International Journal of Biological Macromolecules 183 (2021) 2174–2183

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International Journal of Biological Macromolecules

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Preparation and characterization of guar gum based polyurethanes

Anbreen Anjum a, Mohammad Zuber a, Khalid Mahmood Zia b, *, Muhammad Naveed Anjum a,
Waseem Aftab c
a
Department of Applied Chemistry, Government College University, Faisalabad 38030, Pakistan
b
Department of Chemistry, Government College University, Faisalabad 38030, Pakistan
c
College of Engineering, Peking University Beijing, 100871, China

A R T I C L E I N F O A B S T R A C T

Keywords: Guar gum (plant-based polysaccharide) is a promising candidate with immense potential. It is used as emulsifier,
Guar gum thickener, stabilizer, and as binding agent in many industries. In the present project, it was planned to synthesize
Polyurethanes guar gum based polyurethanes by varying the amount of guar gum. Guar gum (GG) was used along with
Polysaccharides
hydroxyl-terminated polybutadiene (HTPB) as soft segment, which was then reacted with isophorone diiso­
FTIR
cyanate (IPDI) to form PU pre-polymers. In last step, these –NCO terminated pre-polymers were extended with
Solid-state 1HNMR
1,4 butane diol as chain extender. The prepared polyurethane samples were then characterized by using FTIR,
solid-state 1HNMR and X-ray diffraction (XRD). Thermal behavior of the samples was studied by thermogravi­
metric analysis (TGA) and differential scanning calorimetry (DSC). Results indicated that the incorporation of
guar gum in PU backbone improved its thermal behavior and crystallinity.

1. Introduction In recent years, among the growing apprehensions on environmental

issues, the petroleum-based synthetic polymers gradually underline
Polyurethanes (PUs) belong to the class of synthetic copolymers their disadvantages and hazards to the modern world from the percep­
which have also been associated with environmental concerns. Their tion of energy, fuel resources, and environment [8]. So it is necessary to
properties can also be tuned by the incorporation of natural polymers. enhance the properties of petrochemical based synthetic polymers by
Among natural polymers, plant based polysaccharides are most impor­ incorporating naturally renewable polymers, which have their unique
tant biopolymers because of their easy availability and abundance. functional, environmental, economical and commercial advantages. The
Polyurethanes are also called segmented block copolymers. The most apparent properties associated with the natural polymers as
segmented polyurethanes consist of two alternating hard and soft seg­ compared with synthetic polymers are their biodegradability, abun­
ments [1]. The hard segment is usually comprised of diisocyanate such dance, and biocompatibility, low processing cost and non-toxicity [9]. A
as isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), hexam­ large number of polysaccharides such as cellulose, starch, chitin, chi­
ethylene diisocyanate (HDI) etc. and chain extender, while the soft tosan, heparin, alginate etc. have been researched and used for the
segment is composed of various types of polyols with two or more hy­ formulation of products of food, biomedical and cosmetics industries
droxyl terminated groups, polycarbonates, polyether or polyesters [2]. [10,11].
The contribution of soft segment is to provide elasticity to the polymer But these natural polymers are unable to fulfill all necessities in
chains whereas the hard segment of polyurethane usually offers the modern industrial applications because of their structural limitations,
mechanical strength and rigidity to the polymers [3,4]. solubility, colloidal properties, poor machinability, and so on [12].
For the decades, polyurethanes have been used industrially because Gums have shown variety of structures and properties due to their
of their versatile properties. Various applications of PU range from natural abundance and have gained gigantic attention as new families of
elastomers, foams, adhesives, paints, fibers and special coatings [5]. natural polymers [13]. Guar gum is a plant based versatile biopolymer
Different PU compositions have been selected to tailor the physical and for biodegradable plastics. It is also an important industrial poly­
chemical characteristics that are specifically required in certain appli­ saccharide, used in food, cosmetics, paper and pharmaceutical in­
cation [6,7]. dustries etc. [14].

* Corresponding author.
E-mail address: ziakmpkpolym@[Link] (K.M. Zia).

[Link]
Received 3 March 2021; Received in revised form 25 May 2021; Accepted 3 June 2021
Available online 5 June 2021
0141-8130/© 2021 Elsevier B.V. All rights reserved.
A. Anjum et al. International Journal of Biological Macromolecules 183 (2021) 2174–2183

Guar gum, a high-molecular weight, hydrophilic, nonionic, sustain­ Table 1

able, non-toxic, low cost and most abundant natural polysaccharide Formulations and Measurement of Viscosity [mPas] of Guar Gum and HTPB
belonging to the family of Leguminaseae isolated from the seed endo­ Blends.
sperm of the guar plant [15,16]. Chemically it is classified as gal­ Sr # GG (moles) (HTPB) Viscosity at (30 ◦ C) Viscosity at (90 ◦ C)
actomannans and is composed of a straight chain of D-mannose units (moles)
linked by β (1–4) glycosidic bond, which are partially substituted with 1 0.0 1.0 3838 744
D-galactose units united with α (1–6) glycosidic linkage [17]. 2 0.01 0.99 4049 794
Polyurethanes being a prominent class of synthetic polymers are 3 0.05 0.95 4289 936
4 0.1 0.9 4560 1200
receiving much attention as one of the most important materials due to
5 0.2 0.8 5100 1630
their tunable physical and mechanical properties [18]. However, the 6 0.3 0.7 5677 2100
properties of PU need to be further improved to allow more applications. 7 0.4 0.6 6298 2610
Kumar et al. [19] prepared a series of semi interpenetrating polymer
GG = Guar gum.
networks (SIPNs) by using different weight ratios of guar gum i.e. 5, 10, HTPB = Hydroxyl terminated polybutadiene (Mn = 2896).
20 and 30 incorporated into polyurethane/polyacrylonitrile (PU/PAN,
50/50). Biodegradation behavior of the prepared samples was also
stirring, the samples were stored for about 4 h to get uniformity and
studied. Hiremath & Vishalakshi [20] made an IPN system comprising of
homogeneity. All the tests for the measurement of viscosity were
guar gum and polyacrylamide in aqueous medium. Oprea [21] prepared
completed within 24 h after sample preparation by using Micro Visco-
films from multi-crosslinked polyurethane with different contents of
Amylo-Graph unit between temperature ranges 30 ◦ C to 90 ◦ C.
guar gum (1–10 wt%) through a solution-casting method, followed by a
thermal treatment or natural light exposure crosslinking procedure.
2.3. Synthesis of guar gum based polyurethanes
Chandrika et al. [22] prepared cross linked guar gum-g-(acrylate)
porous superabsorbent hydrogels by employing free radical initiated
The guar gum based polyurethanes (GG-PU) were prepared by step
open air grafting polymerization technique. Eswaramma et al. [23]
growth polymerization (two steps) mechanism. The first step involved
prepared a pH sensitive IPN microgel og guargum-g-poly(2-
the preparation of NCO terminated PU prepolymers while in the second
dimethylamino)ethyl-methacrylate and chitosan by emulsion cross
step; PU prepolymers were extended with chain extender, following the
linking method using glutaraldehyde as a cross linker. Iqbal et al. [24]
formulation in Table 2.
prepared a series chitosan/poly(vinyl alcohol)/guar gum blends and
In a four-necked reaction kettle equipped with mechanical stirrer,
evaluated antimicrobial activity. Palem et al. [25] synthesized poly
heating oil bath, reflux condenser, dropping funnel and N2 inlet and
(acrylamide-co-acrylamidoglycolic acid)/guargum‑silver nanoomposite
outlet, one mole of a mixture of guar gum and hydroxyl terminated
hydrogels to study the release of anticancer drug.
polybutadiene (HTPB) were placed. The mixture was stirred continually
Keeping in view of available research works and the intrinsic prop­
at 70 ◦ C to achieve homogenization, then 3.0 mol of diisocyanates (IPDI)
erties of guar gum, it has been observed from the literature that guar
were added to the homogenized mixture with continuous stirring at
gum has been used as grafting material for potential applications. There
90 ◦ C till the formation of guar gum based NCO terminated PU pre-
is a dire need to use guar gum in conjunction with hydroxyl terminated
polymers. The guar gum based NCO terminated PU pre-polymers were
polybutadiene (HTPB) as soft segment. A major advantage of these
then converted into the final guar gum based polyurethanes (GG-PU) by
biopolymers is that they are natural ingredients, which are often
stirring the pre-polymers with chain extender i.e. 1–4 butane diol in the
required for ‘ecofriendly’ labels to replace petroleum based polyols i.e.,
last step.
HTPB. Biodegradable biopolymers come from renewable resources that
To complete the polymerization reaction, a fraction of a drop of
allow them to replace or substitute the fossil fuel–based polymers which
dibutyltin dilaurate (DBTDL) catalyst was also added to speed up the
create a sustainable industry as well as enhancement in various prop­
reaction. The reaction was continued at the same temperature until the
erties such as durability, flexibility, high gloss, clarity, and tensile
color homogeneity was obtained in the reaction mixture. At this stage
strength. Special interest was to achieve better crystalline behavior
the dispersion of the chain extender was supposed to be completed and
along with the greater thermal stability so that prepared material can be
liquid polymer was casted on to a Teflon plate to form a uniform sheet of
used for biomedical applications. So, present research work was
about thickness 2–3 mm. The prepared polymer was kept in open air for
designed to synthesize a series of guar gum based polyurethanes by
few minutes to evaporate the solvents from the material and then placed
varying the ratio of guar gum. The prepared guar gum based poly­
in the circulating hot air at 100 ◦ C and finally cured for 24 h. The cured
urethane samples were characterized by means of FTIR, 1H solid state
sample sheets were stored for one week at ambient temperature (25 ◦ C)
NMR, TGA, DSC, and XRD.
before testing. The whole reaction scheme is given in Fig. 1.
2. Experimental work

2.1. Materials required Table 2

Formulations of Guar Gum Based Polyurethanes by varying the concentration of
Guar gum, isophorone diisocyanate (IPDI), 1,4 butane diol (BDO), guar gum.
dibutylin dilaurate (DBTDL). All the above chemicals were pure upto Sr # Sample GG (HTPB) IPDI BDO
99% and were purchased from Merck (Sigma), Germany. Hydroxyl code (moles) (moles) (moles) (moles)

terminated polybutadiene (HTPB; Mn = 2896) was provided by NES­ 1 BPU 0.0 1.0 3.0 2.0
COM, Pakistan. All the reactants were dried in vacuum for about 24 h 2 GPU1 0.01 0.99 3.0 2.0
3 GPU2 0.05 0.95 3.0 2.0
before use.
4 GPU3 0.1 0.9 3.0 2.0
5 GPU4 0.2 0.8 3.0 2.0
2.2. Preparation of guar gum-HTPB blends and viscosity measurement 6 GPU5 0.3 0.7 3.0 2.0
7 GPU6 0.4 0.6 3.0 2.0
Guar gum and HTPB were mixed in different mole ratios as formu­ GG = Guar gum.
lated in Table 1. Samples were prepared carefully by adding the weighed HTPB = Hydroxyl terminated polybutadiene (Mn = 2896).
amounts of guar gum and HTPB into vortex by mixing with a mechanical IPDI = Isophorone diisocyanate.
stirrer continuously for 30 min at constant temperature (30 ◦ C). After BDO = 1,4 butane diol.

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Fig. 1. Proposed reaction scheme for the synthesis of Guar Gum Based Polyurethanes.

2.4. Spectroscopic and thermal characterization 2.4.2. Solid-state proton NMR (1HNMR) analysis
Solid-state one-dimensional 1HNMR spectrum of GG-PU was recor­
2.4.1. FTIR study ded on Bruker Biospin GmBH with number of scans 16, as the PU sam­
ATR-FTIR spectra of the samples including monomers, guar gum ples were not dissolved in any of the solvent available for solution
1
based NCO-terminated PU pre-polymer and guar gum based poly­ HNMR. The frequency of spectrophotometer was 400.25 Hz at 294.5 K.
urethanes were recorded at room temperature in the range between
4000 cm− 1-400 cm− 1 by using Bruker-IFS48 Fourier transform infrared 2.4.3. X-ray diffraction studies
spectrophotometer (Ettlingen, Germany) accessorized with ATR (dia­ The crystalline pattern of the prepared samples was determined by
mond crystal). The number of scans comprised of 16 with the resolution using an X-Ray diffractometer (Siemens D-5000). It was operated at 40
4 cm− 1. KV (operating voltage) and 10 mA (electric current) with radiation

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source CuKα. The samples were scanned in the 2θ from 5◦ to 40◦ at a guar gum (Fig. 2a), a very strong and broad absorbance peak at, 3280.1
speed of 2◦ /min. cm− 1 assigned to the hydroxyl functional group (–OH) stretching. The
peak at 2922.2 cm− 1 confirmed –CH2– asymmetric stretching vibrations
2.4.4. Thermogravimetric analysis (TGA)/differential scanning calorimetry while peaks at 2087.3 cm− 1 and 1405.7 cm− 1 confirmed the –CH
(DSC) stretching vibrations [28]. The band at 1640 cm− 1 is for ring stretching,
Thermal stability of the prepared polyurethane samples was ob­ 1375.4 cm− 1 is for –CH2– deformation. The peaks observed in the
tained by using TG/DSC technique (SDT Q600 V20.9 Build 20) instru­ spectrum of guar gum between 750 and 1250 cm− 1 indicated the highly
ment. Alumina pan was used for heating the sample at 10 ◦ C/min from coupled stretching vibrations of C–O–C, C–C–O, C–OH, ((1–4), (1–6)
room temperature to 600 ◦ C under N2 atmosphere (100 ml/min). linkage of galactose and mannose units [29,30]. The spectrum of HTPB
in Fig. 2b clearly showed the presence of peak at 3410 cm− 1 because of
3. Results and discussion –OH stretching. Other assigned peaks are; 2914.8 cm− 1 –CH2– asym­
metric stretching; 2844 cm− 1 –CH2– symmetric stretching; 3075.1 cm− 1
3.1. Molecular characterization and 3004.2 cm− 1 (extended = C–H stretching vibrations). Absorption
peaks at 965.4 cm− 1, 909.5 cm− 1 and 682.1 cm− 1 support the trans 1,2
3.1.1. Measurement of viscosity for GG-HTPB blends (T), vinyl and cis 1,4 (C) contributing structures of HTPB respectively.
Table 1 illustrates the viscosities of various blends of guar gum and The peak at 1640 cm− 1 is for –C=C– stretching vibrations. The band at
hydroxyl terminated polybutadiene at 30 ◦ C and at 90 ◦ C. It has been 1438.8 cm− 1 is assigned the –CH deformation vibration of –CH2–
clearly shown that the viscosities of guar gum-HTPB blends increases [31,32]. From the spectrum of IPDI (Fig. 2c), a very sharp and intense
proportionally by increasing the concentration of guar gum in the peak at; 2247.6 cm− 1 has been observed for –NCO stretching vibrations,
blends. This is due to the interaction of galactose side chains of guar gum two peaks at 2926.0 cm− 1 and 2952.1 cm− 1 for –CH2– symmetric and
molecule with hydroxyl terminated polybutadiene. An increase in the asymmetric stretching vibrations present in cyclic ring of IPDI. Other
concentration of guar gum enhances the entanglement and inter- noticeable absorptions are attributed as; 1461.1 cm− 1 for deforming
molecular interaction between the chains, which moves towards the vibrations of –CH in aliphatic –CH2– and –CH3 units; 1364.2 cm− 1
increase in viscosity [26]. (bending vibration of –CH2– groups); 1190 cm− 1 twisting of –CH in
It has also been observed from Table 1 that the viscosities of GG- –CH2– groups [33,34].
HTPB blends are reduced significantly when the temperature is In the spectrum of GG + HTPB (Fig. 3a) major absorption bands are:
increased from 30 ◦ C to 90 ◦ C. This trend occurs because the increase in 3410 cm− 1 for –OH moiety, 2844 cm− 1 and 2914.8 cm− 1 –CH2– sym­
kinetic motion at elevated temperatures promotes the cleavage of metric and asymmetric stretching vibrations, respectively; 3075.1 cm− 1
intermolecular bonds between the adjacent chains [27]. and 3004.2 cm− 1 (=C–H stretching vibrations). FTIR spectrum of GG +
HTPB shows that there is no chemical interaction between guar gum and
3.1.2. ATR-FTIR studies HTPB rather they are mixed homogeneously. FTIR spectrum of guar gum
The ATR-FTIR spectra of guar gum, HTPB and IPDI are illustrated in based PU pre-polymer is illustrated in Fig. 3b.
the Fig. 2. Following major peaks were observed in the FTIR spectrum of The major peaks of urethane group –NH and –C=O are indicated at

Fig. 2. FT-IR spectra of Guar Gum (a), HTPB (b), IPDI (c).

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Fig. 3. FT-IR spectra of GG + HTPB (a), –NCO terminated guar gum based PU pre-polymer (b).

Fig. 4. FT-IR spectra of BPU (a), GPU 1(b), GPU 2(c), GPU 3(d), GPU 4(e), GPU 5(f), GPU 6(g).

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3343.4 cm− 1 and 1722 cm− 1 respectively. A sharp peak at 2258.8 cm− 1 3.7 ppm (H9), 3.9 ppm (H8), 5.4 ppm (galactose anomeric proton, H7),
represents the terminal –NCO group. The symmetric and asymmetric 3.35 ppm (H6), 4.0 ppm (H5), 3.30 ppm (H4), 3.90 (H2− H3), 5.5 ppm
stretching peaks of –CH2– group are shown at 2844 cm− 1 and 2914.8 (mannose anomeric proton, H1). Higher chemical shift values of –NH
cm− 1 respectively. Additional peaks at 1509.6 cm− 1 and 1133.1 cm− 1 group in –NHCOO is due to hydrogen bonding interaction between –NH
were attributed to the –NH bending and –CN stretching, respectively. In group of urethane with neighboring –OH groups from guar gum, BDO, as
the spectrum the disappearance of –OH peak, decrease in the intensity of hydrogen bonding tends to move the –NH signal to higher frequency
–NCO peak and formation of –NH peak confirmed the synthesis of NCO- (lower field) [38].
terminated PU pre-polymer [35].
Fig. 4 represents the FTIR spectra of guar gum based PU samples i.e. 3.3. XRD study
BPU, GPU1-GPU6. In all the spectra, disappearance of –NCO peak at
2258.8 cm− 1 confirmed that there is no unreacted isocyanate in the final X-Ray diffraction study was carried out to investigate the changes in
PU samples. In all the spectra of guar gum based PUs, characteristic the crystalline structure of final guar gum based PUs by using different
bands appeared in the range of 3320–3365 cm− 1 were assigned to the mole ratio of guar gum. XRD patterns of all PU samples i.e. BPU1, GPU1-
–NH stretching vibrations of urethane group. The –NH band overlap the GPU6 are presented in Fig. 6. The 2θ vales of BPU1, GPU1, GPU2, GPU3,
–OH stretching vibration band in the range between 3280.1 cm− 1 and GPU4, GPU5 and GPU6 were 19.49◦ , 19.55◦ , 19.57◦ , 19.80◦ , 19.42◦ ,
3410 cm− 1 [36]. Other peaks at 2914–2920 cm− 1 are ascribed as –CH2– 19.52◦ , 19.77◦ respectively. Due to different mole ratio of guar gum,
asymmetric stretching vibrations; 2839–2846 cm− 1 as –CH2– symmetric peaks were appeared at different 2θ. Segmented polyurethane derives
stretching vibrations; 3034–3074 cm− 1 as = C–H stretching vibrations; their elastomeric properties from phase separation of soft segment (SS)
1695–1703 cm− 1 as stretching vibrations of –C=O of urethane group; and hard segment (HS), which can take place depending on their relative
1522-1532 cm− 1 –NH deformation; 1305–1306 cm− 1 as –CH2– wagging; contents, structural regularity and thermodynamics incompatibility
1235–1238 cm− 1 as –CN stretching; 1132–1151 cm− 1 as C–O–C [39]. In comparison with PU samples i.e. BPU (without guar gum) and
stretching. According to the wave numbers, the –NH and –C=O in all the GPU1-GPU6 (with guar gum), we can observe that the presence of guar
samples of guar gum based PUs are in hydrogen bonded states [37]. gum favors the formation of more ordered structure. Higher peak in­
tensities of the samples (GPU1-GPU5) leading us to conclude that these
3.2. 1
H solid-state NMR study samples have higher crystallinity as compared to BPU. GPU4 shows the
maximum peak intensity and hence it has more uniform structure. It can
The one dimensional (ss) static 1H NMR spectrum of guar gum based also be seen that the sample (GPU6) has shown surprisingly a lower
PU (GPU3) is presented in Fig. 5. The H1-H6 belong to the chemical shift diffraction peak height when compared with BPU, which represents this
values of β-D-mannopyranose unit; H7-H12 relates to the α-D-galactose sample has smallest crystal particles resulting in decrease of crystallinity
unit; H15 and H22 relates to the –NH of urethane linkage; H16-H21 are and made it more amorphous. It might be due to the random distribution
of IPDI; H13-H14 are of HTPB, while H23-H26 belongs to BDO. The of guar gum in final PU. Zia et al. [40] observed the similar behavior that
chemical shift values (ppm) for all the designated protons are given the crystallinity of PU samples increased by increasing the chitin
below; 7.67 ppm (–NHCOO, H15), 6.76 ppm (H22, urethane proton near content.
to –CH2 group of IPDI), 3.54 ppm (H16), 1.67 ppm (H17), 1.32 ppm
(H18), 0.87 ppm (H19), 0.94 ppm (H20), 2.7 ppm (H21), 4.7 ppm 3.4. Thermal study
(H13), 5.9 ppm (H14), 3.90 ppm (H23), 1.61 ppm (H24), 1.5 ppm
(H25), 3.4 ppm (H26), 4.1 ppm (H12), 4.2 ppm (H11), 3.6 ppm (H10), Thermal stability is an important characteristic for structural

Fig. 5. 1H solid-state NMR spectra of GPU3.

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Fig. 6. XRD patterns of guar gum based PUs (BPU, GPU1-GPU6).

material and polyol plays a vital role in determining the thermal stability trend in the thermal behavior was seen by increasing the amount of guar
[41]. The TGA curves of BPU, GPU1-GPU6 are shown in Fig. 7. The gum. TGA results revealed that all the samples showed two stage
thermal decomposition temperatures are given in Table 3. Higher initial decomposition; initial stage of decomposition occurred in the range of
decomposition temperatures were observed for GPU1, GPU3-GPU6 than 175–360 ◦ C which might be due to loss of moisture and disintegration of
BPU. Guar gum based PUs reached a 10% weight loss in the temperature macromolecular chains of guar gum. Keith et al. [42] reported that there
range upto 333 ◦ C compared to that of BPU which took place at 309 ◦ C. is 59.4% weight loss of in the range of 247–330 ◦ C for the degradation of
This difference is maintained throughout the main course of decompo­ guar gum backbone. Final decomposition stage is extended upto 500 ◦ C.
sition. It was also observed that the guar gum based polyurethanes are Major weight loss was observed during final decomposition stage due to
thermally more stable than BPU (without guar gum). The incorporation thermal degradation of PU chains.
of guar gum into polyurethane enhances the thermal stability by DSC analysis is another important tool in addition to XRD to find out
increasing the intermolecular hydrogen bonding. Yet no significant the crystallization behavior of PU samples. DSC analysis was done to

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Fig. 7. TGA curves of guar gum based PUs (BPU, GPU1-GPU6).

Table 3
TGA studied parameters of PU samples.
Sample code Tonseta Tib T10c T20c T30c T50c T80c Tmaxd
◦
C ◦
C ◦
C ◦
C ◦
C ◦
C ◦
C ◦
C

BPU 22.87 ± 0.03 270 ± 0.07 309.01 ± 0.06 352.28 ± 0.06 402.76 ± 0.06 438.38 ± 0.08 462.92 ± 0.03 480 ± 0.06
GPU1 21.47 ± 0.01 304 ± 0.04 332.41 ± 0.05 364.89 ± 0.06 418.08 ± 0.06 446.13 ± 0.06 465.68 ± 0.06 485.02 ± 0.06
GPU2 21.20 ± 0.04 270 ± 0.01 302.25 ± 0.06 354.10 ± 0.05 406.86 ± 0.01 438.69 ± 0.06 463.82 ± 0.05 475.31 ± 0.06
GPU3 23.34 ± 0.06 302 ± 0.07 323.29 ± 0.06 358.52 ± 0.06 412.00 ± 0.06 444.18 ± 0.04 464.24 ± 0.04 490.37 ± 0.04
GPU4 22.25 ± 0.01 300 ± 0.08 320.27 ± 0.07 349.79 ± 0.04 400.36 ± 0.06 441.65 ± 0.05 462.66 ± 0.05 490.56 ± 0.04
GPU5 25.25 ± 0.02 301 ± 0.06 322.82 ± 0.02 351.21 ± 0.06 402.94 ± 0.05 443.38 ± 0.05 465.13 ± 0.06 480.03 ± 0.04
GPU6 27.22 ± 0.04 300 ± 0.07 316.15 ± 0.06 338.26 ± 0.02 370.98 ± 0.06 437.01 ± 0.06 462.69 ± 0.06 490 ± 0.04
a
Temperature from which TG analysis starts.

b
Temperature at which decomposition of samples starts in TGA.

c
Temperature at which 10%, 20%, 30%, 50%, 80% weight losses of the samples were obtained from TGA.

d
Maximum decomposition temperature obtained from TGA.

scrutinize the influence of guar gum on the properties and structure of and abolition of volatile products.
polyurethanes. DSC thermographs of PU samples are presented in Fig. 8.
In all PU samples, changes are observed between 20 and 600 ◦ C. All DSC 4. Conclusion
thermographs are characterized by endotherm below 100 ◦ C due to
evaporation of absorbed moisture and impurities. All DSC thermographs In this study, the synthesis of PUs were carried out by reacting a
show two exothermic and two more endothermic transitions. An in­ mixture of guar gum and HTPB with IPDI to form NCO terminated
crease in melting temperature of guar gum based PUs clearly showed the polyurethanes pre-polymers which were then extended with BDO.
presence of strong intermolecular hydrogen bonding among the polymer Different PU samples were made by varying the concentration of guar
chains. Increase in the heat of crystallization confirmed the crystalline gum. Disappearance of NCO peak and formation of characteristics peak
nature of guar gum based PUs as compared to PU without guar gum. of –NH in FTIR spectra of all PU samples confirmed the formation of
Endothermic peaks correspond to the ignition of combustion of PU urethane linkage and the completion of reaction. The solid-state static
1
samples and also the decomposition of galactose and mannose units of HNMR also confirmed the formation of urethane linkage. XRD patterns
guar gum in guar gum based PUs. Exothermic peaks shown in the DSC showed that the guar gum based PUs have higher peak intensities and
curve relates to the oxidative and thermal decomposition, vaporization crystallinity as compared to PU without guar gum (BPU). Guar gum

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