
Component Weight% Weight% was supplied from Global Chemicals
(Unheated) (Heated) (Thailand). All chemicals were used as
1 Anacardic Acid 70-77 0-2 received unless otherwise mentioned.
2 Cardol 15-20 15-20
3 Cardanol 1-9 71-86
2.2 Cardanol modification
4 2-Methyl Cardol 1-4 1-4 Epoxidation
As seen in the Table 1, cardanol Epoxidation of cardanol was carried
becomes the major component when CNSL out by peracetic acid generated in situ
is heated, because of an endothermic process reaction in the presence of amberlite IR 120H
called decarboxylation, a removal of ion exchange resin as a catalyst. Calculated
carboxyl group as CO2. For this reason, amounts of cardanol, toluene, acetic acid and
cardanol was used as a model compound for amberlite IR 120H were placed in a three-
CNSL in this research. neck round bottom flask and stirred for 30
min at room temperature under nitrogen
atmosphere. Then 40% hydrogen peroxide
was added dropwise and very slowly by using
a separatory funnel. After hydrogen peroxide
addition, the reaction was kept for 5 hours at
Figure 2. Decarboxylation of anacardic acid. 65°C, and then, the reaction mixture was
filtered to remove the catalyst and washed
According to Malaysian Rubber with saturated sodium chloride solution until
Export Promotion Council (MREPC), Yearly becomes neutral. Finally, toluene and water
global rubber production is around 29 million were evaporated. The epoxidized cardanol
tons. Considering the processing oil content (EC) was characterized by FTIR and 1H
of 5-20 phr for rubber compounding, the oil NMR.4,5
required is 1.5-6.0 million tons. Getting all of
this oil from fossil fuel resources would have PC231

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 rpm. Vulcanization was achieved by
compression molding at 150°C.4,8
2.4 Rubber characterization and testing
Mooney viscosity
Mooney viscosity of four rubber
formulas were tested at 100°C by using
Mooney viscosimeter according to ASTM
D1646.4,8
Figure 3. Epoxidation of cardanol by Table 2. The formulas of NR/CR (50:50)
peracetic acid generated in situ reaction. rubber compounding.
Acetylation
Concent
Acetylation process was carried out
Ingredients Manufacturer ration
by solvent free method in the presence of zinc (phr)
oxide as a catalyst. Calculated amounts of
cardanol and zinc oxide were placed in a Thaihua Rubber
1 NR 50
(Thailand)
three-neck round bottom flask and stirred for
15 min by mechanical stirrer under nitrogen 2 CR Denka (Japan) 50
atmosphere. Then acetyl chloride was added Global Chemicals
dropwise and the reaction was continued for 3 ZnO 5
(Thailand)
another 30 min. After the reaction was
4 MgO 1
completed, the mixture was filtered to
remove zinc oxide and washed with sodium PT. Cisadane Raya
bicarbonate solution by using a separatory Chemicals
5 Stearic acid (Indonesia) 2
funnel to remove excess acetyl chloride and
hydrogen chloride, a byproduct. Finally, the
water was evaporated. The characterization Carbon Global Chemicals
of acetylated cardanol (AC) was 6 50
black (Thailand)
1 6,7
accomplished by FTIR and H NMR.
N: Global
Processing
7 Chemicals 5
oil
(Thailand)

General Quimica S.
8 6 PPD 1
A. (Spain)

Figure 4. Acetylation of cardanol by solvent General Quimica S.

9 ETU 1
A. (Spain)
free method.
2.3 Rubber compounding General Quimica S.
10 CBS 0.5
Four different natural rubber (NR)- A. (Spain)
chloroprene rubber (CR) (50:50) Sahapaisal Industry
formulations were prepared, which differ 11 Sulfur 1
(Thailand)
only by the processing oil used for
compounding. The processing oils were C,
EC, AC and naphthenic oil (N). The rubber
formulations were prepared by two-roll
external mill at 50 ̊C and the rotor speed of 35 PC232

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Cure characteristics AC. The peak at 597 cm-1 for AC represents
Cure characteristics of the rubber C-Cl bond as a result of HCl addition to
formulas were studied by Moving die unsaturation in alkyl chain.
rheometer at 150°C according to ASTM
D5289.4,8
Swelling Behavior
Specimens of 1x1x0.2 cm3 were
immersed in toluene at 28°C for 96 hours.
The weights of specimen were recorded
before and after being exposed to toluene.4
Bleeding
Test samples of 5x5x0.2 cm3 were
prepared and placed in an oven at 70°C for 24
hours under the pressure of 5 kg. The test and
weight loss measurement were studied
according to ISO 177.4
Tensile Properties Figure 5. FTIR spectra of C, EC and AC.
1
C-type dumbbell specimens were H NMR results, shown in Figure 6,
prepared and subjected to accelerated aging confirm epoxidation by the disappearance of
process in an oven with air circulation at 70 ̊C the vinyl protons at 5.4 ppm and the
for 168 hours according to ASTM D573. appearance of new oxirane protons at 3 ppm.
Tensile properties were measured before and New peak at 2.3 ppm represents the signal of
after aging according to ASTM D412 using a proton of acetate group evidencing the
universal testing machine.4,8 acetylation for AC. Disappearance of peak at
Hardness 5.4 ppm shows that unsaturation of side chain
Hardness of each rubber formula was removed for AC.
were measured before and after aging
according to ASTM D2240 by using a Shore
hardness tester.

3. Results & Discussion

Epoxidation takes place on the
unsaturation of side chain of cardanol, while
phenolic ring stays unchanged. According to
FTIR results in Figure 5, peak at 3007 cm-1
indicates the unsaturation in the alkyl chain
of C and disappears for EC. The broad peak
of phenolic hydroxyl at 3340cm-1 which is
visible for C and EC, vanishes for AC,
proving acetylation on hydroxyl group. A
new peak at 825 cm-1 represents epoxy bonds
in sidechain for EC and the other at 1765 cm-
1
shows carbonyl group of phenyl ester for Figure 6. 1H NMR spectra of C, EC and AC.
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Mooney viscosity and cure
characteristics results are given in Table 3.
Having the similar Mooney viscosity values,
four rubber formulas have similar molecular
weights. According to cure rate index (CRI)
results, AC has the similar results to N, where
EC has the smallest cure rate, which is due to
the time required for oxirane ring opening
and crosslink formation. Figure 7. Swelling percent results of C,
EC, AC and N used rubber formulas.
Table 3. Mooney viscosity and cure test
results.
Sample Mooney ts2 t90 CRI
Viscisity (min) (min) (min-1)
C 26.0 3.0 9.0 16.7
EC 26.5 1.2 12.5 8.8
AC 23.0 1.4 7.0 17.8
N 25.4 1.6 5.5 25.6
Figure 7 shows swelling percent
results for four rubber formulas. It was
Figure 8. Bleeding test results for C, EC,
already expected that cardanol and its
AC and N used rubber formulations.
derivatives would cause lower crosslink
density and so that bigger swelling percent
because of the stearic effect of long alkyl
chain. This factor seems to be minimized for
C, since the unsaturated parts of its side chain
may contribute to the crosslink formation.
In Figure 8, bleeding test results
reveal that all rubber formulas are within the
acceptable range according to ISO 177.
Table 4 and figure 9 show tensile and Figure 9. Shore hardness test results for
hardness test results. Among all rubber rubber formulas prepared using C, EC, AC
formulations, the one with EC indicates and N as processing oil.
superior tensile properties than others.
Tensile strength and M100 values increase, 4. Conclusion
while elongation at break and hardness In this study cardanol, model
decrease for all rubber formulas after aging, compound for CNSL, was epoxidized and
as a result of the increase in crosslink density acetylated to form EC and AC respectively.
during aging. The hardness of the AC after Both modified compounds, the alternative to
aging is the least affected. naphthenic oil, can be used as a processing oil
for NR/CR rubber blend.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
Table 4. Tensile test results for rubber formulations prepared by using C, EC, AC and N
processing oils before (BA) and after aging (AA).
Processing oil Tensile strength (MPa) Elongation at break (%) M100 (MPa)
BA AA BA AA BA AA
C 13.40 15.50 321 314 2.94 3.74
EC 14.21 15.45 397 350 2.65 3.56
AC 13.01 13.68 305 285 3.20 3.68
N 14.68 15.00 334 276 3.26 4.41

Although both modifications were Reference

achieved, there was an unexpected result for
1. Puchot, L. Cardanol: a bio-based building
acetylation, due to HCl addition in side chain.
block for new sustainable and functional
EC showed better mechanical properties,
materials. 198.
resulting in a better compatibility. AC,
although requires more improvement, 2. Sadavarte, N. V. Difunctional monomers
indicated good anti-aging properties starting from cashew nut shell liquid (CNSL)
corresponding to those of commercial, and high performance polymers therefrom.
petroleum-based oil. Ph.D. Thesis, University of Pune, Pune, 2012
3. Caillol, S. Cardanol. Curr. Opin. Green
Acknowledgements Sustain. Chem. 2018, 14, 26–32.
I would like to express my sincere 4. Raksawong, S.; Jangchud, I. New
appreciation to those, who helped me during Bioadditives from Modified Cashew Nut Shell
this study by any means of contribution and Liquid (CNSL) for Natural Rubber. 5.
support. 5. Rigoussen, A.; Raquez, J.-M.; Dubois, P.;
First of all, I would like to express my Verge, P. Eur. Polym. J. 2019, 114, 118–126.
sincere gratitude to my research advisor, 6. Kazemi, M.; Sanchez-Mendoza, A.;
Assoc.Prof.Dr.Ittipol Jangchud for his Ghobadi, M. Solvent-Free Acylation of
guidance and support despite his very busy Alcohols, Phenols, Thiols and Amines. 2019,
schedule. 8.
I owe my sincere thanks to my research 7. Tamaddon, F.; Amrollahi, M. A.; Sharafat,
co-advisor, Dr. Watthana Klairutsamme for his L. Tetrahedron Lett. 2005, 46 (45), 7841–
continuous support and help. 7844.
Last, but not least, I would like to 8. Surya, I.; Ginting, M.; Ismail, H. MATEC
gratefully acknowledge Ms.Suppanapang Web Conf. 2018, 197, 12005.
Raksawong for her contributions.

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Electrospun nylon 6,6 nanofibers functionalized with β-cyclodextrin as
solid phase extraction sorbent for determination of parabens
Tassanee Kuakul1, Puttaruksa Varanusupakul2*
1
Program of Petrochemical and Polymer Science, Faculty of Science, Chulalongkorn University,
Bangkok 10330, Thailand
2
Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
*E-mail: [email protected]

In this study, electrospun nanofibers of nylon 6,6 functionalized with β-cyclodextrin

(nylon 6,6/β-CD) were fabricated and applied as a sorbent in solid phase extraction (SPE) for
determination of paraben in water. The electrospinning parameters such as polymer
concentration, nylon 6,6/ β-CD ratio and electric field strength were investigated in order to
obtain uniform nanofibers. The morphology and physical properties of obtained fibers were
characterized by Scanning electron microscope (SEM), Fourier transform infrared
spectroscopy (FTIR) and BET surface area analysis. The electrospun nylon 6,6/β-CD were
achieved with fiber diameters in the range of 120 - 150 nm. The additional of β-CD slightly
increased the fiber diameters and decreased the surface area of nylon 6,6/β-CD nanofibers.
Finally, the nylon 6,6/β-CD nanofibers were examined as a sorbent in solid phase extraction of
parabens in water.
of parabens in the environment, water or
1. Introduction wastewater.
Parabens are esters of para- Most of the method for
hydroxybenzoic acid with an alkyl or determination of parabens in water samples
benzyl group. Because of their broad rely on the use of solid phase extraction
antimicrobial spectra, chemical stability, (SPE) followed by liquid chromatography
low toxicity and low price, they are very (LC). SPE is a technique that extensively
effective antimicrobial agents and mainly and widely used for extraction and
used as preservatives in foods, cosmetics preconcentration of trace analyzes.3-4, 15-16
and pharmaceutical drugs. Recently, many Fibers format of sorbent for SPE was
studies revealed that parabens are involved intensively interest because it can
in the occurrence of breast cancer in overcome the limitation of particle format
females, show endocrine disrupting effects of sorbent regarding a high back pressure.5
1,2
and relation with male infertility. Electrospinning technology has
Parabens have attracted growing attention been extensively explored as a simple and
due to their potential effects on human versatile method for preparing polymeric
health. The European Food Safety fibers. Notably, electrospun fibers has a
Authority (EFSA) established an nanoporous structure and diameter in the
acceptable daily intake (ADI) of 0-10 range from nano-to micrometer which
mg/kg (body weight) bw-day for sum of resulting to a high surface area to volume
methy paraben, ethyl paraben acid ester and ratio.6
their sodium salts. But now it does not Nylon 6,6 is a type of polyamide,
have the regulation regarding to the which has a good hydrophilicity surface,
presence stability and high resistance to organic
solvent. It can easily fabricate into a fiber
format and its properties are suitable to PC236

© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
used as an adsorbent in extraction 2.2 Nylon 6,6/β-CD electrospun
technique.13,14 nanofibers preparation
Beta-cyclodextrin (β-CD) is a The nylon 6,6/β-CD solution was
cyclic polysaccharide which presents a prepared. Firstly, β-CD was dissolved in
hydrophilic external surface and a formic acid (85 wt%). Then nylon 6,6 was
hydrophobic internal cavity. This structure added and stirred overnight at 35 °C. 3 mL
enables cyclodextrins to form full inclusion of this solution was applied for the
complexes with small molecules or partial fabrication of electrospun nanofibers. The
inclusion complexes with macromolecules, electro-spinning experiment was set-up as
hence improving the physicochemical and follow; the distance between needle tip-to-
biological properties of the complexed collector is 15 cm, the flow rate of polymer
compound.7-10, 12 There have been reports of solution was 0.3 mL hr-1 and 30 kV for the
studies showing that parabens are able to high voltage power supply. The nanofiber
interact with β-CD.11,12 production was carried out under
The aim of this work was to prepare temperature and humidity in range 25-29
nylon 6,6/β-CD electrospun nanofibers. °C and 30-40 %RH, respectively.
Moreover, nylon 6,6/β-CD nanofibers were 2.3 Characterization
applied as a sorbent in solid phase The morphology and surface of
extraction for determination parabens in prepared nylon 6,6/β-CD electrospun
water sample. nanofibers were characterized by scanning
electron microscopy (SEM) using JEOL
2. Materials and Methods JSM-IT100 Series and BET analysis with a
2.1 Materials Belsorp-mini II analyzer (MicrotracBEL
Methyl paraben (99%), ethyl Corp., Japan). FT-IR analysis was
paraben (99%), propyl paraben (99%) and performed using a Nicolet 6700 model
butyl paraben (99%) were purchased from spectrometer.
Alfa Aesar, USA. Nylon 6/6 (MW 262.35 2.4 Solid-phase extraction
g/mol), beta-cyclodextrin (98%) and formic Parabens in water were extracted
acid (85 wt%) were AR grade and used for using nylon 6,6/β-CD electrospun
preparation of nylon 6,6/β-CD electrospun nanofibers as a sorbent in SPE. The nylon
nanofibers. The organic solvents 6,6/β-CD electrospun nanofibers were cut
(methanol, acetonitrile, ethanol) for in a circle with diameter of 13 mm and
extraction and HPLC analysis were HPLC assembled in the syringe filter holder. In
grade. SPE process, nylon 6,6/β-CD sorbent was
Stock solutions (1000 mg mL-1) of conditioned with 3 mL of methanol and 3
parabens were prepared monthly in mL of water. Then, 5 mL of sample were
methanol and stored at 4 °C. Working passed through the SPE tube at 1 mL min-1.
standard solutions at different After SPE extraction, analytes were eluted
concentrations were prepared daily by with 250 µL methanol and 10 µL of the
dilution of the stock solution. The pH of solution were injected to HPLC-DAD for
sample solutions was adjusted with 0.10 M quantitative analysis.
hydrochloric acid or 0.10 M sodium
hydroxide.
2.5 Chromatographic conditions
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 Chromatographic separation was ImageJ 1.52a software. The average
performed by Agilent 1260 HPLC system diameter of fibers prepared from 15%,
(Agilent, USA) using Eclipse XDB-C18 16%, 17% wt of nylon 6,6 polymer solution
column, 5.0 µm (4.6 x 150 mm) (Agilent were 125 nm, 128 nm and 150 nm,
Technologies, USA). The column respectively. The diameters of nylon 6,6
temperature was set at 25 °C. electrospun fibers were increased as the
Acetonitrile:water in the ratio of 50:50 increase of nylon 6,6 concentration in
%v/v was used for the mobile phase at a polymer solution. This caused by a higher
flow rate of 1.0 mL min-1. The wavelength viscosity of polymer solution resulting in
of detector was set at 256 nm. The total resistance to stretching and elongation of
chromatographic run time was 7.50 min. the electrified jet of nylon 6,6 solution.
3. Results & Discussion
In addition, when β-CD was added
3.1 Characterization
into nylon 6,6 solution, its was not
3.1.1 SEM analysis
significantly affect to the morphology of
Scanning electron microscopy
electrospun nanofibers. Smooth and
(SEM) was used to investigate the
uniform nanofibers were obtained as shown
morphology of the nanofibers and
in Figure 2. Moreover, as the content of the
determine a diameter of the nanofibers. The
β-CD increased from 25% to 75% wt, the
morphology of the electrospun nylon 6,6
larger diameter of electrospun nanofibers
nanofibers at various concentration (10%-
were obtained. The average diameters of
18% wt) was shown in Figure 1. Bead
nylon 6,6 with 25% wt β-CD(nylon 6,6/25
formation on the fibers was observed when
β-CD), 50% wt β-CD (nylon 6,6/50β-CD)
concentration of nylon 6,6 was lower than
and 75% wt β-CD (nylon 6,6/75β-CD)
12% wt. Smooth and uniform fibers were
were 132 nm, 136 nm and 143 nm,
obtained when fabricated using15%-
respectively. Due to the viscosity increase
18%wt nylon 6,6 solution. In addition, the
and interaction (H bonds) between the β-
uniformity of the fibers were increase with
CD molecules and nylon 6,6 polymer
the increase of polymer solution
chains.14
concentrations.

(a) (b)

Figure 1. SEM images of the nylon 6,6

nanofiber at difference concentration of
nylon 6,6 polymer solution. (c) (d)

The fiber diameter was determined

by measuring the SEM images using
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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
 The FT-IR was used to evaluate the
functional groups in nylon 6,6 nanofiber.
The spectrum of nylon 6,6 nanofibers
exhibited main characteristic peak at 3301
Figure 2. SEM images of electrospun cm-1 (N-H stretching vibration), 2934 cm-1
nanofibers (a) nylon 6,6 (b) nylon 6,6/25 β- (-CH2 stretching vibration), 2860 cm-1 (-
CD (c) nylon 6,6/50β-CD and (d) nylon CH- symmetric stretching vibration), 1637
6,6/75β-CD. cm-1 (C=O stretching vibration) and 1536
3.1.2 BET analysis cm-1 (N-H bending vibration) as shown in
The specific surface area and Figure 3a.
porous structures of electrospun nylon 6,6 The spectrum of nylon 6,6/50β-CD
and nylon 6,6/β-CD nanofibers were nanofibers (Figure 3(b)) exhibited main
determined using the Brunauer-Emmett- characteristic peaks at 1027.87 cm-1 (-OH
Teller (BET) method. The unmodified bending vibration) and 1150 cm-1 assigned
nylon 6,6 nanofibers yielded a BET surface to the antisymmetric stretching vibration of
of 18.373 m2.g -1. The surface area of nylon the C-O-C glycosidic bridge. In addition,
6,6/25β-CD, nylon 6,6/50β-CD and nylon there is a new peak at 1715 cm-1 (C=O
6,6/75β-CD nanofibers are 18.373, 12.575, stretch dimer H-bonded) occur which
10.727 and 9.7695 m2 g-1 respectively confirmed the H-bonding interaction
(Table 1). Nevertheless, when the content between β-CD and nylon 6,6.
of β-CD increased from 25% to 75% (w/w,
with respect to nylon 6,6) surface area of
the nanofibers are decreased. A possible
reason for the surface area decrease may be
the existence of CD on the surface of the
nylon 6,6/CD nanofibers.
Barrett-Joyner-Halenda model
(BJH) was also calculated to evaluate the
pore diameters of nylon 6,6/β-CD
electrospun nanofibers as shown in Table 1
indicating a mesoporous structure as
defined by IUPAC definition, which
classifies the mesoporous materials to have
a diameter of 2-50 nm. (a)
Table 1. Specific Surface area (BET) and
Pore sizes of nylon 6,6/ β-CD electrospun 120

nanofiber. 100
-1
2860 cm
surface area pore diameter -1
Transmittance (%)

80 CH stretch 3301 cm
Nanofiber 2934 cm
-1
N-H stretch
(m2 .g-1) (nm) 60 -1 CH2 stretch
1536 cm
Nylon 6,6(15%) 18.373 7.6406 CH stretch
40 1637 cm-1
Nylon 6,6/25β-CD 12.575 7.0169 C=O stretch

Nylon 6,6/50β-CD 10.727 6.9268 20

nylon 6,6 nanofibers
Nylon 6,6/75β-CD 9.7695 6.6535 0
500 1500 2500 3500
3.1.3 FT-IR analysis Wavenumber (cm-1)

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© The 2020 Pure and Applied Chemistry International Conference (PACCON 2020)
(b)
120
100
Transmittance (%)

2860 cm-1
80 1715 cm-1 CH stretch
C=O stretch 2934 cm-1 -1
60 dimer H-bond CH2 stretch 3301 cm
1150 cm-1 N-H stretch
1027 cm-1 OH stretch
OH stretch
40 1637 cm-1
1536 cm-1 C=O stretch
20
nylon 6,6/β-CD nanofibers
0
500 1500 2500 3500 Figure 4. Influence of the nanofiber with
Wavenumber (cm-1)
different β-CD content on % recovery of
Figure 3. FT-IR spectrum of (a) nylon 6,6 the analytes.
nanofibers (b) nylon 6,6/β-CD nanofibers
3.2 Application of nylon 6,6/β-CD 4. Conclusion
nanofibers as a sorbent in SPE In this study, the diameter of
To determine the efficiency electrospun nylon 6,6/β-CD nanofibers
extraction of the nylon 6,6/β-CD nanofibers were increased with increasing the
as a sorbent in solid phase extraction of concentration of nylon 6,6 solution. The
parabens, it was evaluated by determining specific surface area of nylon 6,6/β-CD was
the recoveries of sample spiked with 10 ng decreased when the amount of β-CD in the
mL-1 of paraben in water. The results fibers increase because β-CD was covering
revealed that the electrospun nylon 6,6/25β- on the surface of nylon 6,6 nanofibers.
CD nanofiber gave a high efficiency Finally, the electrospun nylon 6,6/β-CD
extraction for butyl paraben and propyl was applied as a sorbent in extraction of
paraben which was better than nylon 6,6,
parabens in water. The electrospun nylon
nylon 6,6/50β-CD and nylon 6,6/75β-CD
6,6/25β-CD which has the largest surface
nanofibers. For small molecules of analyte
(ethyl paraben and methyl paraben), the area gave the highest extraction efficiency.
extraction efficiency of nylon 6,6 and nylon
6,6 /25β-CD nanofibers was similar. The Acknowledgements
hydrophobic properties of analytes were This work was supported by Thesis
significant influence the extraction Scholarships of Program of Petrochemical
efficiency causing by the formation of and Polymer Science, Faculty of Science,
inclusion complex of cyclodextrins and Chulalongkorn University,
anlytes.12 On the other hand when the Chromatography and Separation Research
content of β-CD was increased, the Unit.
efficiency of extraction were decreased due
to β-CD covered on the surface of nylon References
6,6 nanofiber, which corresponds to the
1. Soni, M.G.; Taylor, S.L.; Greenberg,
BET results indicated that the surface area
N.A.; Burdock, G. A. Food Chem. Toxicol.
was reduced when increasing the amount of
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