Indian Journal of Chemical Technology

Vol. 18, May 2011, pp. 234-243

Homogeneous grafting of PMMA onto cellulose in presence of Ce4+ as initiator

B Tosh* & C R Routray
Department of Chemistry, Orissa Engineering College, Bhubaneswar 751 007, India
Received 14 June 2010; accepted 22 March 2011
Poly (methyl methacrylate) (PMMA) is successfully grafted onto cellulose in homogeneous medium in N,N-dimethyl
acetamide/LiCl solvent system. The method is based upon ring opening reaction of cellulose with Ce4+ ion. Ceric ammonium
nitrate (CAN) forms free radical on cellulose back bone in presence of DMSO via ring opening mechanism and PMMA is
grafted through homogeneous breaking of the acrylic double bond. Methylene blue was used as an inhibitor to check the
formation of homopolymer. The graft yield and grafting efficiency was studied by varying reaction time, temperature, and
monomer concentration. The products are characterized by FTIR and 1H-NMR analysis and a possible reaction mechanism is
deduced. Thermal degradation of the grafted products is also studied by thermo-gravimetric analysis (TG).
Keywords: Methyl methacrylate (MMA), Homogeneous medium, N,NDimethyl Acetamide/LiCl, Ceric ammonium nitrate
(CAN), DMSO, Grafting, Ring opening, FTIR, Grafting efficiency, Methylene blue, Inhibitor

Cellulose is the most abundant naturally occurring

polymer and its derivatives have many important
applications in fiber, paper and paint industries. The
polymeric material with desired properties is a current
need of the society. To control the properties such as
hydrophobicity, adhesivity, selectivity, drug delivery,
wettability
and
thermosencitivity,
graft
copolymerization of suitable monomer is the versatile
technique for cellulose modification1. Although
cellulose has good properties it has some undesirable
ones such as low tensile strength, high moisture
regain, and low strength against microbial attack and
hence grafting of synthetic polymers on cellulose
eliminates these drawbacks and allows the acquisition
of additional properties of grafted polymers without
destroying its own properties2. Heterogeneous
grafting of synthetic polymers onto cellulose back
bone has been carried out by many researchers1-10.
The discovery of new solvents for cellulose
dissolution opened the possibility of performing
derivatization
and/or
grafting
reactions
in
homogeneous conditions, thus assuring important
advantages, such as a better control of the degree of
substitution11, a more uniform distribution of
substituents along the polymer and a higher
conversion yield12,13 .
During past few years a number of cellulose
derivatives has already been synthesized under

Corresponding author (E-mail: bntosh@yahoo.com)

homogeneous conditions11,14-16 and work on

homogeneous grafting of vinyl monomers onto
cellulose and some cellulose derivatives in nondegradable solvent systems such as DMSO/
PF14,15,17,18, DMSO/PhMe19,20 and DMAc/ LiCl12,13,21,22
have been tried using different initiators
like
ammonium
persulfate
(APS),
azobisisobutyronitrile(AIBN), and benzoyl peroxide,
but so far work on homogeneous graft
copolymerization of cellulose dissolved in N,Ndimethyl acetamide/lithium chloride (DMAc/LiCl)
solvent system using ceric ammonium nitrate(CAN)
has not been investigated.
CAN in presence of nitric acid is an efficient
initiator for graft copolymerization of vinyl
monomers onto cellulose1-3 in heterogeneous medium
but in homogeneous conditions this will produce gel
confirming the regeneration of cellulose from
DMAc/LiCl solvent system. It is only reported that
CAN in presence of dimethyl sulfoxide (DMSO) can
produce Ce4+ ion12 and can be a suitable redox system
to initiate graft copolymerization process, but hardly
any work is reported on this system. It is also reported
that presence of methylene blue in the reaction system
reduces the formation of homopolymers in the graft
copolymerization process23.
Therefore, in the present study we describe the
homogeneous
graft
copolymerization
of
methylmethacrylate (MMA) onto cellulose in
DMAc/LiCl solvent system taking CAN in presence

TOSH & ROUTRAY: HOMOGENEOUS GRAFTING OF PMMA ONTO CELLULOSE

of DMSO as initiator. The effect of varying in

reaction time, temperature, concentration of initiators
and monomer were studied to optimize the conditions
under which grafting would occur most effectively.
The effect of methylene blue on homopolymers
formation is also studied. The grafted products
obtained were characterized by Fourier transformation
infrared (FTIR) and proton nuclear magnetic
resonance (1H-NMR) spectroscopy and their
molecular weight and number of grafts per cellulose
backbone were determined. Finally, thermal
degradation of the grafted products was studied by
thermo-gravimetric (TG) analysis.
Experimental Procedure
Materials

Cellulose powder from cotton linters, having

viscosity 50-150 cP (Brookfield RTV, Spindle # 1,
20 rpm (lit)) was obtained from Sigma Aldrich
Chemicals Pvt. Ltd. It was purified by washing with
methanol, acetone, and de-ionized water and finally
dried in an oven at 50C for 7 days. The viscosity
average molecular weight of cellulose was calculated
by nitrating the sample and using Mark-HouwinkSakurada equation24 and was found to be 33,500.
Methyl methacrylate purchased from Sigma Aldrich
was purified from the inhibitor (hydroquinone
monomethyl ether) by extracting with aqueous
sodium chloridesodium hydroxide solution and dried
over sodium sulfate. The stabilizer free monomer
was vacuum distilled and stored below 5C. DMAc
(sd-fine chemicals) was distilled under CaH2 and stored
on molecular sieve (4 ) under nitrogen atmosphere.
Ceric ammonium nitrate and DMSO (E-Merck) were
of reagent grade and used without further purification.
Methylene blue was procured from E-Merck and is a
0.05% (w/v) aqueous solution. N2 gas was passed
through alkaline pyrogallol, sulfuric acid and
potassium hydroxide solution before it was passed
into the reaction mixture.
Preparation of cellulose solution

A 2% solution of cellulose was prepared by taking

8 g of cellulose in 400 mL of DMAc, heated at 150C
for 26 min in a round bottom flask equipped with a
short path condenser. Then 40 g LiCl was added and
heated up to 165C for 8 min. It was stirred overnight
to get a clear solution11,13. The solution was made 1%
during grafting.

235

Grafting

25 mL of 1% cellulose solution (1.45 mmol of

the corresponding anhydroglucose unit) was taken in
a three necked round bottom flask, equipped with
a magnetic stirrer and temperature controlled oil
bath. To this different amount of CAN ranging from
0.5 to 0.7 g (0.91-1.28 mmol) dissolved in 10 mL
DMSO was added followed by addition of 1.252.0 mL (11.7-18.7 mmol) of MMA. All the reactions
were carried out in a dry nitrogen atmosphere. The
reaction was carried out at different temperatures
between 60 and 80C for 2-6 h. The reaction was
terminated by addition of hydroquinone14. The
polymerization mixture was poured into cold distilled
water with vigorous stirring and kept overnight at 5C
and then filtered, washed thoroughly in cold distilled
water and dried at 50C and weighed. Then the
products were soxhlet extracted with acetone for 24 h
to remove any adherent homopolymer. The extracted
cellulose-grafted products were then dried at 50C
and stored over P2O5.
A comparative study was also carried out to study
the effect of methylene blue in the formation of
homopolymer by adding 0.7 mL (1.09 ppm) of
methylene blue to the reaction at 80C having
monomer concentration 18.7 mmol and initiator
concentration 1.28 mmol.
The graft yield (GY), total conversion of monomer
to polymer (TC), grafting efficiency (GE) and number
of graft per cellulose chain were calculated on the
basis of oven-dried weight of the cellulose from the
increase in weight after grafting by using the
following relations25.
GY (%) =

CA
100
A

GE (%) =

CA
100
B A

TC (%) =

B A
100
D

Number of grafts per cellulose chain =

Molecular weight of cellulose
GY

Moleculr weight of grafted PMMA 100

Where A is the weight in grams of the original

cellulose taken for the reaction; B is the weight in
grams of the grafted cellulose before extraction; C is

236

INDIAN J. CHEM TECHNOL., MAY 2011

the weight in grams of the grafted product after

extraction and D is the weight in grams of monomer
charged.
Molecular weight

Cellulose grafted with PMMA was hydrolyzed

with 72% H2SO4 to isolate PMMA14. The intrinsic
viscosities [] (cm3g-1) of isolated graft polymers
were measured at 25C, taking acetone as a solvent to
estimate the viscosity average molecular weight by
using the following Mark-Houwink-Sakurada
equation14.
[]Acetone = 5.3 10-3 M0.73
FTIR analysis

IR spectra of the grafted and ungrafted cellulose

samples were recorded on a PerkinElmer
spectrometer
(Spectrum
RX1,
PerkinElmer,
Singapore) using KBr pellet technique, in the range
4000-400 cm-1, with a resolution of 2 cm-1, using
4 scans per sample.
NMR analysis

The 1H-NMR spectra of the grafted products were

collected on a Bruker WM 400 spectrometer
operating at 300 MHz for proton. All the chemical
shifts were reported in parts per million (ppm) using
tetramethylsilane (TMS) as the internal standard and
CDCl3 as the solvent for the samples.

Thermal analysis

Thermo gravimetric (TG) analysis of the grafted

products was carried out using a Simadzu thermal
analyzer 30, in the temperature ranges from 40-800C
at a heating rate 10C.min-1, in air atmosphere. Alphaalumina was used as reference material for the study.
7 - 9 mg of the samples were taken for analysis.
Results and Discussion
Effect of reaction time

The graft co-polymerization of MMA onto cellulose

is carried out at 60, 70, and 80C with reaction time
ranging from 2-6 h with 1 h interval. The data on
weight gain with respect to reaction time at different
temperatures are shown in Tables 1-4. Figures 1-3
represent the percentage weight gain versus reaction
time at temperatures 60, 70 and 80C, respectively with
MMA concentration 11.7 mmol and CAN
concentration 0.91 mmol. Figures 4 and 5 represent the
reactions at 80C with CAN concentration 0.91 mmol
and monomer concentrations 14.0 and 18.7 mmol.
Figures 7 and 8 show the percentage weight gain
versus reaction time at 80C with MMA concentration
18.7 mmol and CAN concentration 1.1 and 1.28 mmol.
It is observed that the %GY and %TC is increased with
increase in reaction time in all the cases.
Effect of temperature

Grafting reactions are carried out by varying the

temperature from 60 to 80C and the data of weight

Table 1Graft co-polymerization of MMA onto cellulose at different temperatures with MMA concentration 5% (11.7 mmol)
and CAN concentration 5% (0.91 mmol) in 10 mL DMSO
Reaction
temperature (C)

Sample code

Reaction
time (h)

%
GY

%
GE

%
TC

Mw of
PMMA

No of grafts/cellulose
chain

60

Cell-g-PMMA-01
Cell-g-PMMA-02
Cell-g-PMMA-03
Cell-g-PMMA-04
Cell-g-PMMA-05

2
3
4
5
6

8
12
16
20
28

28.6
30.0
23.5
26.3
29.2

5.6
8.0
12.8
15.2
19.2

2172
2760
3135
3564
4404

1.23
1.45
1.71
1.88
2.13

70

Cell-g-PMMA-06
Cell-g-PMMA-07
Cell-g-PMMA-08
Cell-g-PMMA-09
Cell-g-PMMA-10

2
3
4
5
6

12
16
20
28
36

60.0
57.1
62.5
77.8
47.4

4.2
6.0
6.8
7.7
16.2

3268
4014
4189
4258
4385

1.23
1.34
1.60
2.21
2.75

80

Cell-g-PMMA-11
Cell-g-PMMA-12
Cell-g-PMMA-13
Cell-g-PMMA-14
Cell-g-PMMA-15

2
3
4
5
6

20
24
28
32
40

57.1
55.6
50.0
57.2
58.8

6.0
7.7
10.2
12.0
14.5

2974
2956
3695
3829
4573

1.80
2.27
2.60
2.80
2.93

237

TOSH & ROUTRAY: HOMOGENEOUS GRAFTING OF PMMA ONTO CELLULOSE

Table 2Graft co-polymerization of MMA onto cellulose with different monomer concentration at 80C and CAN concentration
5% (0.91 mmol) in 10 mL DMSO
Monomer
concentration

Sample code

Reaction
time (h)

%
GY

%
GE

%
TC

Mw of
PMMA

No of grafts/cellulose
chain

6%
(14.0 mmol)

Cell-g-PMMA-16
Cell-g-PMMA-17
Cell-g-PMMA-18
Cell-g-PMMA-19
Cell-g-PMMA-20

2
3
4
5
6

20
24
28
36
44

62.5
50.0
70.0
60.0
61.1

5.7
5.7
7.1
10.7
12.8

6280
6664
9553
6546
6065

1.06
1.20
0.98
1.84
2.43

8%
(18.7 mmol)

Cell-g-PMMA-21
Cell-g-PMMA-22
Cell-g-PMMA-23
Cell-g-PMMA-24
Cell-g-PMMA-25

2
3
4
5
6

36
40
44
52
56

69.2
62.5
61.1
46.4
40.0

7.5
8.5
9.6
14.9
18.7

6305
8441
8340
6888
6496

1.45
1.58
1.76
2.53
2.89

Table 3Graft co-polymerization of MMA onto cellulose with different initiator concentration at 80C and MMA concentration
8% (18.7 mmol)
Initiator
concentration

Sample code

Reaction
time (h)

%
GY

%
GE

%
TC

Mw of
PMMA

No of grafts/cellulose
chain

6%
(1.1 mmol)

Cell-g-PMMA-26
Cell-g-PMMA-27
Cell-g-PMMA-28
Cell-g-PMMA-29
Cell-g-PMMA-30

2
3
4
5
6

40
44
48
52
60

58.8
50.0
48.0
39.4
40.5

9.1
11.8
13.4
17.6
19.8

6826
9246
7703
7653
5685

1.96
1.88
1.91
2.10
2.35

7%
(1.28 mmol)

Cell-g-PMMA-31
Cell-g-PMMA-32
Cell-g-PMMA-33
Cell-g-PMMA-34
Cell-g-PMMA-35

2
3
4
5
6

44
48
52
56
60

55.0
45.8
7.1
28.0
29.4

10.7
12.8
18.6
26.7
27.2

7566
9665
9128
7096
6406

1.94
1.66
1.90
2.83
2.93

Table 4Graft co-polymerization of MMA onto cellulose at 80C with CAN concentration 7% (1.28 mmol) and MMA concentration
8% (18.7 mmol) and methylene blue 0.7 mL (1.09 ppm).
Sample code

Reaction
time (h)

%
GY

%
GE

%
TC

Mw of
PMMA

No of grafts/cellulose
chain

Cell-g-PMMA-36
Cell-g-PMMA-37
Cell-g-PMMA-38
Cell-g-PMMA-39
Cell-g-PMMA-40

2
3
4
5
6

44
48
52
56
60

52.4
54.5
56.5
63.6
62.5

11.2
11.8
12.3
12.8
13.4

3495
3550
3403
3303
3137

4.2
4.5
5.1
5.7
6.1

gain are given in Table 1 and Figures 1-3. It is

observed that at a particular reaction time the %GY of
the MMA grafted product is also increased with
increase in reaction temperature.

and 8% (18.7 mmol) (Samples; Cell-g-PMMA-21 to

Cell-g-PMMA-25; Table 2). Figures 3-5 show the
%GY, %GE and %TC of the grafted products. %GY
and %TC increase with increase in reaction time and
monomer concentration.

Effect of monomer concentration

At a reaction temperature of 80C, keeping the

CAN concentration at 5% (0.91 mmol) the
concentration of MMA is changed from 5% (11.7
mmol) (Samples; Cell-g-PMMA-11 to Cell-gPMMA-15; Table 1) to 6% (14.0 mmol) (Samples;
Cell-g-PMMA-16 to Cell-g-PMMA-20; Table 2)

Effect of initiator concentration

Grafting reactions are carried out at 80C at MMA

concentration 8% (18.7 mmol) and CAN
concentration is changed from 5% (0.91 mmol)
(Samples; Cell-g-PMMA-21 to Cell-g-PMMA-25;
Table 2) to 6% (1.1 mmol) (Samples; Cell-g-PMMA-

238

INDIAN J. CHEM TECHNOL., MAY 2011

Fig. 1Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 60C: cellulose, 1% (1.45 mmol); MMA, 11.7
mmol; CAN, 0.91 mmol

Fig. 2Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 70C: cellulose, 1% (1.45 mmol); MMA, 11.7
mmol; CAN, 0.91 mmol

Fig. 4Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 14.0
mmol; CAN, 0.91 mmol

Fig. 5Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 18.7
mmol; CAN, 0.91 mmol

26 to Cell-g-PMMA-30; Table 3) and 7% (1.28 mmol)

(Samples; Cell-g-PMMA-31 to Cell-g-PMMA-35;
(Table 3). Figures 5-7 indicate the effect of CAN
concentration on the weight gain with respect to
reaction time. As evident from the tables and figures,
the %GY and %TC increase with increase in the
initiator concentration at a particular reaction time.
Effect of inhibitor

Fig. 3Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 11.7
mmol; CAN, 0.91 mmol

To study the effect of methylene blue as the

inhibitor for the formation of homopolymer, the
reaction is carried out by taking 25 mL of 1%
cellulose solution, CAN concentration 7% (1.28
mmol), MMA concentration 8% (18.7 mmol) at 80C,
with addition of 0.7 mL (1.09 ppm) methylene blue
and the data are shown in Table 4 and Fig. 8.A
comparative study of Table 3 and 4 shows that,
the %GY of the grafted product remains the same
but the %TC of the grafted product without methylene

TOSH & ROUTRAY: HOMOGENEOUS GRAFTING OF PMMA ONTO CELLULOSE

239

blue goes on increasing rapidly with reaction time

(Table 3), where as in the presence of the inhibitor the
%TC increases very slowly. There is not much more
variation in the %GE in the later case (Table 4).
Molecular weight of PMMA and number of grafts per
cellulose chain

Fig. 6Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 18.7
mmol; CAN, 1.1 mmol

Fig. 7Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 18.7
mmol; CAN, 1.28 mmol

Fig. 8Effect of reaction time on grafting of MMA onto cellulose in

presence of CAN at 80C: cellulose, 1% (1.45 mmol); MMA, 18.7
mmol; CAN, 1.28 mmol; Methylene blue, 0.7 mL (1.09 ppm)

The molecular weight of PMMA extracted from

the grafted samples prepared under different reaction
conditions were determined and reported in the
respective tables. As seen in Table 1, the grafting
reactions with monomer concentration 11.7 mmol and
CAN concentration 0.91 mmol, in the three
temperature conditions give the grafted product
having well control on the molecular weight of the
PMMA and number of grafts per cellulose chain. At
monomer concentration 14.0 and 18.7 mmol (Table 2)
the molecular weight of PMMA goes on increasing up
to a reaction time of 3-4 h and then decreases slowly.
But the number of grafts per cellulose chain goes
on increasing with increase in reaction time. The
same trend is also observed at a monomer
concentration of 18.7 mmol with MMA concentration
1.1 and 1.28 mmol (Table 3). For the reactions with
methylene blue as the data show (Table 4), there is
almost no change in the extracted polymer molecular
weight and the number of grafts per cellulose chain
increases slowly in comparison to other conditions.
This shows that, methylene blue acts as a good
inhibitor for the formation of homopolymer and
controls the molecular weight of the graft copolymer
and increases the grafting sites in the cellulose chain
as evident from Table 4.
Moreover, as seen from the Tables 1-3, the grafting
efficiency is maximum of 77.8% for sample Cell-gPMMA-09, but for this sample the GE is only 28%
and also the molecular weight of the homo polymer is
4258. The samples prepared in the presence of
methylene blue as inhibitor (Table 4) give better
result than the former. By observing the tables, the
conditions for getting the sample Cell-g-PMMA-39 is
considered as the optimum conditions, which is
grafting at 80C for 5 h with a monomer
concentration 18.7 mmol, initiator concentration 1.28
mmol and inhibitor concentration 1.09 ppm. For this
sample the % GE is 56,% GE is 63.6, molecular
weight of the homo polymer is 3303 and number of
grafts per cellulose chain is 5.7.
FTIR studies

FTIR spectra of the grafted cellulose in the absence

of methylene blue (Cell-g-PMMA-35) and presence

240

INDIAN J. CHEM TECHNOL., MAY 2011

of methylene blue (Cell-g-PMMA-39) are shown in

Fig. 9. Both the products show identical peaks at
3432 cm-1 (OH str of cellulose), 2948 cm-1 (CH2- of
PMMA), 1728cm-1 (>C=O str. of PMMA), 1632 cm-1
(C-C str of PMMA), 1484 cm-1 (OH bending
of cellulose), 1447 cm-1 (CH bending of cellulose),
1397 cm-1 (CH deformation of cellulose), 1261 cm-1
( C-O-C- str of PMMA), 1190 and 1147 cm-1 (C-C str
of cellulose and PMMA), 1014 cm-1 (CH2- wagging
of cellulose), 801 and 745 cm-1 (CH rocking
vibrations of cellulose and PMMA), thereby
indicating the formation of MMA-grafted cellulose.
NMR studies

1H-NMR spectra of the grafted cellulose with

PMMA (Cell-g-PMMA-35 and Cell-g-PMMA-39)

are shown in Fig. 10. Both the products show

identical peaks and the peak at 3.53 ppm is due to the
OCH3 group of the grafted polymer. The CH2
group shows peaks at 2.02, 1.83 and 1.75 ppm and the
peaks at 1.18, 0.95 and 0.78 ppm are for the CH3
group26. The peak at 4.0 ppm is due to the OH group
of the cellulose chain27.
Mechanism of polymerization

It is known that metallic cations form complexes

with carbon hydrates. After complexation with
cellulose, ceric ion is reduced to cerous ion, the bond
between C2 and C3 is broken and a free radical
appears on C2 or C328. Then this free radical initiates
the monomer grafting and the polymerization reaction
of MMA. The FTIR and 1H-NMR spectra of the

Fig. 9FTIR spectra of PMMA grafted cellulose (a) in presence of methylene blue and (B)

TOSH & ROUTRAY: HOMOGENEOUS GRAFTING OF PMMA ONTO CELLULOSE

grafted products also shows the peacks for the OH

group which proves that the grafting occurs by
breaking of a C-C bond and not at the OH group.
Hence the mechanism is the one which is shown in
Scheme 1.

241

Methylene blue acts as inhibitor and affects the

termination step and the rate of the reaction will be
affected29. This is also evident from Table 4 that all the
samples prepared in the presence of methylene blue
show uniformity in the homo polymer molecular weight.

Fig. 101H-NMR spectra of (a) PMMA grafted cellulose and (b) PMMA grafted cellulose prepared in presence of methylene blue

242

INDIAN J. CHEM TECHNOL., MAY 2011

Scheme 1Mechanism of grafting of PMMA onto cellulose by Ce4+ ion

Table 5Thermal stability of cellulose grafted products in air at heating rate 10 C.min-1.
Sample code
Cell-g-PMMA-35
Cell-g-PMMA-39
a

IDTa (C)
170
210

Wt loss (%)
200C

250C

300C

350C

400C

450C

500C

6.5
0.7

11.2
8.5

21.4
28.2

32.0
40.1

58.8
61.3

81.2
82.5

81.2
82.5

IDT is the initial decomposition temperature.

Thermogravimetric analysis

Figure 11 shows the TG curves of grafted samples

Cell-g-PMMA-35 and Cell-g-PMMA-39. The
percentage weight loss of these samples with
temperature are given in Table 5. The initial
decomposition for Cell-g-PMMA-35 started at 170C
where as that for Cell-g-PMMA-39 is 210C. This
may be due to the increase in the percentage of
grafting and molecular weight of the homopolymer
for the former case. The results reveal a decrease in
the thermal stability with an increase in the
percentage of grafting30 and molecular weight of the
grafted polymer. Up to a temperature 250C the
thermal degradation of Cell-g-PMMA-39 is less in
comparison to Cell-g-PMMA-35 (Table 5) and from

Fig. 11Thermogravimetric (TG) analysis of (a) PMMA grafted

cellulose and (b) PMMA grafted cellulose prepared in presence of
methylene blue

TOSH & ROUTRAY: HOMOGENEOUS GRAFTING OF PMMA ONTO CELLULOSE

300C and above both samples show nearly equal

degradation profile.
Conclusions
Homogeneous graft copolymerization of MMA
onto cellulose in DMAc/LiCl solvent system was
carried out by using CAN as an initiator in presence
of DMSO. The formation of grafted products is
confirmed by FTIR spectroscopy. The effect of
reaction time and temperature, monomer and initiator
concentration on the %GY, %GE and %TC is
evaluated. Graft copolymerization of cellulose in
presence of Ce4+ proceeds through ring opening of
cellulose and formation of free radical in the cellulose
chain, which initiates the polymerization by free
radical mechanism. It is concluded that in presence of
methylene blue as the inhibitor for homopolymer
formation, the grafted products shows uniform
molecular weight of the grafted chain. It is also
concluded that the increase in the percentage of
grafting and molecular weight of the homopolymer
decrease the thermal stability of the compound.
Acknowledgement
The authors are thankful to the Department of
Science and Technology, New Delhi, for financial
support to carry out the work and to the Principal and
President G.B., Orissa Engineering College,
Bhubaneswar, India, for their encouragement and
support.

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13
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