Available online at: http://journal.ippi.ac.

ir
 Kinetics of Graft Copolymerization of Acrylic Acid
Iranian Polymer Journal
onto Cannabis indica Fibre
20 (11), 2011, 913-929
 *
Amar S Singha and Ashvinder K Rana

Department of Chemistry, National Institute of Technology,

Hamirpur-177005, H.P., India

Received 3 June 2011; accepted 26 September 2011

AB STRACT
 N atural fibres have received vast attention because of their combustible, non-
toxic, low cost, hydrophilic and biodegradable properties. In this study, functionalization of
cannabis indica fibre has been carried out by its grafting with acrylic acid (AAc) using a
3+
Ce -HNO3 redox initiator in an aqueous medium. Different reaction parameters such as
reaction time, pH, reaction temperature, concentrations of initiator, monomer and nitric acid
were optimized to achieve the maximum percentage of grafting (21.08%). The low graft
yield obtained with acrylic acid was because of its high affinity towards water. A suitable
mechanism to explain initiation, propagation and termination of graft copolymerization has
also been proposed. The kinetics of the graft copolymerization of acrylic acid onto
cannabis indica fibre has also been studied. It has been found that the rate expression for
0.63 1.22
graft polymerization is (R g) = k[I] [AAc] . The overall activation energy for the graft
copolymerization of AAc onto cannabis indica fibre was found to be 15.25 kJ/mol within the
temperature range of 25-45C. Besides kinetic study the grafted samples were also
evaluated for their physicochemi-cal properties such as swelling behaviour in different polar
and non-polar solvents along with resistance towards acid and base. Graft copolymerized
samples have been found to show less resistance towards chemicals as compared to the
raw fibre. Furthermore, the grafted samples were characterized by different techniques
such as Fourier transform infrared (FTIR), scanning electron microscope (SEM),
thermogravi-metric analysis (TGA) and X-ray diffraction (XRD) studies. Thermal stability of
Key Words: the fibre has been found to decrease after graft copolymerization which is also supported
by
cannabis indica; activation energy (Ea) values calculated both for raw and grafted fibres.
acrylic acid;
 g addresse bility polymer Kinetics of their surface
r d. E-
INTR [3,4], s that Graft grafting with
Copolymerizati
a mail:
ODUC cation can AAc by
on of Acrylic
f assingha
TION exchan absorb Acid ... chemical
t @gmail. ge water reactions and
com Today, proper and -radiation
and thus these
c graft ty [5] retain a method has
materials can
o copolym and high been reported
be used in
p erization dyeabi volume by Kaur et al.
many fields
o of vinyl l-ity of [13]. They
such as
l monome with aqueous reported that
horticulture,
y rs onto the fluids the graft
gel actuators,
m cellulosi basic copolymerizat
drug-delivery
e c fibres dyes ion through -
system, water
r is a withou radiation
purifier and
i subject t method is a
coal
z of advers better method
dewatering of grafting in
a intense ely [6-8], etc. comparison to
t studies. affecti Extensive chemical
i A ng attention has method in
o remarka their been given by leading to
n ble intrinsi various higher
; change c workers thermal
in the proper towards
k stability.
physico ties. superabsorbe
i
Kinetic study
chemica The nt polymers of graft
n l produc prepared copolymerizat
e properti ts can under ion of AAc
t es of the be different and
i grafted used conditions methacrylate
c fibres as through graft onto starch
has been supera copolymerizat using a ceric
s
demonst bsorbe ion of vinyl ion initiator
t
rat-ed nts monomers has been
u
by and onto natural studied by
d
various ion- polymers [9- Taghizadeh et
y
workers exchan 11]. al. [14]. Sun
;
[1,2]. ge Grafting et al. prepared
thermal
Grafting compo of vinyl and
stability.
of sites, monomers characterized
acrylic etc. onto cellulose the graft
acid Supera and its copolymers
(AAc) bsorbe derivatives of
onto nts are using UV- carboxymethy
cellulosi radiation has l chitosan
cross-
c fibres been reported with
linked
by Geacintov methacrylic
enhance networ
et al. [12]. acid by FTIR
(*) To whom s their ks of
The change in 1
correspond water hydrop and H NMR
rayon fibres
ence to be absorba hilic spectroscopy
properties for
and elemental Lyocell fibre Singhadifferent
AS et al. Materials
analysis [15]. grafted with physical and Cannabis Acrylic acid
Chauhan et al. thermosensiti Afganistan chemical indica fibres (AAc) was
have used ve poly- and other proper-ties were collected purified by
ceric isopropylacryl surrounding such as from higher distillation
ammonium -amide using moisture reaches of under reduced
areas.
nitrate as a CAN was resistance, Himalayan pressure at
Cannabis
redox initiator studied for swelling region in 40C and the
indica fibre (a
for the graft their thermal behaviour, Himachal middle
high molecular
copolymerizat and swelling thermal Pradesh. The fraction of
weight
ion of MMA behaviour by stability, distillate was
polysaccharide fibres were
onto the Carrillo et al. surface used for
) contains first washed
cannabis [20]. Khan morphology, further
reactive OH thoroughly
indica fibres synthesized chemical studies after
groups which with 2%
[16]. They photo-induced resistance drying over
are convenient detergent
have also graft behaviour and
for graft solution and anhydrous
studied the copolymer of percent
polymerizatio then dried in calcium
effect of methacrylic
n of crystallinity. hot air oven at chloride.
grafting on acid onto
hydrophilic The present 70C for 24 h. Ceric
the thermal natural
vinyl study also The dried ammonium
stability of the biodegradable
monomers in investigates fibres were nitrate (CAN)
cannabis ligno-
order to the kinetics of designated as obtained from
indica fibres. cellulosic
achieve the graft untreated Merck
Different fibre and
superabsorben copolymerizati fibres. Then Chemicals
authors have reported 42%
t like on of the cannabis (Germany)
made kinetic increase in
properties. acrylic acid was used as
studies for the hydrophilic indica fibres
graft character Since not onto cannabis were subjected an initiator.
copolymerizat [21]. much work indica fibre. Weighing of
to Soxhlet
ion of AAc has been The main aim the samples
Cannabis extraction with
onto starch reported on of the kinetic was done on
indica fibres acetone for 72
using ceric the surface study was to Libror AEG-
collected from h at 50C
ammonium modification determine the 220
higher reaches followed by
nitrate (CAN) of cannabis relationship (Shimadzu,
of the washing with
as an initiator indica fibre between the Japan)
Himalayan double
[17-19]. through graft rates of electronic
region have distilled water
Pourjavadi et copolymerizati grafting with balance.
been found to and air drying
al. on method acrylic Humidity
contain to remove
synthesized a [22,23], acid/ceric chamber of
approximately waxes and
novel therefore it is ammonium Swastika
68% other water
biopolymer- con-sidered nitrate made was
cellulose. soluble
based worthwhile to concentration used to study
Cannabis impurities
superabsorben graft and to the moisture
indica is a prior to graft
t hydrogel copolymerize correlate some absorbance
short plant, copolymerizati
through AAc onto kinetic behaviour of
chemically usually less on.
cannabis parame-ters the graft
cross-linked than 6 ft in with grafting copolymers.
indica fibre
graft height but percentage.
using CAN as
copolymers of rarely over 8
a redox
k-carrageenan ft and found
initiator and
and acrylic in India, EXPERIME
study its
acid. Recently Pakistan, NTAL
914 Iranian Polymer Journal / Volume 20 Number 11 (2011)
Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...
Synthesis of Cannabis indica-g-poly(AAc)
Activation of the cannabis indica fibre was done by
its immersion in 100 mL of distilled water at room
temperature for 24 h prior to graft copolymerization
process. After the activation of the active sites on the
polymeric backbone the fibre samples were trans-
ferred into a reaction kettle containing 100 mL of
distilled water used as a solvent in the grafting
reaction. A definite amount of CAN and nitric acid
was added to the reaction flask followed by dropwise
addition of monomer with continuous stirring of the
reaction mixture. The reaction was carried out at
definite reaction time and temperature. Optimum
conditions of time, temperature, pH, CAN, nitric acid
and monomer concentration were worked out so as to
acquire maximum graft yield. Homopolymer formed
during the graft copolymerization was removed by
extraction with hot water. The grafted samples were
then dried in hot air oven at 60C to a constant
weight. The amount of graft added onto the fibre was
determined gravimetrically. The grafting percentage
(Pg), efficiency percentage (Pe) and rate of grafting
(Rg) were calculated as per the following methods [24].
Grafting Pg (%) = wg w
100
w
w w
Efficiency Pe (%) = g
100
wm
100 (mol / L.s)
Rate of grafting (Rg ) = Pgw1000
100VtM
where w is the weight of raw fibre, wg is the weight
of grafted fibre, wm is weight of monomer, V is the
volume of the reaction mixture, t is the reaction time
and M is the molecular weight of the monomer.
Chemical Resistance Behaviour
The chemical resistance of the grafted fibre was stud-
ied as a function of percentage weight loss of fibre
when treated with different chemicals. A known
amount (wi) of the raw and grafted fibres was sepa-
rately treated with a fixed volume of hydrochloric
acid and sodium hydroxide of different strengths for
a time interval of 24 h. The fibres were then washed
2-3 times with distilled water and finally dried in an
oven at 70C to a constant weight. The samples were
weighed again to obtain the final weight (wf). The
percentage of weight loss was determined using the
following formula [24]:
wi w f
Weight loss (%) = 100
wi
Swelling Behaviour
The swelling behaviour of the raw and surface modi-
fied samples of cannabis indica fibre was studied in
polar and non-polar solvents such as water, butanol,
dimethylformamide and carbon tetrachloride. Dry
samples of grafted fibre as well as raw fibres were
subjected to the evaluation of swelling behaviour by
immersing the known weights of the fibres in certain
amounts of different solvents for 24 h. The samples
were then removed and excess solvent was removed
by being pressed between the folds of the filter
paper. The samples were weighed again to obtain the
final weight. The degree of swelling was calculated
by using the following relationship [24]:
w f wi
Swelling (%) = 100
wi
where wi is the initial weight of the dried fibre and
wf is the final weight after the swelling.
Moisture Absorbance Study
The moisture absorbance study of the grafted and
raw fibres was performed at different humidity levels
ranging from 20% to 80% in humidity chamber.
Percentage of humidity level during moisture
absorbance studies was maintained by controlling the
temperature. Each sample was subjected to a particu-
lar humidity level for a fixed time interval of 2 h.
The percent moisture absorbance was studied as a
function of weight gain and was calculated using the
following formula [24]:
wf wi
Moisture absorbance (M abs , %) =
100 wi
where Wf is the final weight of the sample removed
from the humidity chamber and Wi is the weight of
the dried samples.
Iranian Polymer Journal / Volume 20 Number 11 (2011) 915
Kinetics of Graft Copolymerization of Acrylic Acid ...
Infrared Spectroscopy
Infrared (IR) spectra of the graft copolymerized and
the raw fibre were recorded with KBr pellets on a
Perkin Elmer RXI Spectrophotometer (USA).
Scanning Electron Microscopy
Scanning electron microscopic (SEM) studies of
raw/surface modified cannabis indica fibres were
carried out on a Leo 435 VP electron microscope
Thornwood, NY). All the samples were gold plated
to become conducting. Scanning was synchronized
with microscopic beam for the maintenance of small
size over large distance relative to the specimen. All
the images were taken at a resolution of 1000X.
Thermal Analysis
Thermogravimetric analysis (TGA) of the raw and
graft copolymerized cannabis indica fibres was
conducted on a TGA with an auto sampling (Mettler
Toledo, Switzerland) analyzer at a heating rate of
15C/min. The thermograms were recorded over a
temperature range of 0C to 900C in presence of
nitrogen atmosphere at a flow rate of 20 mL/min.
X-Ray Diffraction Studies
X-Ray diffraction studies were performed on a
Brucker X-ray diffractometer (D8 Advance,
Germany), using CuK (1.5418 A) radiation, a Ni-
Filter and a scintillation counter as a detector at 40
kV and 40 mA on rotation from 5 to 60 at 2 scale.
Each sample was finely powdered into a small
particle size and homogeneously mixed before
subjected to X-ray exposure. The finely powdered
sample was distributed in the cavity of the sample
holder with the help of glass slide. The randomly
oriented powdered sample with uniform surface was
exposed to X-rays from all possible planes. The
angle of scattering of diffracted beam was measured
with respect to incident beam of X-rays and the
relative intensity was obtained.
Crystallinity index (CI) was determined by using
the wide angle X-ray diffraction counts at 2 angle
close to 22 and 15. The counter reading of peak
intensity close to 22 and 15 is said to represent the
crystalline and amorphous materials in cellulose,
respectively. The crystallinity percentage and
Singha AS et al.
crystallinity index (CI) were calculated using the
following formula [25]:
100
Cr (%) = IC
IC + I A
I I
CI = C A
IC
where IC and IA are the crystalline and amorphous
intensities at 2 scale close to 22 and 15 angles.
RESULTS AND DISCUSSION
Reaction Mechanism
C2, C3 and C6 hydroxyls and C-H groups are the
active sites for the incorporation onto polymeric
chains through grafting with cellulosic fibres like
cannabis indica fibre. Grafting reaction proceeds
through redox mechanism in which Ce(IV) ions are
reduced to Ce(III) ions by the transfer of electron
from the cellulose molecules, and hence active sites
are generated on the polymeric backbone at which
monomer radicals can attack to form graft copoly-
mers. The breaking of C2-C3 bonds of glucose
molecules in cellulose chain results in the formation
of free radical sites on the polymeric backbone. The
grafting of acrylic acid onto cannabis indica (CI)
backbone is supposed to take place through the
mechanism [26,27] shown in Scheme I.
Ceric ions form complexes with the carbon chain
of polymer backbone as well as with monomer and
generate free radicals (eqns 1 and 2). Monomer free
radicals then result in the formation of graft copoly-
mer [CIC-g-poly(AAc)] by reacting at the active
sites of the polymeric backbone (eqns 3 and 4).
Monomer may also combine with CIC-g-poly(AAc)
macro-radical to form graft copolymer (eqn 5).
While, the ceric ions and poly(AAc) free radicals
combine with CIC-g-poly(AAc) free radicals and
CH-free radicals, respectively, leading into
termination reactions (eqns 6 and 7).
Effect of Time
The graft copolymerization has been recorded at
916 Iranian Polymer Journal / Volume 20 Number 11 (2011)
 Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...
OH OH OH

OH
k O
O 4+ HO O
HO O + Ce HO O
O HO O O
OH 4+ OH
Ce
OH OH
CI cellulose
4+
Complex(CI cellulose-Ce )
-H k
d
OH OH 3+
Ce

O +

HO O H O O
O
OH
Chain initiation OH
CI cellulose free radical (1)
O O

'
+ k
Ce4+ OH
OH
AAc free radical (2)
AAc
OH OH OH
OH
HO O O ki HO O O O
H
H O O
O
O OH + O O OH
O OH
OH
HO
CI cellulose free radical
OH (3)
Chain propagation
OH OH OH

OH
HO O HO O O
H O O kp O
O O H
O O OH O O
HOH2C
OH O OH
+
HO n HO
OH
(4)
O OH continued

Iranian Polymer Journal / Volume 20 Number 11 (2011) 917

Kinetics of Graft Copolymerization of Acrylic Acid ... Singha AS et al.
 OH OH OH
O OH
HO O O O
O H O HO O O
+ kp O H

HOH2C O O OH O
OH HOH2CO OH
AAc
HO HO

O OH O OH (5)

Chain termination
OH OH OH OH

O
HO O O HO O
k H O
O H O 4+ O
+ Ce t

HOH2CO O HOH2C O O 3+
+ Ce
OH
HO HO
O OH O OH

CIC-g-poly(AAc) free radical CIC-g-poly (AAc) (6)

OH OH

OH
OH HO O O
O ko O H O
HO O
O H O HOH2C O
O
O + O
OH
OH OH HO
CI cellulose free radical O O OH

OH CIC-g-poly (AAc)
O

HO (7)
Poly(AAc)
Scheme I. A possible mechanism for graft copolymerization of acrylic acid onto cannabis indica fibre.
different stages ranging from 60 to 180 min at fixed
concentration of ceric ammonium nitrate, AAc and
nitric acid at 45C (Figure 1). With increase in
reaction time, Pg increased rapidly and maximum
grafting was observed at 120 min and then decreased
again with further increase in the reaction time. This
probably happens due to generation of increasingly
monomer radicals with extended time which
interacts
918 Iranian Polymer Journal / Volume 20 Number 11 (2011)
Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...
Cell H COOHH Cell H COOH COOH

COOH
C C C C C C CH2 + CH

H H H H H

H COOHH COOH H COOHH COOH

C C C C C C C C H

H H H H
H H H H Cell
Cell

Scheme II. Chain cleavage leads to lower degree of grafting.

with the active sites on the polymeric backbone
resulting in increased Pg. Beyond the optimized point,
at higher reaction time, Pg decreases due to irreversible
termination by radical coupling reactions. This may
also be due to the mutual destruction of growing
polymeric chains [13] leading to homopoly-merization
of the reaction monomer radicals and backbiting by the
active radicals (Scheme II).
Effect of Temperature
The effect of temperature on graft copolymerization
is depicted in Figure 2. It can be seen that both P g
and Pe show an increasing trend up to 45C as the
temperature enhancement can increase the dynamic
energy of the monomer molecules, which in turn
1. Effect of time on the graft copolymerization. merization.
increases the diffusion of monomer molecules onto
the polymeric backbone resulting in increased P g
and Pe. On further increase in temperature, P g and
Pe decreased, which may be due to increased chain
termination reactions between monomer molecules
and grafted chains. Combination of free monomer
radicals at higher temperature may also result in
decreased grafting yield [28].
Effect of Initiator
The effect of initiator concentration on graft copoly-
merization of polymeric backbone has been depicted
in Figure 3. It can be established from the figure that
Pg increases with the increase in CAN concentration
Figure 2. Effect of temperature on the graft copoly-Figure
Iranian Polymer Journal / Volume 20 Number 11 (2011) 919
Kinetics of Graft Copolymerization of Acrylic Acid ... Singha AS et al.

Figure 3. Effect of CAN concentration on the graft Figure 4. Effect of nitric acid concentration on the graft
copolymerization. copolymerization.

-2 -1 However, Pg decreases with further increase in the nitric

up to 1.8210 mol.L at constant concentration of acid concentration beyond an optimum value
+ -
+
monomer and nitric acid, and after that P g shows a H 2O
HNO H (aq) NO3 (aq)
downward trend. This behaviour can be easily under- 3
stood in terms of increase in CAN concentration OH

which results in more free radical active sites on the OH

polymeric backbone, which may lead to greater P g. HO O O

However, with further increase in CAN O

HO O
concentration, it accelerates the dissociation rate of OH
Ce(IV), which reduces the concentration of CAN
participating in graft copolymerization. OH H

Effect of Nitric Acid Concentration OH

4+
In aqueous medium CAN exists as Ce , OH
3+ 6+ HO O O
[Ce(OH)] and [Ce-O-Ce] ions (eqns 8 and 9).
O H O
Due to their large size, these ions are not able to form
complexes with polymer backbone. However, in the HO
OH
presence of HNO3, equilibrium shifts further towards
4+ OH
Ce ions, therefore graft copolymerization increases
with increase in nitric acid concentration. H2O Slow
OH OH
Ce 4+ + H 3+] + H + (8)
2O [Ce(OH )
3+ 6+ (9) OH + H
2[Ce(OH ) ] [Ce O Ce] + H2O HO + HO O
O HO O
OH

Figure 4 shows the effect of nitric acid concentration OH

on grafting parameters. It can be seen that P g increas- Scheme III. Hydrolysis of the cellulosic fibre due to
es significantly with the increase in nitric acid
increased HNO3 concentration.
concentration, and Pe also follows a similar trend.
920 Iranian Polymer Journal / Volume 20 Number 11 (2011)
Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...
 increases up to pH 7, but beyond pH 7 there is a
decrease in the graft yield as depicted in Figure 5.
This may be due to the fact that at higher pH the OH
radicals are generated in basic medium which
combine with the backbone free radicals to terminate
the chain reaction (Scheme IV) [13].

Effect of Monomer Concentration

The effect of monomer concentration on graft copoly-
merization onto polymeric backbone at constant
concentrations of CAN and nitric acid at temperature of
45C is depicted in Figure 6. It can be established from
the figure that Pg increases with increase in AAc
-1 -1
concentration up to 2.91 10 mol.L beyond which
Figure 5. Effect of pH on the graft copolymerization.
Pg shows a downward trend. The above behaviour of
-1 -1 the monomer concentration may be explained on the
(2.88 10 mol.L ) probably due to termination of basis of greater free radicals which reach polymeric
growing grafted chains, which has been accelerated
because of formation of considerable amount of backbone, resulting in increased P g. The decrease in Pg
4+ 3+ beyond optimum value of AAc was probably due to
[Ce ] and [CeOH] [28]. Also increased preferential homopolymerization over graft copoly-
concentra-tion of nitric acid may result in hydrolysis merization as well as due to restricted movement of free
of the fibre graft (Scheme III). radicals onto polymer backbone because of increased
viscosity. Needless to say, the increase in the chain
Effect of pH transfer to monomer molecules may be another possible
With increase in pH of the reaction medium, Pg reason for the diminished grafting at

OH OH

HO O O
O H O
+
O O OH OH
OH
HO H O
H
 H OH OH
OH

HO O O
O H O
O O + +
H2 O H
OH OH

HO O
H
H OH

Scheme IV. Termination of the growing grafted chains leads to lower Pg.
Iranian Polymer Journal / Volume 20 Number 11 (2011) 921
Kinetics of Graft Copolymerization of Acrylic Acid ... Singha AS et al.

Figure 6. Effect of monomer concentration on the graft
copolymerization.
higher AAc concentrations [13,28] (Scheme V).
Kinetics of Graft Copolymerization
The mechanism of graft copolymerization is quite
complex as it involves various stages like propaga-
tion, termination, homopolymerization and copoly-
merization reactions. However, kinetically, the rate of
the graft copolymerization (Rg) with respect to
monomer and initiator concentrations can be written
as follows [29]:
m n (10)
Rg = k[initiator] [monomer]
Here, m and n can be experimentally determined by
the logarithmic form of the equation given above:
m n
log Rg = log k + log[initiator] + log[monomer] (11)
The experimental results show a change in the rate of
grafting with the changes in concentration of the
CAN keeping the concentration of the acrylic acid
constant (Table 1).
The slope of the log Rg vs. log [CAN] graph
plotted by the data given in Table 1 showed that the
rate of grafting was proportional to 0.63 power of the
CAN concentration.
Likewise the initial rates of grafting were deter-
mined by changing the concentration of acrylic acid
from 1.75 to 2.91 mol/L and keeping the CAN
concentration constant (Table 2).
The slope of the log R g vs. log [AAc] graph
plotted using the data in Table 2 showed that the rate
of grafting was proportional to the 1.22 power of the
acrylic acid concentration.
 H H
O H O H

Cell H O Cell H O

O H O H
C CHR C CHR
H2 H

Scheme V. A three-component complex leads to increased homopolymerization.

Table 1. Kinetic data showing the change of initial rate of grafting with CAN concentration.

[CAN] 10
-2 P Log [CAN] + 3
Rg 10
-5
Log Rg + 5
g
-1 -1 -1
(mol.L ) (mol.L .s )
0.91 10.76 0.95 1.03 0.015
1.36 14.56 1.13 1.40 0.140
1.82 16.68 1.26 1.60 0.200
-1
[AAc]: 0.29 mol.L , T: 45C, t: 120 min, HNO3: 1.2 mL, pH: 7.0.
922 Iranian Polymer Journal / Volume 20 Number 11 (2011)
 Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...

where A, Ea and T indicate collision parameter in the

Arrhenius equation, activation energy and absolute
temperature, respectively. The final equation may be
written as:

Table 2. Dependence of rate of grafting (Rg) on acrylic acid concentration.

[AAc] P Log [CAN] + 1

Rg 10
-5
Log Rg + 5
g
-1 -1 -1
(mol.L ) (mol.L .s )
0.17 11.20 0.24 1.07 0.03
0.23 14.66 0.36 1.41 0.15
0.29 21.08 0.46 2.03 0.30
-2 -1
[CAN]: 1.82 10 mol.L , T: 45C, t: 120 min, HNO3: 1.2 mL, pH: 7.0.
Therefore:
0.63 1.22
Rg = k[I ] [ AAc]

Kinetics of graft copolymerization of ethyl acrylate

onto cellulose by using ceric ammonium nitrate as an
initiator have also been studied by Gupta et al. [30].
They found that the grafting rate is proportional to 1.5
power of ceric ion and activation energy was found to
be 28.9 kJ/mol. Graczyk et al. have report-ed grafting
rate is proportional to the powers 0.5 and 1 of their
respective ceric ion and monomer concen-trations at
low concentration of CAN [31].
Since grafting reaction was carried out at
different temperatures and other conditions
-1
remaining con-stant therefore we may equalize the Figure 7. Arrhenius plot of log Rg vs. 1/T (K ) for grafting
reaction rate with grafting rate. Substitution of the of AAc onto cannabis indica fibre.

Arrhenius relation by general rate equation yields

studies reported [32,33].
the following equation:
 m n Ea/ RT
Rg = A[CAN ] [ AAc] e Swelling Behaviour
The swelling percentage of raw and grafted cannabis
Log Rg = Logk' Ea / RT indica fibres in different solvents such as water,
methanol, dimethylforamide (DMF) and carbon
tetrachloride was studied as a function of the percent-
age of grafting at 35C and the results are shown in
Figure 8. The following swelling order in different
(12) solvents has been observed both with grafted as well
as raw fibres.
 -
This implies that when the plot of log R g vs. 1/T (K
1 H 2O > C2 H 5OH > DMF > CCl4
) is a straight line, the activation energies of the
reaction can be evaluated. The result is depicted in
A high swelling percentage in water is expected
Figure 7 which shows that plot of log Rg vs. 1/T is a because water enters into hydrogen bonding with
straight line. Thus, the overall activation energy for hydroxyl group of the cannabis indica fibre.
the graft copolymerization of AAc onto cannabis
indica fibre is found to be 15.25 kJ/mol. The results Amorphous region of the fibre is generally
obtained in our laboratory are consistent with other responsible for H-bonding where hydroxyl groups
Iranian Polymer Journal / Volume 20 Number 11 (2011) 923
Kinetics of Graft Copolymerization of Acrylic Acid ... Singha AS et al.
 H2C CH
C

O OH
HO O
C
H2C CH

Figure 9. Formation of inter and intramolecular hydrogen

bonding between carboxyl groups.

groups that are not affected by the presence of the

added solvent (Figure 9).
Figure 8. Effect of Pg on swelling behaviour for different
The lower swelling of acrylic acid graft copoly-
merized fibres in carbon tetrachloride was due to
solvents.
lower interaction of CCl 4 with carboxyl groups in
are exposed for such interactions. Further dielectric comparison to hydroxyl groups of the raw fibre.
constant values of different solvents also have great
effect on the swelling behaviour of the fibre. As Acid/Base Resistance
regards the dielectric constants, the order of the The chemical resistance has been studied in terms of
solvents studied is as follows: a weight loss of the fibre with dilute solutions of
strong acids and bases. The effects of acid (HCl) and
H 2O > C2 H 5OH > DMF > CCl4 the base (NaOH) were studied by keeping the raw
and cannabis indica-g-poly(AAc) fibres in basic and
acid solutions for a period of 24 h and the result
( = 78.35) ( = 24.30) ( = 36.71) ( = 2.24) obtained are shown in Figures 10 and 11. From these
figures it is clear that chemical resistance of grafted
Water, having a higher value easily enters into H- fibres decreases with increases in degree of grafting
bonding with the fibre leading to maximum swelling. both with acid and base. The maximum weight loss
DMF, as an aprotic solvent, is a polar molecule with was found at high Pg (21.08%). This probably could
high which interacts with the hydroxyls group of the
fibre leading to a substantial degree of swelling. In case
of carbon tetrachloride which has low dielec-tric
constant ( = 2.24) a lower degree of swelling has been
observed. It is also observed in Figure 8 that percent
swelling of the acrylic acid grafted cannabis indica
fibre in water is higher than the raw fibre. The
maximum degree of swelling is observed at 17.24%
graft level. The degree of swelling in butanol and DMF
for 17.24% graft level is also higher, while in carbon
tetrachloride it is less than that of raw cannabis indica
fibre.
It was further observed that the degree of swelling
decreases with increased Pg. This may be due to the
formation of inter and intramolecular hydrogen-bonded
structures between the pendant carboxyl Figure 10. Effect of Pg on resistance to acid.
924 Iranian Polymer Journal / Volume 20 Number 11 (2011)
Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...
Figure 11. Effect of Pg on resistance to base.
be due to the formation of acrylic acid sodium salts and
to some extent due to the solubility of polyacrylic acid
chain. However, at lower Pg the grafted samples
showed little resistance towards bases or acids.
Moisture Absorbance
Raw cannabis indica fibres have been found to show
1.91, 2.45, 3.21 and 3.75% moisture absorbance at
20%, 40%, 60% and 80% humidity levels in the
given order (Figure 12). From the figure, it is also
clear that cannabis indica-g-poly(AAc) fibre showed
higher moisture absorption which increases with
increases in Pg. This could be due to the fact that
with increase in the graft yield, more carboxyl
groups are available for formation of the hydrogen
bond with the water molecules.
FTIR Analysis
FTIR Spectrum of raw cannabis indica fibre showed a
-1
broad peak at 612.6 cm (due to out-of-plane -OH
-1
bending), 897.6 cm (due to -glycosidic linkage),
-1
1252.1 cm (due to -C-O-C- and -C=O stretchings in
xylan side substituent and lignin aromatic C=O
-1
stretching), smaller peaks at 1376.2-1429.3 cm (due
-1
to -CH, -CH2 and -CH3 bending), 1635.0 cm (due to
H-O-H bending of absorbed water and for lignin C-H
-1
deformation), 2143.2 cm (due to O-H stretch-ing of
-1
absorbed moisture), 2335.5 cm (due to C-H
-1
stretching in polysaccharide chains), 2922.3 cm (for
C-H stretching vibration of aliphatic methylene
Figure 12. Effect of Pg on moisture absorption behaviour.
group) and an intense broad peak ranging from 3024
-1
to 3691 cm (due to the hydrogen bonded -OH
vibration of the cellulose structure fibre). However,
in FTIR spectra of the cannabis indica-g-poly(AAc),
-1
characteristic absorption bands at 1729.9 cm and
-1
1570 cm were obtained due to carbonyl stretching
of pendant carboxylic acid group and unsaturated
group, respectively.
Morphological Studies
Surface morphology of both treated and untreated
cannabis indica fibres was studied through scanning
electron microscopy and the results are shown in
Figure 13. The comparison of SEM micrographs of
the raw and acrylic acid grafted cannabis indica
fibres showed that the morphology of the fibre
changes upon grafting, indicating that the chains of
polymeric AAc have been incorporated onto
cannabis indica fibre.
Thermal Stability
The TGA analysis of the raw and cannabis indica-g-
poly(AAc) fibres is shown in Figure 14 and the
corresponding thermal characteristics are given in
Table 3. Thermal behaviour of both raw and grafted
fibres was studied as a function of weight percentage
residue with increase in temperature. In the case of
raw cannabis indica fibre, at the beginning, depoly-
merization, dehydration and glucosan formation took
place between the temperature range of 25.0C and
Iranian Polymer Journal / Volume 20 Number 11 (2011) 925
Kinetics of Graft Copolymerization of Acrylic Acid ... Singha AS et al.

(a) (b)

Figure 13. Surface morphology of: (a) raw and (b) grafted cannabis indica fibres.
250.0C followed by the cleavage of C-H, C-C and C-
O bonds [25,34]. For the raw fibre, the initial
decomposition temperature (IDT) has been found to
be 256.33C (6.91% weight loss) and final decom-
position temperature (FDT) to be 383.25C (61.12%
weight loss). In the case of AAc grafted cannabis
indica fibre, the IDT has been found to be 236.9C
Figure 14. Thermogravimetric analysis of the raw and
cannabis indica-g-poly(AAc) fibres.
(7.88% weight loss) and FDT to be 388.68C
(54.85% weight loss). Decrease in IDT of grafted
fibre could be due to decomposition of anhydride
(formed due to dehydration of carboxylic acid
groups) of poly(AAc) chains to carbon dioxide and
intermediate species such as ketones, ketenes and
unsaturated compounds in the temperature range of
200-275C, accompanied by an overall decrease in
the acrylic acid content [35]. However if we take
decomposition temperature (DT) at 20% and 60%
weight losses for both raw and grafted fibres as a
standard of comparison then it has been observed
that at higher temperature cannabis indica-g-
poly(AAc) fibres are thermally more stable than the
raw fibres. Analysis of the activation energy also
supports the above trend (Figure 15). The activation
energy has been calculated within the temperature
range of 250-400C by using Broido equation as
given below:
ln [ln(1/ y) = E {(1/ T ) + K} (13)
R
Table 3. TGA and activation energy analyses of the raw cannabis fibre and cannabis indica-g-poly(AAc) fibres.
No. Sample IDT FDT DT (C) DT (C) Residual Activation
designation (C) (C) at 20% (by at 60% (by weight (%) at energy
weight) loss weight) loss 600C (kJ/mol)

1 Raw cannabis indica fibre 250.33 383.25 329.61 383.25 27.04 56.12
2 Cannabis indica-g-poly(AAc) 236.90 388.68 329.18 447.00 27.84 43.94
926 Iranian Polymer Journal / Volume 20 Number 11 (2011)
 Singha AS et al. Kinetics of Graft Copolymerization of Acrylic Acid ...

Table 4. Degree of crystallinity (%) and crystallinity index (CI) of raw and cannabis indica-g-poly(AAc) fibre.
No. Sample Sample Crystallinity Crystallinity

I I (%) index (CI)

22 15
1 Raw 709.00 348.00 67.07 0.509
2 Cannabis indica-g-poly(AAc) 603.65 314.89 65.71 0.478
Figure 15. Variation of ln[ln(1/y)] for raw and grafted
cannabis indica fibres.
where R is gas constant, T is temperature in Kelvin, K
is a constant, y is a normalized weight (w t/wo), wt
denotes the weight of the samples at any time t, while
wo denotes the initial weight of the samples. From
Figure 15, it is clear that the value of activation ener-gy
was higher for raw fibres, for which the thermal
stability has also been found higher than grafted fibre.
XRD Study
The polymorphism of cannabis indica fibre was stud-
ied before and after graft copolymerization, using X-
ray diffraction. For the raw fibre, two responses were
noticed at 2 = 15 and 22 which indicate that
cannabis indica fibre is a semi-crystalline material. The
same responses appeared in case of the cannabis
indica-g-poly(AAc) fibre but with different intensi-ties
(Figure 16). The relative degree of crystallinity of both
fibres was calculated and it is given in Table 4. As
shown in this table an increase in degree of grafting
was accompanied by a decrease in the rela-tive degree
of crystallinity. This could be explained on the basis
that grafting causes disturbance in the
Figure 16. XRD Patterns of the raw and cannabis indica-
g-poly(AAc) fibres.
crystalline region of the fibre by creating amorphous
region. Thus, as the degree of grafting increases, the
amorphous regions become predominant and over-
shadow the crystalline feature of the fibres.
CONCLUSION
Cannabis indica fibres have been successfully
modified through grafting in air by free radical
polymerization. The optimum conditions for the
maximum degree of grafting (21.08%) onto
cannabis indica fibres have been found to be: time:
-2
120 min, temperature: 45C, [CAN]: 1.82 10
-1 -1 -1
mol.L , [HNO3]: 2.88 10 mol.L and [AAc]:
-1 -1
2.91 10 mol.L . The rate of grafting has been
found to be more dependent upon monomer
concentration. The degree of swelling of grafted
samples in polar and dipolar aprotic solvents has
been found to be better
Iranian Polymer Journal / Volume 20 Number 11 (2011) 927
 Kinetics of Graft Copolymerization of Acrylic Acid ...
than that of the raw fibres. The grafted fibres have been
found to have high FDT compared to that of raw fibre
which ensures their high temperature applica-tions.
Due to high moisture absorbance behaviour of the
grafted fibres these can be used as water superab-
sorbent as well as for the removal of harmful ion like
Pb, As and etc. from the water sources.
ACKNOWLEDGEMENT
Authors are highly thankful to the Director, National
Institute of Technology, Hamirpur (H.P), India, for
providing the laboratory facilities and Ministry of
Human Resources and Development for financial
support.
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