European Journal of Scientific Research

ISSN 1450-216X Vol.64 No.4 (2011), pp. 587-597

EuroJournals Publishing, Inc. 2011
http://www.europeanjournalofscientificresearch.com

Optimization of Synthetic Conditions of a Novel Graft

Copolymer Based on Alginate
Mohammad Sadeghi
Corresponding Author, Department of Chemistry, Science Faculty
Islamic Azad University, Arak Branch, Arak, Iran, P.O. Box 38135-567
E-mail: m-sadeghi@iau-arak.ac.ir
Tel: +98-916-1613256; Fax: +98-861-3670017
Nahid Ghasemi
Department of Chemistry, Science Faculty
Islamic Azad University, Arak Branch, Arak, Iran, P.O. Box 38135-567
Tel: +98-916-1613256, Fax: +98-861-3670017
Fatemeh Soleimani
Department of Chemistry, Science Faculty
Islamic Azad University, Arak Branch, Arak, Iran, P.O. Box 38135-567
Tel: +98-916-1613256; Fax: +98-861-3670017
Abstract
This article describes the synthesis biocopolymer based on sodium alginate (NaAlg)
and polymethacrylonitrile (PMAN). In this process, Large numbers of cyanide functional
groups were introduced onto sodium alginate by grafting with polymethacrylonitrile. A
proposed mechanism for biocopolymer formation was suggested and Infrared spectroscopy
was carried out to confirm the chemical structure of the biocopolymer by comparing FTIR
spectra of NaAlg and the graft biocopolymer as well as solubility characteristics of the
products. The thermal properties of pure NaAlg and grafted with monomers were also
evaluated with a simultaneous thermal analysis system. The synthetic conditions were
systematically optimized through studying the influential factors including temperature,
concentration of the initiator, methacrylonitrile monomer and sodium alginate.

Keywords: Sodium alginate; methacrylonitrile; biocopolymer; graft copolymerization.

1. Introduction
Among polysaccharides, alginates have been considered as one of the most promising candidates for
the future primarily because of an attractive combination of availability, price and performance.
Alginate is a collective term for naturally derived polysaccharides, i.e. alginic acid, its salts, and its
derivatives. Alginates are composed of (1
4)-linked -D-mannuronic acid and -L-guluronic acid
in a non-regular, block-wise pattern along the linear chain, which varied in amount and sequential
distribution along the polymer chain depending principally upon the seaweed species (Fig. 1), Heinze
& Liebert (2001). These polysaccharides are widely used in various applications such as chelating and
thickening agents, emulsifiers, stabilizers, encapsulation, swelling and suspending agents, or used to
form gels, films, and membranes. Among unique properties of alginates, gelation in the presence of

Optimization of Synthetic Conditions of a Novel Graft Copolymer Based on Alginate

588

multivalent metal cations is important. However, ionic-crosslinked alginate gels show low
absorbencies due to high crosslink density. Therefore, chemically crosslinking of alginate salts
would be better than ionic crosslinking, due to facile control of crosslinking degree and higher
crosslink length.
Among the diverse approaches that are possible for modifying polysaccharides, grafting of
synthetic polymer is a convenient method to add new properties to a polysaccharide with minimum
loss of the initial properties of the substrate,(Athawale & Rathi (1997). Graft copolymerization of vinyl
monomers onto polysaccharides using free radical initiation has attracted the interest of many
scientists. Up to now, considerable works have been devoted to the grafting of vinyl monomers onto
the substrates, specially cellulose,Sandle et al., (1987). Of the monomers grafted, methacrylonitrile
(MAN) has been the most frequently used one, mainly due to its highest grafting efficiency,Athawale
& Rathi (1997); Athawale & Rathi (1999 ), improving the thermal resistance of the graft copolymer
(Hebeish & Guthrie,1981) and also the subsequent alkaline hydrolysis of the grafting product to obtain
water absorbents,Athawale & Rathi (1997); Okieimen & Ogbeifun(1996) .
The literature survey, however, reveals that few of the modifications deal with chemical
grafting of a pre-modified polysaccharide such as sodium alginate. Ceric-initiated grafting of vinyl
monomers such as methyl acrylate, ethyl acrylate and ethyl methacrylate,Okieimen, (1998); Okieimen
& Ogbeifun(1996). acrylamide (AAm) ,Okieimen( 2003); Leza et al.(1989), and 4-vinylpyridine
(Fanta & Doane(1986); Leza et al,(1990) onto sodium alginate has been reported. However, to the best
of our knowledge, no report has been published on the optimization of MAN graft polymerization onto
sodium alginate using ceric-saccharide initiating system. As a part of our research program on
polysaccharide modification, herewith we report the optimized CAN-induced synthesis of sodium
alginate -g-polymethacrylonitrile under an inert atmosphere.

2. Materials and Methods

2.1. Materials
Sodium alginate (chemical grade, MW 50000 and follow chemical stracture) was purchased from
Merck Chemical Co. (Germany). methacrylonitrile (MAN, Merck) was purchased and distilled before
use. Ceric ammonium nitrate (CAN, Fluka) was used without purification. All other chemicals were of
analytical grade.
Figure 1: Repeating disaccharide units of sodium alginate(NaAlg).
+ NaOOC

O
HO

HO

HO
O
+NaOOC

HO

2.2. Graft Polymerization

At the first, the initiator solution was prepared by dissolving 2.74 g ceric ammonium nitrate in 50.0 mL
of 1.0 N HNO3. Generally, 3.50 mL of this stock solution (0.10 M) was used for each experiment
except for the experiments by which the effect of the initiator concentration was studied. Then, sodium
alginate solution was prepared in a 100-mL two-neck flask equipped with magnetic stirrer, gas inlet,
and reflux condenser. Total volume of the aqueous solution was 50 mL in all experiments. To control
the reaction temperature, the reactor was immersed in a thermostated water bath. After complete
dissolution of Alg to form a homogeneous solution, the various amount of methacrylonitrile (1.50-4.50
mL) was dispersed in the reaction mixture and stirred for 10 min. The mixture was continuously stirred
at the desired temperature until completion of the reaction (2 h). After adding hydroquinon solution
(0.5 wt%, 2 mL), cooling to room temperature, and adding few droplets of a molar sodium hydroxide

589

Mohammad Sadeghi, Nahid Ghasemi and Fatemeh Soleimani

solution to neutralize the remaining acid, the product was then precipitated in excess amount of
methanol while mild stirring for ten minutes. The product was filtered, thoroughly washed with
methanol and dried at 50 oC for one hour. To separate the polymethacrylonitrile (PMAN)
homopolymer, 0.50 g of the crude product was poured in 50 mL of dimethylformamide (DMF) and
stirred gently at 30 oC for 24 h. After centrifugating and decanting the supernatant (PMAN in DMF),
the NaAlg-g-PMAN was precipitated in methanol, thoroughly washed with methanol, and dried at 50
o
C to reach a constant weight.

3. Results and Discussion

3.1. Synthesis and Mechanism Aspects
Graft copolymerization of the sodium alginate and polymethacrylonitrile was carried out in aqueous
solution. A general reaction mechanism for NaAlg-Poly(PMAN) biocopolymer formation is shown in
Scheme 1. At the first step, the hydroxyl ions abstracts hydrogen from the OH group of NaAlg
substrate to form corresponding alkoxide anions. Then,these macroalkoxides initiate crosslinking
reaction between some adjacent polymethacrylonitrile pendant chains. This reaction leads to
intermediate formation of naphthyridine cyclic structures (including imine, -C=N-, conjugated bonds)
with dark red color.
Scheme 1: Proposed mechanistic pathway for synthesis of NaAlg-g-PolyMAN copolymer.
OH
NaOO C
O
HO

HO
O
O

NaOO C

OH

S o d io u m A lg in a te (N a A lg )
A lg
OH

C AN

A lg

A lg

I nitia t o r

OH

A lg
O

A lg
O

n m ol

N
P M AN backbo ne

g r a ft c o p o l y m e riz a ti o n
C

CN

CN

N
CN

CN

C
P M A N backbo ne

P M A N backbo ne

CN

CN
N

Alg
b ack b o ne
O

CN

CN

N
C
P M A N backbone

Optimization of Synthetic Conditions of a Novel Graft Copolymer Based on Alginate

590

The PMAN grafting was also confirmed by the differences between FTIR spectra of the
substrate and that of the graft copolymer.Figure 2 shows the FTIR spectra of pure Alg and the resulted
biocopolymer, NaAlg-polyMAN.The existence of a sharp intense peak at 2244 cm-1 in IR spectra of
the graft copolymers is a certain evidence of grafting. This absorption band arises from stretching
vibration mode of the nitrile (CN) groups. Most of the other peaks are related to the carbohydrate
backbone. Since PMAN could be extracted nearly completely from a physical mixture of PMAN and
polysaccharide by DMF, the presence of appreciable amounts of nitrile groups in our reaction products
after extraction is an additional proof for grafting of polymethacrylonitrile onto the polysaccharide.
Figure 2: FTIR spectra of pure NaAlg (a), NaAlg-g-PolyMAN (b).

3.2. Thermogravimetric Behavior

The grafting was also supported by thermogravimetric analysis (Fig. 3). TGA of pure NaAlg (Fig. 3a)
shows a weight loss in two distinct stages. The first stage ranges between 15 and 120 oC and shows
about 17% loss in weight. This may correspond to the loss of adsorbed and bound water,Zhang &
Tan(2000) . No such inflexion was observed in the TGA curve of NaAlg-g-Poly(MAN). This indicated
that the grafted copolymers were resistant to moisture absorption. The second stage of weight loss
starts at 330 oC and continues up to 440 oC during which there was 60% weight loss due to the
degradation of NaAlg. Grafted samples, however, show almost different behavior of weight loss
between 15 and 550 oC (Fig. 3b). The first stage of weight loss starts at 205 oC and continues up to 330
o
C due to the degradation of NaAlg. The second stage from 370 to 480 oC may contribute to the
decomposition of different structure of the graft copolymer. The appearance of these stages indicates
the structure of NaAlg chains has been changed, which might be due to the grafting of
polymethacrylonitrile chains. In general, the copolymer had lower weight loss than NaAlg. This means
that the grafting of NaAlg increases the thermal stability of NaAlg in some extent.
Figure 3: TGA curves of (a) pure NaAlg and (b) NaAlg-g-Poly(MAN).

591

Mohammad Sadeghi, Nahid Ghasemi and Fatemeh Soleimani

3.3. Optimization of the Reaction Conditions

In the present investigation, the effect of concentration of NaAlg, CAN and MAN, along with
temperature of reaction was studied, to optimize the reaction conditions. The conversion as well as the
grafting parameters, i.e. homopolymer content (Hp), grafting ratio (Gr) and the grafting add-on values
was calculated using the following equations,Fanta & Doane(1986):
Gr % = 100 (W2 W0) / W0
(1)
Ad %= 100 (W2 W0) / W2
(2)
Hp % = 100 (W1 W2) / W1
(3)
where W0, W1, and W2 are the weight of the initial substrate, total product (copolymer and
homopolymer), and pure graft copolymer (after DMF extraction), respectively.
Reaction Rate
The rates of polymerization (Rp) and graft copolymerization (Rg) may be evaluated as measures of the
rate of monomer disappearance by using the following equations,Zhang et al., (2000) :

Rp mol. s 1 .m 3 =

Rg mol. s 1 .m 3 =

Weight of total polymer formed

Molecular weight of monomer [ rection time ( s )] volume ( m 3 )

(4)

Weight of grafted polymer

Molecular weight of monomer [ rection time ( s )] volume ( m 3 )

(5)
The calculation of Rp values may be of significant importance in confirming a proposed
reaction mechanism and kinetics. Therefore, we investigated the relation between rate of graft
copolymerization and concentration of CAN, MAN and NaAlg. Figures 4-6 show that the plots of Rp
versus the monomer concentration, [MAN], half-order of the initiator concentration, [Ce+4]1/2 and the
polysaccharide concentration, [NaAlg]1/2, are linear. This is in agreement with a modified kinetic
scheme already explored for CAN-initiated Methacrylonitrile grafting onto sodium alginate . The
statement of rate of polymerization according to the scheme is as follows:
(6)
Rp = kp (K kd / kt )1/2 [NaAlg]1/2 [ Ce+4 ]1/2 [MAN]
The coefficient K is the equilibrium constant, kp, kd, and kt are the rate constants for
propagation, NaAlgceric complex dissociation, and termination reactions, respectively. Therefore, we
preliminarily conclude that the CAN-initiated grafting of MAN onto NaAlg is also fitted with this kind
of rate statement.
Figure 4: Plot of Rp versus monomer concentration.

Optimization of Synthetic Conditions of a Novel Graft Copolymer Based on Alginate

592

Figure 5: Plot of Rp versus initiator concentration.

Figure 6: Plot of Rp versus polysaccharide concentration.

The overall activation energy (Ea) of the graft polymerization reaction was calculated by using
of the Equation (5) and the slope of the plot LnRg versus1/T (Figure 7) based on Arrhenius
relationship [kp=Aexp(-Ea/RT)]. Therefore, Ea for the graft copolymerization was found to be 17.35
kJ/mole.
Figure 7: Plot of LnRg versus 1/T for estimating the activation energy of the graft polymerization reaction.

593

Mohammad Sadeghi, Nahid Ghasemi and Fatemeh Soleimani

3.3.1. Effect of NaAlg Concentration

The effect of NaAlg concentration on graft copolymerization was depicted in Figure 8. With increasing
the NaAlg amount, more reactive grafting sites are formed which is favorable for grafting. This can
account for initial increment in grafting parameters up to 0.66 %W/V of NaAlg value. Beyond this
amount, the grafting values were diminished. This may be ascribed to the increase in viscosity of
reaction mixture and the termination reaction between macroradical-macroradical and macroradicalprimary radicals as well. This observation is in close agreement with the results obtained by other
investigators,Kuwabara & Kuboka(1996); Ibrahim et al.(2002).
Figure 8: Effect of NaAlg concentration on the grafting parameters.

Reaction conditions: CAN 0.0005 M, MAN 1.30 mol/L, temperature 40C, time 120 min.

3.3.2. Effect of Initiator Concentration

The grafting dependence on CAN concentration can be concluded from Figure 9. The highest grafting
ratio (321%) was achieved at 0.0004 mol/L of CAN where homopolymer content was 11%. Increased
CAN concentration resulted in more radical sites on the polysaccharide backbone that in turn led to
higher Gr and add-on values and lower homopolymer formation. However, since the CAN initiator
solution is used as dilute HNO3, at CAN concentration higher than 0.0004 mol/L, a more acidic pH
probably causes partially termination of the macroradicals on NaAlg. As a result, increased free
radicals on NaAlg are compensated by partial termination of the macroradicals. Thus Gr and add-on
values were diminished at higher amounts of the initiator,Kuwabara & Kuboka(1996); Ibrahim et
al.(2002).
The percent of graft decreased with the increase of the initiator concentration beyond the
optimum condition. This behavior can be attributed to:
a) A relatively high concentration of the initiator may cause a reduction of the grafting of
MAN due to an increase in the number of NaAlg radicals terminated prior to MAN
addition.
b) At high concentration of CAN, was an increase in the homopolymer (PMAN), which
competed with the grafting reaction for available monomer.
These observations are in agreement with similar observations reported by others,Flefel &
Ibrahim (2002).

Optimization of Synthetic Conditions of a Novel Graft Copolymer Based on Alginate

594

Figure 9: Grafting parameters as functions of initiator concentration.

Reaction conditions: NaAlg solution 0.66 %W/V, MAN 1.30 mol/L, temperature 40C, time 120 min.

3.3.3. Effect of Monomer Concentration

The Acrylamide concentration was varied from 0.40 to 1.60 mol/L to study its effects on grafting
parameters (Figure 10). These parameters were found to be increased by enhancement of AAm
concentration from 0.4 up to 0.9 mol/L. This behavior can be attributed to the increase of monomer
concentration in the vicinity of the NaAlg backbone and consequent greater availability and
enhancement chances for molecular collisions of the reactants. The decrease in %Gr and %Ad after a
certain level of MAN (0.9 mol/L) is probably due to preferential homopolymerization over graft
copolymerization as well as increasing the viscosity of reaction medium, which hinders the movement
of free radicals,Berlin & Kislenco(1992); Pourjavadi& Zohuriaan-Mehr(2002).
Figure 10: Effect of the methacrylonitrile concentration on the grafting parameters.

Reaction conditions: NaAlg solution 0.66 %W/V, CAN 0.0004 mol/L,temperature 40C, time 120 min.

595

Mohammad Sadeghi, Nahid Ghasemi and Fatemeh Soleimani

Needless to say, the increase in the chain transfer to monomer molecules may be other possible
reason for the diminished grafting at higher AAm concentrations. Similar observations have been
reported for the grafting of ethyl acrylate onto cellulose and methyl acrylate onto starch,Pourjavadi &
Zohuriaan-Mehr( 2002).
3.3.4. Effect of Reaction Temperature
The grafting reactions were carried out at different temperatures between 30 and 75C, keeping the
other variables constant. As shown in Figure 11, it is found that %Gr and %Ad increase initially and
then decrease to some extent with further increase in temperature. This is attributed to the fact that
increasing the temperature favours the activation of macroradicals as well as accelerates the diffusion
and mobility of the monomers from the aqueous phase to the backbone,Doyle(1961). However, a
further increase in temperature decreases %Gr and Ad parameters, which can be ascribed both to the
acceleration of termination reaction and to the increased chance of chain transfer reaction, accounting
for the increase in the amount of homopolymer. This observation indicates that the optimal reaction
temperature is 60C. Similar behavior was observed in the case of grafting of acrylic acid onto methyl
cellulose and acrylamide onto xanthan gum,Zohuriaan et al.(2005).
Figure 11: Effect of the water bath temperature on the grafting parameters.

Reaction conditions: NaAlg solution 0.66 %W/V, CAN 0.0004 mol/L, MAN 0.95 mol/L , time 120 min.

4. Conclusion
Graft copolymerization was employed as an important technique to obtain a chemically modified
natural polysaccharide, sodium alginate (NaAlg). The grafting of methacrylonitrile onto NaAlg was
carried out using CAN as an efficient initiator. The characteristic absorbing peaks in the FTIR spectra ,
TGA analysis and gravimetric analysis have proven That sodium alginate participates in graft
copolymerization with methacrylonitrile. The main factors affecting the grafting parameters, including
concentration of the initiator, monomer and sodium alginate and reaction temperature was studied .
The optimum reaction conditions were found to be CAN 0.0004 mol/L, MAN 0.9 mol/L, NaAlg 0.66

Optimization of Synthetic Conditions of a Novel Graft Copolymer Based on Alginate

596

%W/V, and reaction temperature 60C. Under the optimized conditions the grafting parameters were
calculated to be Gr 376 %, , Ad 115 %, and Hp 8.0 %.

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