Graft Copolymerization of Methyl Acrylate onto Sago

Starch Using Ceric Ammonium Nitrate as an Initiator

LUTFOR RAHMAN, SIDIK SILONG, WAN MD ZIN, M. ZAKI AB RAHMAN, MANSOR AHMAD, JELAS HARON

Department of Chemistry, Faculty of Science and Environmental Studies, University Putra Malaysia,
43400 UPM Serdang, Selangor, Malaysia

Received 12 March 1999; accepted 9 August 1999

ABSTRACT: The graft copolymerization of methyl acrylate onto sago starch was carried
out by a free radical initiating process. The free radicals were produced by the chemical
initiation method in which ceric ammonium nitrate was used as an initiator. It was
found that the percentages of grafting, grafting efficiency, and rate of grafting were all
dependent on the concentration of ceric ammonium nitrate (CAN), methyl acrylate
(MA), sago starch (AGU), mineral acid (H2SO4), and reaction temperature and period.
The variables affecting the graft copolymerization were thoroughly examined. The
optimum yield of grafting was obtained when the concentration of CAN, MA, AGU, and
H2SO4 were used at 8.77 ⫻ 10⫺3, 0.803, 0.135, and 0.175 mol L⫺1, respectively. The
optimum reaction temperature and period were 50°C and 60 min, respectively. The rate
of graft polymerization was explored on the basis of experimental results and reaction
mechanism. The evidence of grafted copolymers was investigated by using FTIR spec-
troscopy, TG, and DSC analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76:
516 –523, 2000

Key words: graft copolymerization; sago starch; free radical; monomer and poly
(methyl acrylate) polymer

INTRODUCTION is susceptible to fungal attack. The formation of

poly(methyl acrylate) graft onto the rigid starch
Graft copolymerization of vinyl monomers onto matrix produces graft copolymers that yield
starch by a free radical initiating system is an leathery plastics on extrusion processing.4 Graft-
excellent method for preparing composites of ing has been used as an important technique for
starch with synthetic polymers; numerous mono- modifying physical and chemical properties of
mers with a free radical initiating system have polymers. For example, by grafting various mono-
been investigated.1,2 The graft copolymer of acry- mers onto starch, it is possible to modify many
late monomers onto starch may be used as biode- different properties in the polymer, such as elas-
gradable mulch in agriculture, medicine, and food ticity, sorbancy, ion exchange capabilities, ther-
packages. Dennerberg et al.3 reported that graft mal resistance, and resistance to microbiological
copolymerization of methyl acrylate (MA) onto attack.5,6 A redox system generally comprises the
corn starch initiated by ceric ammonium nitrate transition metal ions that exist in various oxida-
(CAN) and the starch portion of these extradites tion states. Such oxidized metal ions may directly
oxidize sago starch to initiate the transition of
Correspondence to: S. Silong. free radicals for grafting. A detailed study of MA
Contract grant sponsor: IRPA, Ministry of Science and with sago starch (AGU) has been presented by
Education, Malayasia; contract grant number: 51321.
Journal of Applied Polymer Science, Vol. 76, 516 –523 (2000)
CAN initiation, and it will be further extended to
© 2000 John Wiley & Sons, Inc. the preparation of ion-exchange materials.
516
 MA GRAFT COPOLYMERIZATION 517

EXPERIMENTAL sulfuric acid (H2SO4 : H2O; 1 : 1) was added to the

reaction mixture. After 5 min the required milli-
Materials and Methods liters of 0.1M CAN solution was added, and the
reaction mixture was mixed homogeneously. Ex-
AGU was purchased from Tepung Sago Indus-
actly 10 min later, the required amount of mono-
tries Ltd. (Malaysia). It was dried at 60°C for 24 h
mer (MA) was added to the mixture, and the
before use. The MA monomer was obtained from
mixture was stirred for specific periods. When the
Merck Co. (Rahway, NJ). To remove inhibitor,
reaction was complete, the product was cooled
MA was passed through columns filled with chro-
under running tap water and poured into 200 mL
matographic grade activated alumina. The mono-
of methanol to induce precipitation. The grafted
mer was stored at ⫺10°C; CAN (BDH Chemicals,
products were washed several times with metha-
Poole, UK), methanol (Beaker), and other chemi-
nol/water (4 : 1), and then the products were oven
cals used were analytical reagent grades.
dried at 50°C to constant weight.
Graft Copolymerization
Extraction of Homopolymer and Determination of
The reactions were carried out in 250-mL three- Graft Level
neck flasks equipped with a stirrer and condenser
and immersed into thermostat water bath. The Exactly 2000 g of the above crude products was
N2 gas was purged into the flask to remove the taken and extracted with the acetone in a
presence of oxygen during the operation. The soxhlets extractor for 24 h to remove poly(methyl
starch slurry was prepared from 1.25 g AGU, and acrylate) homopolymer, and pure copolymers
50 mL distilled water was preheated at 80°C for were then dried at 50°C to constant weight.4
about 30 min with stirring. After it was gelati- The percentage of grafting (P g) and grafting
nized, the flask contents were then cooled to the efficiency (G e); rate of graft polymerization (R g)
required temperature and then 1.05 mL diluted were determined by the following formula7:

weight of grafted polymer

Percentage of grafting (P g) ⫽ ⫻ 100
weight of backbone

weight of grafted polymer

Grafting efficiency (G e) ⫽ ⫻ 100
weight of grafted polymer ⫹ weight of homopolymer

weight of grafted polymer

Rate of graft polymerization (R g) ⫽
(MW of monomer) ⫻ [reaction time (s)] ⫻ [volume (mL)]
⫻ 1000 共mol L ⫺1 s ⫺1兲

Side-Chain Separation tate was thoroughly washed to neutral state

and dried at 50°C to a constant weight.
Grafted side chains were removed from the
starch backbone using the procedure recom- FTIR Analysis
mended by Dennerberg et al.3 Approximately
0.50 g of poly(methyl acrylate) grafted AGU Infrared (IR) spectra of polymer samples were
sample was placed in a 100-mL flask with 50 obtained from Fourier transform–IR (FTIR) spec-
mL glacial acetic acid. The flask was fitted with trometer (Perkin-Elmer 1725, Norwalk, CT). The
a condenser, and the mixture was refluxed for KBr pellets of AGU, poly(methyl acrylate)–
grafted AGU, and side-chain poly(methyl acry-
1 h. After swelling the grafted side chains, 5 mL
late) were prepared for the IR spectra recordings.
of perchloric acid (60%) was added dropwise,
and within a few minutes, the mixture turned
Thermogravimetry Analysis
into a clear solution. The product was immedi-
ately poured into ice water to precipitate the Thermogravimetry (TG) experiments were car-
poly(methyl acrylate) side chains. The precipi- ried out using a DuPont Thermal Analyzer
518 RAHMAN ET AL.

Figure 1 FTIR spectra of (a) sago starch, (b) poly(methyl acrylate) grafted sago
starch, and (c) side-chain poly(methyl acrylate).

(Model 990, Wilmington, DE). The analysis was COH stretching and bending, respectively [Fig.
carried out in N2 atmosphere from room temper- 1(a)]. IR spectrum of purified poly(methyl acry-
ature to 1000°C at a heating rate of 10°C min⫺1 late)– grafted AGU shows a new characteristic
with an N2 flow rate of 50 mL min⫺1. Thermo- absorption band of poly(methyl acrylate) at 1741
grams were obtained by plotting percent residual cm⫺1 of CAO stretching mode in addition to the
weight against temperature. same absorption bands of starch shown in Figure
1(b). In Figure 1(b), the poly(methyl acrylate) can
Differential Scanning Calorimetry Analysis be identified in copolymers on the basis of the
band at 828 cm⫺1. The spectrum of side-chain
Differential scanning calorimetry (DSC) experi-
polymer was identical to the spectrum of stan-
ments were performed using Polymer Laborato-
dard poly(methyl acrylate) shown in Figure 1(c).
ries differential scanning calorimeter with an N2
These results proved that the polymeric product
flow rate of 50 mL min⫺1. The DSC thermograms
was poly(methyl acrylate)– grafted AGU.
were obtained from samples of AGU and poly
(methyl acrylate)– grafted AGU packed into ordi-
nary Al pans and heated at the rate of 10°C Reaction Mechanism
min⫺1.
Although several reports have been published
on the graft copolymerization mechanisms of
the vinyl monomer onto starch macromole-
RESULTS AND DISCUSSION
cules,3,4,8 the proposed mechanism used in this
study was based on the same principle as that
Evidence of Grafting by FTIR Spectra
by Ceresa.8 The first step of the mechanism is
Infrared spectrum of AGU is shown in Figure that the cerium ion attacks the starch mole-
1(a); it indicates the characteristic absorption cules and forms a starch– ceric complex. The
bands of starch at 3402 and 1646 cm⫺1, due to Ce4⫹ ion in the complex is then reduced to a
OOH stretching and bending modes, respec- Ce3⫹ ion, and a hydrogen atom is oxidized. Con-
tively. Additional characteristic absorption bands sequently, a free radical is formed onto starch,
of AGU appear at 2930 and 1024 cm⫺1, due to while the bond is broken into carbon atoms 2
 MA GRAFT COPOLYMERIZATION 519

and 3 of the glucopyranose unit. The polymeric copolymerization is through a combination of

starch free radical so formed may react with two radicals. The reaction scheme of MA with
monomer to initiate graft copolymerization. In AGU initiated by CAN is as follows:
the presence of vinyl monomer, the starch free
radical was added to the double bond of vinyl
and
monomer, resulting in a covalent bond between

ST• ⫹ CH2ACH 3 STOCH2OCH•

P P
COOCH3 COOCH3
(1)

monomer and starch to create the chain reac- where ST• is free radical of sago starch
tion for propagation. Termination of the graft molecule.

Propagation:

STOCH2OCH• ⫹ CH2ACH 3 STO(CH2OCH)nOCH2OCH•

P P P P (2)
COOCH3 COOCH3 COOCH3 COOCH3

Termination:

STO (CH2OCHOCH2OCH•)n ⫹ 共 •CHOCH 2OCHOCH 2)mOST 3 STO(CH2OCHOCH2OCHO CHOCH2OCHOCH2)n⫹mOST

P P P P P P P P
COOCH3 COOCH3 COOCH3 COOCH3 COOCH3 COOCH3COOCH3 COOCH3

(3)

Effect of Reaction Temperature yield, as mentioned above, may be explained as

due to the operation of factor (vi) in the pres-
Temperature constitutes one of the vital factors ence of other factors.
in determining the extent of grafting. In gen- In this study the effect of temperature on the
eral, grafting yield increases with the increase yield of grafting was investigated at four differ-
of temperature until a limit is attained.6 In- ent temperatures: 30, 40, 50, and 60°C. The
crease of temperature, in fact, may lead to sev- percentage of grafting increased with the in-
eral effects on grafting, such as (i) starch may crease of temperature from 30 to 50°C. The
be swelled to larger extent; (ii) solubility of the maximum 54.40% of grafting was observed at
monomer may be increased; (iii) diffusion of 50°C, which was presumably the optimum con-
monomer to the grafting sites may be increased; dition of grafting. Beyond the temperature, the
(iv) initiating redox system may be easily de- percentage of grafting was decreased as shown
composed; (v) rate of initiation and propagation in Table I. This was attributed to the fact that
may be enhanced; and (vi) rate of termination with an increase in temperature, more and
may increase. If one considers all these factors, more radicals are formed, which enhance the
it is immediately evident that the operation of grafting. However, the increase in temperature
factors (i–v) will lead to an increase in grafting, beyond a specific limit causes increased extent
whereas the factor (vi) will have the reverse of radical termination, thus reducing the graft
effect on grafting. The limitation in grafting level.
520 RAHMAN ET AL.

Table I Effect of Reaction Conditions on the Yield of Graft Copolymers

Effect of Temperature Effect of Acid Concentration Effect of Reaction Period

Temperature % of [H2SO4] Reaction % of

(°C)a Grafting (/mol L⫺1)b % of Grafting Period (min)c Grafting

30 45.90 0.087 52.01 30 26.80

40 51.00 0.175 54.40 60 54.40
50 54.40 0.350 47.90 120 20.10
60 51.20 0.526 45.79 180 19.96

Concentrations of [AGU], [MA], and [CAN] were 0.135, 0.385, and 8.77 ⫻ 10⫺3 mol L⫺1, respectively.
a
Other conditions: reaction period, 60 min and [H2SO4], 0.175 mol L⫺1.
b
Other conditions: temperature, 50°C and reaction period, 60 min.
c
Other conditions: temperature, 50°C and [H2SO4], 0.175 mol L⫺1.

Effect of Acid Concentration tion for the leveling off of grafting values with
time is the reduction in the number of sites avail-
The process of graft copolymerization, whether
able for grafting.
initiated chemically or otherwise, has been
strongly dependent on the pH of the medium from
Effect of Initiator Concentration
which the grafting is carried out. The effect of
sulfuric acid concentration on percentage of graft- In the case of grafting initiated by a chemical
ing is presented in Table I. The optimum percent- initiator, the extent of grafting increases with the
age of grafting (54.40%) was achieved at 0.175 increase of initiator concentration up to a certain
mol L⫺1 H2SO4; beyond this acid concentration, limit, beyond which grafting no longer increases.
the grafting percentage decreased. The use of This has been ascribed to the decay of the macro-
mineral acids in the grafting process assists in radicals themselves by their reaction with the
the enhancement of graft level both by causing initiator.6 The effect of Ce4⫹ initiator on the yield
inter- and intracrystalline swelling of the sub- of grafting increased with the increase of CAN
strate.9 Acids also acted as a catalyst in the hy- concentration from 1.20 to 8.77 ⫻ 10⫺3 mol L⫺1,
drolysis of starch, leading to uncoiling of the as shown in Figure 2. The highest percentages of
chains and improving the monomer’s accessibil-
ity. A higher concentration of acid, however, can
cause degradation of the backbone as well as of
the graft chains. Initial increase in the extent of
grafting may be associated with the fact that the
acid catalyses the grafting reaction and enhances
the oxidizing capacity of the initiator. The subse-
quent decrease in grafting may be related to the
abundance of H⫹, which may act as a free radical
terminator.

Effect of Reaction Period

The effect of the reaction period on the percentage
of grafting is also shown in Table I. The maximum
percentage of grafting (54.40%) was observed at
60 min, and thereafter gradually decreased until
it leveled off. The decrease in grafting rates and
eventual leveling off of the grafting values have Figure 2 Effect of initiator [CAN] concentration on
been attributed to decreases in monomer and cat- the percentage of grafting. Temperature, 50°C; [MA],
alyst concentrations as well as to the retardation 0.385 mol L⫺1; [AGU], 0.135 mol L⫺1; reaction period,
of diffusion because of the formation of polymer at 60 min; [H2SO4], 0.175 mol L⫺1. —{—, grafting (%);
the starch surface.10 Another possible explana- —E—, efficiency (%).
 MA GRAFT COPOLYMERIZATION 521

grafting and grafting efficiencies were obtained 8.77 ⫻ 10⫺3 mol L⫺1 not only facilitates the more
using the CAN concentration at 8.77 ⫻ 10⫺3 mol active centers on the backbone, but also facilitates
L⫺1. The percentages of grafting and efficiency the homopolymerization.
attained a maximum of 54.35% and 84.60%, re-
spectively, when CAN concentration used was Effect of Monomer Concentration
8.77 ⫻ 10⫺3 mol L⫺1. Thereafter, the graft level
decreased with a further increase in CAN concen- It has been discussed that the initiation of graft
tration. The decrease of graft level at higher con- copolymerization by means of a redox couple in-
centrations of CAN may be due to the efficiency of volves primarily the formation of a complex be-
Ce4⫹ to take part in the termination of growing tween the initiator, starch, and the monomer.
grafted chains and homopolymerization.11 Efficiency of this evidently depends on the con-
The initial increase in percent graft with in- centration of the monomer present in the system,
creased catalyst concentration may either be due that is, the larger the concentration of monomer,
to catalyst exhaustion or an increase in rate of the more favored will be the formation of such a
grafting at low concentration.12 The decrease in complex that triggers the grafting process. An-
percent grafting at higher initiator concentration other parameter that is important in assessing
could be due to a decrease in the rate of polymer- the effect of monomer concentration on grafting is
ization. At higher ceric ion concentration, an in- gel effect, which arises from the solubility of ho-
crease was expected in the reaction steps involv- mopolymer in the monomer itself. A consequence
ing ceric ions, leading to an increase in the num- of this gel effect is a higher monomer concentra-
ber of starch radicals terminated prior to tion. As a result of this effect, the termination
monomer addition. Another factor contributing to rate decreases. Besides this, the gel effect helps in
a decrease in grafting levels at higher initiator swelling the starch, which ultimately facilitates
concentration is an increase in the homopolymer the diffusion of monomer to the active sites on the
formation, which competes with the grafting re- starch backbone, thereby enhancing the grafting.
action for available monomer. Though in general, grafting increases with the
The relation between rate of grafting and ceric increasing concentration of monomer, there is al-
ion concentration is shown in Figure 3. The rate of ways a limitation beyond which grafting is not
grafting increased linearly with ceric ion concen- favored. One of the reasons might be that swell-
tration from 1.20 to 8.77 ⫻ 10⫺3 mol L⫺1 CAN, ing of the base polymer at a higher monomer
and thereafter, the rate of grafting decreased be- concentration is not favorable for grafting.6
yond 8.77 ⫻ 10⫺3 mol L⫺1 (the deviation is omit- In this study the effect of monomer concentra-
ted in Fig. 3). As pointed out earlier, a significant tion on the percentage of grafting is presented in
increase in the initiator concentration beyond Figure 4. The percentage of grafting and grafting
efficiency increased with the increase of monomer
concentration from 0.178 to 0.803 mol L⫺1 MA.
The percentages of grafting and efficiency
reached a maximum of 130.01% and 82.20%, re-
spectively, at a monomer concentration of 0.803
mol L⫺1. The contribution of this effect would be
more pronounced at higher monomer concentra-
tions. As a result of this effect, the termination
rate was decreased. However, at higher concen-
tration of monomer beyond 0.803 mol L⫺1, the
percentages of grafting and efficiency decreased
because the highest percentage of homopolymer
was formed in the starch-graft-poly(methyl acry-
late). It is expected that swelling of the base poly-
mer at higher monomer concentrations was not
favorable for grafting.
The relation of rate of grafting and monomer
concentration is shown in Figure 5. It was found
Figure 3 Effect of initiator [CAN] concentration on that when monomer concentration increased from
the rate of grafting. Other conditions as in Figure 2. 0.178 to 0.803 mol L⫺1, the rate of grafting in-
522 RAHMAN ET AL.

Figure 4 Effect of monomer [MA] concentration on Figure 6 Thermograms of poly(methyl acrylate)–

the percentage of grafting. Temperature, 50°C; [AGU], grafted sago starch and sago starch. Plot of residual
0.135 mol L⫺1; [H2SO4], 0.175 mol L⫺1; reaction period, weight loss percentage versus temperature.
60 min; [CAN], 8.77 ⫻ 10⫺3 mol L⫺1. —{—, grafting
(%); —E—, efficiency (%).
grafted AGU are presented in Figure 6. The
weight loss occurred between 290 and 380°C for
creased linearly and decreased beyond 0.803 mol AGU, whereas the weight loss occurred between
L⫺1. At higher monomer concentrations, the rate 325 to 500°C for poly(methyl acrylate)– grafted
of grafting decreased beyond 0.803 mol L⫺1, pre- AGU. The poly(methyl acrylate)– grafted AGU
sumably due to the formation of more homopoly- was thermally stable as compared to AG up to
mer in the growing grafted chain. 490°C, although there was a little moisture dehy-
dration in both the samples up to 100°C. The
Thermogravimetry Analysis sharp decomposition, about 64% weight loss, tem-
perature was found for AGU at 330°C. In case of
The thermal behavior of AGU and poly(methyl
poly(methyl acrylate)– grafted AGU, the same
acrylate)– grafted AGU was examined by the TG
weight loss, 64%, occurred at 460°C. After 490°C,
analyses under N2 atmosphere at heating rate
the poly(methyl acrylate)– grafted AGU loses
10°C min⫺1. The TG curves for the thermal deg-
radation of AGU and poly(methyl acrylate)–

Figure 7 DSC thermograms of poly(methyl acry-

Figure 5 Effect of monomer [MA] concentration on late)– grafted polymer and sago starch. Plot of heat flow
the rate of grafting. Other conditions as in Figure 4. (mcal s⫺1) versus temperature.
 MA GRAFT COPOLYMERIZATION 523

weight more rapidly than AGU; in fact, the de- mineral acid and the reaction temperature and
composition was high in this region from 490 to period. The grafted copolymers were character-
1000°C. The poly(methyl acrylate)– grafted AGU ized by using FTIR spectroscopy, TG, and DSC
decomposed completely; therefore, the residual analysis.
weight of poly(methyl acrylate)– grafted AGU was
lower than that of AGU.
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and poly(methyl acrylate)– grafted copolymer are Press: Boca Raton, FL, 1986; p 149.
presented in Figure 7. AGU showed an endother- 2. Mingzhu, L.; Cheng, R.; Wu, J.; Cheng, M. A. J
mic transition at 321°C, with a little moisture Polym Sci Part A Polym Chem 1993, 31, 3181.
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lymerization were all dependent on the concen- Polym Sci 1982, 10, 1.
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