ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. (2009)

Published online in Wiley InterScience
(www.interscience.wiley.com) DOI:10.1002/apj.261

Research Article
Kinetics and modeling of charge transfer polymerization of
methyl methacrylate
P. G. Rao,1 R. Vijayaraghavan,2 K. V. Raghavan3 and P.S.T. Sai4 *
1
North East Institute of Science & Technology (CSIR), Jorhat, India
2
School of Chemistry, Monash University, Clayton, Australia
3
Indian Institute of Chemical Technology, Hyderabad, India
4
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai, India

Received 19 September 2008; Revised 9 December 2008; Accepted 12 December 2008

ABSTRACT: The charge transfer polymerization of methyl methacrylate (MMA) in presence of n-butyl amine (nBA)
and carbon tetrachloride (CCl4 ) with dimethyl sulfoxide (DMSO) as solvent was experimentally investigated. The
variables include concentrations of MMA, nBA, CCl4 , DMSO and reaction temperature. The effect of these variables
on monomer conversion, number and weight average molecular weights is discussed. A reaction mechanism is proposed
and overall kinetics, propagation, chain transfer and termination constants are evaluated. A mathematical model is
proposed for estimating monomer conversion, number and weight average molecular weights. The proposed model is
validated using the kinetic constants and compared satisfactorily with experimental data of the present study.  2009
Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: charge transfer polymerization; methyl methacrylate; kinetics; modeling

INTRODUCTION charge transfer polymerization of MMA are summa-

There has been an increasing interest in initiation
of polymerization by charge transfer complexes. The
application of this technique is important with reference
to narrow molecular weight distribution in polymer for-
mulations for paints, leather and special additives for
petroleum. Kinetics of charge transfer polymerization
is complex because of the direct participation of charge
transfer agents in the initiation, propagation and ter-
mination steps. Commercial application of this class
of polymerization requires a careful study of kinetics
and modeling of reaction system to achieve improved
molecular weight distribution by evolving optimum
temperature policies.
Polymerization of methyl methacrylate (MMA) initi-
ated by charge transfer complex can be conducted at rel-
atively low temperatures compared to thermal-initiated
polymerization, which requires temperatures more than
60 ◦ C. In addition, thermal-initiated polymerization
requires strict parameter control for obtaining narrow
molecular weight distribution.
The details of various systems and experimental con-
ditions employed by earlier investigators in respect of
*Correspondence to: P.S.T. Sai, Department of Chemical Engineer-
ing, Indian Institute of Technology Madras, Chennai-600036, India.
E-mail: psts@iitm.ac.in
 2009 Curtin University of Technology and John Wiley & Sons, Ltd.
rized in Table 1. Matsuda and Ishiroshi[1] investigated
kinetics initiated by transfer complex of poly-2-vinyl
pyridine and liquid sulfur dioxide in the presence of car-
bon tetrachloride (CCl4 ). They studied the effect of con-
centrations of complex, monomer and CCl4 on the rate
of polymerization and reported that both equilibrium
constant and overall rate of polymerization decreased
with increasing molecular weight of polymer donor.
Contrary to this, the molecular weight of poly-MMA
formed increased with increase in molecular weight
of polymer donor. Gupta and Nandi[2] used dimethyl
sulfoxide (DMSO) as solvent and evaluated the chain
transfer coefficient of solvent. Hussain et al .[3] stud-
ied kinetics with dimethyl formamide, CCl4 and elec-
tron donors such as methyl amines and cyclohexamine.
They reported that no polymerization took place in
the absence of CCl4 and the molecular weight of
poly-MMA decreased with increase in concentration of
cyclohexamine.
The charge transfer initiation of MMA in the pres-
ence of CCl4 and DMSO was investigated by Baruah
and Dass[13] with isopropylamine and with n-butyl
amine (nBA) by Sen and Dass.[5] While the former
observed a rapid increase in rate of polymerization up
to a limiting concentration of CCl4 and independent
beyond that, the latter reported different dependency of
monomer concentration when [C]/[A] that is, the ratio
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

Table 1. Details of earlier experimental investigations on charge transfer polymerization.

Donor Conversion
Maximum Overall rate
Concentration [CCl4 ] [MMA] reaction time constant
Name (mol/L) (mol/L) (mol/L) (Wt%) (@ h) studied (h) T (K) (L/mol.s × 106 ) Reference
Methyl amine 2.20 1.03 1.79 1.50 1.0 5.0 303 [3]
Cyclohexaylamine 0.87 1.03 0.94 3.45 1.0 – 303 [3]
Dinitrophenyl 0.0424 1.03 1.86 13.70 0.5 2.5 333 [13]
hydrazine
Isopropylamine 1.87 1.87 1.87 5.00 5.0 7.0 303 2.10 [13]
n-Butylamine 1.87 1.03 1.89 8.80 5.0 5.0 303 [5]
n-Butylamine 1.87 2.48 2.81 2.25 2.0 2.0 303 1.36 [5]
n-Butylamine 1.87 2.48 1.87 1.97 2.0 2.0 303 1.46 [5]
n-Butylamine 1.87 2.48 3.70 2.85 2.0 2.0 303 1.50 [5]
Melamine 0.0133 0.68 1.88 1.70 1.0 4.0 333 1.42 [24]
Urea 0.012 0.68 1.88 0.60 1.0 2.5 333 [10]
Oxalic acid 3 × 10−9 1.04 1.81 1.00 1.0 1.0 333 [25]
Malonitrile 6 × 10−9 1.81 0.95 Trace 3.0 NA 333 [8]
Decylamine 0.57 0.76 1.77 3.00 1.0 1.0 353 [27]
2-Aminoheptane 1.27 1.96 1.77 1.00 1.0 1.0 353 [4]
Ethanolamine 1.96 2.00 2.90 303–323 7.10 [26]

of concentration of CCl4 to amine is ≤1 and ≥1. These
authors reported overall rate and average polymerization
rate constants.
Saha and Choudhuri[14] studied the effect of various
substituted amines on polymerization initiated with
ferric laurate-amine as initiator employing CCl4 at
60 ◦ C. Amines used were nBA, di-nBA and tri-nBA
and it was reported that rate of polymerization follows
the order: tertiary > secondary > primary amine.
Baruah and Subramanyam[12] studied the kinetics with
dimethyl formide initiated by ethanolamine and CCl4
and reported average rate constant and overall activation
energy.
Vijayaraghavan and MacFarlne[15] studied the effect
of hydrophobic and hydrophilic organic salts on charge
transfer polymerization of styrene, and recently Jahan-
zad et al .[16] studied in situ polymerization of MMA in
a single batch reactor and obtained polymer beads with
a very broad size distribution.
In spite of extensively reported experimental work
on kinetics of charge transfer polymerization of MMA,
investigations on modeling aspects are few. Louie
et al .[17,18] analyzed several control strategies with
a detailed constitutive model incorporating gel and
glass effects. The model developed by them has flex-
ibility to study the effect of optimal temperature
history, photoinitiation intensity and variation and pro-
grammed monomer and solvent addition. Takechiro
et al .[19] proposed a new method for calculating reac-
tor temperature and initiator concentration in order to
obtain a polymer with a prescribed molecular weight
distribution.
Ponnusamy and Penlidis[20] used conversion, number
and weight average molecular weights data obtained
over different operating conditions to estimate initiator
 2009 Curtin University of Technology and John Wiley & Sons, Ltd.
decomposition and propagation rate constants employ-
ing a batch reactor model. Penlidis et al .[9] derived
a mechanistic model and suggested simplifications
using various assumptions and approximations. Model
responses were compared in order to check whether
simplifications degraded predictive capabilities of orig-
inal model. Srour et al .[21] studied optimal control
policies for emulsion polymerization of MMA in a
semi-batch reactor using multiobjective dynamic opti-
mization method.
A critical analysis of literature indicates that most
investigations were limited to initiation mechanism, par-
ticularly to study the effect of various electron donor
and acceptor molecules and at temperatures above 60 ◦ C
involving a small amount (<5 mL) of reaction mixture
in a dilatometer. There appears, however, no study in
respect of propagation, chain transfer and termination
together with initiation mechanism. In addition, a com-
prehensive theoretical understanding of charge trans-
fer mechanism is not available. This communication
addresses the aforementioned aspects to study the effect
of various variables on monomer conversion, number
and weight average molecular weights for charge trans-
fer polymerization of MMA in the presence of nBA and
CCl4 with DMSO as solvent. A kinetic mechanism is
proposed and the overall kinetics, initiation, chain trans-
fer and termination constants are evaluated. A model
for predicting monomer conversion, number and weight
average molecular weights is developed and validated.
EXPERIMENTAL
Experiments were conducted in a specially fabricated
glass ‘H’ tube (Fig. 1) kept in a constant temperature
Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE

bath for maintaining isothermal conditions. The H tube
consists of two limbs joined together through a connect-
ing tube section for transferring contents in one limb to
another. Each limb has two nozzles with valves, one
for feeding reactants, solvents etc. and the other for
nitrogen purging.
Dried H tube was purged with nitrogen and measured
quantities of MMA and CCl4 were taken in one limb
while amine and solvent were taken in the other limb.
After creating inert atmosphere in the system, the
contents in each limb were brought to the desired
temperature. The contents of one limb were then mixed
with those of the other limb and reaction was allowed
to proceed for a fixed time maintaining the temperature
constant. At the end of the reaction period, reacted
polymer was precipitated in methanol with traces of
hydroquinone to arrest further polymerization. The
product was filtered and dried till constant weight was
reached. The monomer conversion was calculated from
the weight of polymer and the number and weight
average molecular weights were obtained from GPC
interfaced with an integrator. The range of variables
investigated in the present study is detailed in Table 2.
1 temperatures. This is in contrast to polymerization
40
2 2
200
RESULTS AND DISCUSSION
Effect of variables
Experiments were conducted to identify the mode of
addition of reactants and inert medium to be employed
in reaction environment. The mode of addition of
reactants has significant effect on conversion and rate of
polymerization at higher temperatures when [C]/[A] ≤
1 and even at lower temperatures when [C]/[A] > 1.
The conversion levels obtained when the monomer
and amine in one limb were added to CCl4 and
DMSO in the other limb with the reaction being
carried out in nitrogen atmosphere were higher. Hence,
this combination was used in all further experiments.
The conversions obtained with this combination were
better than those reported by Sen and Dass[5] for the
same system, but with different mode of addition. The
effect of mode of addition of reactants on monomer
conversion was not reported earlier. There is a good
scope for investigations on semi-batch mode of addition
of reactants to tailor product molecular weights or
characteristics.
From the experimental data on monomer conversion
at different conditions, it is observed that monomer
conversion was less than 20% except at very high
initiated by peroxide initiators. This phenomenon was
not reported by earlier investigators and is because
of the mode of addition of reactants employed in
the present study. A typical variation in monomer
conversion and rate of polymerization with time is
shown in Fig. 2.

LIMB 1 LIMB 2 30 4

25
20
3

Polymerization rate x 105

100 1 Inert gas inlet/outlet
Percent Conversion

2 Reactants inlet/product outlet 20

All dimensions are in mm T= 333K

15 [M]=2.5 2
Figure 1. Details of the experimental set-up. [A]=1.87
[C]=2.48
10 [S]=4.2

Table 2. Range of variables investigated in the present 1

study. 5

Variable Range
3 0 0
Temperature (K) Concentration (mol/m ) 301–333
MMA 1.500–3.500 0 5 10 15 20 25
CCl4 0.750–2.135 Time. h
nBA 0.735–2.127
DMSO 2.030–6.360 Figure 2. Variation of conversion and rate of polymerization
with time when [C]/[A] ≤ 1.
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

The effect of concentration of MMA on monomer 12

conversion when [C]/[A] ≤ 1 and >1 are, respectively, t=2h 303 K
shown in Figs 3 and 4. In general, the rate of polymer- 10 313 K
ization increased with increase in monomer concentra- 323 K

% Conversion
8 333 K
tion, but decreased marginally at lower temperatures.
On the other hand, monomer conversion decreased 6
with increase in monomer concentration at and below
313 K. But at and above 323 K, it increased both when 4
[C]/[A] ≤ 1 and >1.
The solvent concentration was varied at different 2
temperatures by keeping the ratio of [CCl4 ]/[MMA]
and [nBA]/[MMA] constant. The monomer conversion 0
0.5 1 1.5 2 2.5 3
decreased with decrease in solvent concentration, while
[DMSO]/[MMA]
the rate of polymerization increased. The variation in
monomer conversion with concentration of solvent at Figure 5. Variation of conversion with [DMSO]/
different temperatures is shown in Fig. 5. [MMA] when [C]/[A] ≤ 1.
The concentration of nBA was varied between 0.8
and 2.1 mol/m3 and the variation in conversion with
[nBA]/[MMA] is shown in Fig. 6 at four different 16
temperatures. The variation in monomer conversion 303 K
313 K
12 323 K

% Conversion
333 K
16
303 K
[A] = 1.896 8
313 K
[C] = 1.023
12 t=2h 323 K
333 K 4
% Conversion

t=1h
8 0
0.2 0.6 1 1.4
[nBA]/[MMA]
4
Figure 6. Variation of conversion with [nBA]/
[MMA].
0
1.5 2 2.5 3 3.5 4
[MMA], moles/m3 and rate of polymerization with increases in amine
concentration was not significant at higher temperatures
Figure 3. Variation of conversion with [MMA]
when [C]/[A] ≤ 1.
(333 and 323 K), but at lower temperatures (313 and
303 K) they showed a maximum at nBA concentration
of 1.4 mol/m3 .
20 The concentration of CCl4 was varied between 0.7
[A] = 0.998
303 K and 2.2 mol/m3 and variation in monomer conversion
313 K with [CCl4 ]/[MMA] is shown in Fig. 7. The variation in
[C] = 1.841
16 323 K
t=2h monomer conversion and rate of polymerization when
333 K
[C]/[A] ≤ 1 is not significant at higher temperatures,
% conversion

12 but at lower temperatures they decreased. As the

temperature decreases the change is more pronounced
8 at very high [C]/[A] ratio.
From the preceding results, it is evident that monomer
4 conversion and rate of polymerization show a distinct
trend when [C]/[A] ≤ 1 and >1. Hence it was decided
to study the variation in monomer conversion with
0
1 1.5 2 2.5 3 3.5 4 [C]/[A] and the results are shown in Fig. 8. The
[MMA], moles/m3
increase in [C]/[A] ratio indicates increase in [C]
and/or decrease in [A], while decrease in [C]/[A] ratio
Figure 4. Variation of conversion with [MMA] indicates increase in [A] and decrease in [C]. No
when [C]/[A] > 1. significant change in conversion was observed when
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE

8 5

rate of polymerization, x 105

303 K
t =1 h
4 313 K
6 323 K
% Conversion

333 K
3
4
303 K
2
313 K
2 323 K
333 K 1

0 0
0.2 0.6 1 1.4
0 1 2 3 4 5
[C]/[MMA]
[MMA], moles/m3
Figure 7. Variation of conversion with [CCl4 ]/
[MMA]. Figure 9. Variation in rate of polymerization with
[MMA] when [C]/[A] ≤ 1.

14
t=1h 303 K study are compared with those reported in literature[13]
12 [M] = 2.5 313 K in Table 3. The polydispersity was found to be constant
[S] = 4.4 323 K and is above 2.5 except at 333 K where it is near to
10
% Conversion

333 K
2 when [C]/[A] > 1. This suggests that charge trans-
8 fer polymerization leads to narrow molecular weight
6 distribution or higher polydispersity. But polydispersity
decreased with increase in temperature because of ther-
4
mal polymerization as indicated.
2

0
0.2 0.6 1 1.4
[C]/[MMA]
Reaction mechanism

Figure 8. Variation of conversion with [C]/[A].
[C]/[A] ≤ 1. When [C]/[A] > 1, conversion decreased
with increasing [C]/[A] up to a reaction temperature
of 323 K, while at 333 K an opposite trend was
observed. This indicates that when [C]/[A] > 1, excess
CCl4 participates in termination. At 333 K, a part of
polymerization might be due to thermal polymerization
in spite of the presence of solvent. Hence, there is an
increase in conversion at 333 K even though there is
excess CCl4 . A similar trend was observed for rate of
polymerization (Fig. 9).
The number and weight average molecular weights
decreased with increase in [C]/[A] ratio. The decrease
is more rapid at lower temperatures than at higher tem-
peratures. The molecular weights obtained in the present
The reaction mechanism together with rate equations
for charge transfer polymerization of MMA in presence
of nBA and CCl4 with DMSO as solvent is presented
in Table 4.
The initiation of free radicals by interaction of amine,
CCl4 and monomer is proposed. The possibility of
DMSO producing free radicals is not considered in
the present study because of its inability to initiate
polymerization of MMA.
The amine acts as electron donor and MMA acts as
electron acceptor to form charge transfer complex I.
The charge transfer complex thus formed reacts with
CCl4 to provide a primary radical (M1 ) to initiate
polymerization as shown:
k1
⇔
(C9 H9 )NH2 + MMA I
k−1

Table 3. Comparison of molecular weights obtained in the present study with literature.

System T (K) t (h) Conversion, % Mn Mw PD Reference

MMA, DMSO, CCl4 , nBA 333 3.0 8.92 48 918 122 151 2.50 Present study
MMA, DMSO, CCl4 , nBA 333 8.0 13.87 44 329 130 663 2.95 Present study
MMA, AIBN(0.05 mol/L) 338 1.0 13.70 83 100 145 000 1.75 [6]
MMA, AIBN (0.05 mol/L) 338 0.5 9.00 76 900 125 000 1.62 [7]

AIBN, azobisisobutyronitrile. PD, Polydispersity

 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

Table 4. Reaction mechanism for charge transfer present study. In addition to termination by transfer or
polymerization. combination and/or disproportionation, it is proposed
in the present study that CCl4 also participates in the
Initiation
k1 termination step based on experimental observations.
A + M k⇔
−1
I
k2
I + C−−−→M1 + RN+ H2 Cl−
k3 Model development
A + C k⇔
−3
II
k4
II + M−−−→M1 + RN+ H2 Cl− On the basis of mechanism proposed a mathematical
Propagation model is formulated to predict monomer conversion
kp and number and weight average molecular weights of
M1 + M−−−→M2 the polymer. Since the reaction was carried out in the
kp absence of oxygen, it is assumed that the mechanism
Mx −1 + M−−−→Mx
contains free radicals that are formed by reaction of
Chain transfer
ktrm
charge transfer complexes with monomer etc. It is
Mx + M−−−→M1 + Px also assumed that thermal polymerization does not take
ktrs
Mx + S−−−→S1 + Px place.
ktra
Mx + A−−−→A1 + Px Rate of initiation
ktrc
Mx + C−−−→C1 + Px The rate of formation of charge transfer complex I is as
ktrco follows:
Mx + I−−−→I1 + Px d[I]
= k1 [A][M] − k−1 [I][C] (1)
Termination dt
ktc
Mx + M−−−→Pxy Apparently, the charge transfer complexes are too
ktd
Mx + My −−−→Px + Py reactive to be detected in presence of monomer and thus
kth
Mx + C−−−→Px + C
justify the application of pseudo-steady state hypothesis
(PSSH). Hence
k1 [A][M]
[I] = (2)
k2 k−1 + k2 [C]
I + CCl4 M1 + (C4 H9 )N+ Cl−
−−→ k2 k1 [A][M][C]
Ri ,I = k2 [I][C] = (3)
The above steps are in accordance with Seanor[11] k−1 + k2 [C]
who reported initiation of polymerization by charge k4 k3 [A][M][C]
transfer complex formed on reaction between MMA Ri ,II = k4 [II][M] = (4)
k−3 + k4 [M]
and an aliphatic amine such as methyl, isopropyl and
cyclohexane. The rate of termination of radicals by reacting among
The amine also reacts with CCl4 to form charge themselves is very small compared to the rate of
transfer complex II, which on further interaction with formation and hence the disappearance of radicals by
MMA, provides primary free radical. termination due to interaction among themselves is
neglected.
k3
⇔
Assuming a fraction ‘δ’ of reacted amine is used for
(C4 H9 )NH2 + CCl4 II formation of complex I and (1 − δ) for complex II, the
k−3
rate of formation by both charge transfer complexes is
k4
II + M M1 + (C4 H9 )N+ H2 Cl− as follows:
−−→
k1 k2 [A][M][C] k3 k4 [A][M][C]
If [C]/[A] ≤ 1, the charge transfer complex I and Ri = δ + (1 − δ) (5)
k−1 + k2 [C] k−3 + k4 [M]
if [C]/[A] > 1, the charge transfer complex II pre-
dominate.[22] In addition, minimum concentrations of Assuming k2 [C]  k−1 and k4 [M]  k−3 , the above
CCl4 and amine are required for charge transfer mech- equation reduces as follows:
anism to occur. In the present study, the occurrence of
one of these mechanisms is considered depending on Ri = δ k1 [A][M] + (1 − δ)k3 [A][C] (6)
the value of [C]/[A].
The conventional propagation and chain transfer Concentration of radicals
mechanisms as applicable to polymerization by thermal- The rate of change of concentration of radicals of
or peroxide-initiated free radicals are considered in the chain length M1 is obtained by subtracting rates due
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE

to propagation, transfer and termination from initiation. initial and minimum concentrations of CCl4 required
Following Cutter and Drexler[23] approach for termination to take place or for propagation rate
to be independent of concentration of CCl4 , then
d[M1 ] ([C0 ] − [Cm ]) is the concentration of CCl4 available for
= Ri − {kp [M][M1 ]}
dt termination reaction. Introducing the concentrations of
− {(ktrm [M] + ktrs [S] + ktra [A] CCl4 and charge transfer complex in Eqs 7 and 8
+ ktrc [C])([M1 ] − [R])}
d[M1 ]
−{(ktd + ktc )[R][M1 ] − (kth [C][M1 ])} (7) = Ri − {kp [M][M1 ]}
dt
 
(ktrm [M] + ktrs [S] + ktra
The overall rate of change of radicals of chain length
− [A] + (ktrc [C0 ] − [Cm ]))
M2 and greater is
([M1 ] − [R])
d[Mx ] −{(ktd + ktc )[R][M1 ] − (kth [C0 ]
= {kp [M][Mx −1 ] − kp [M][Mx ]}
dt − [Cm ]))([M1 ])} (11)


(ktrm [M] + ktrs [S] + ktra [A] + ktrc [C])
− d[Mx ]
([Mx ]) = {kp [M][Mx −1 ] − kp [M][Mx ]}
dt
−{(ktd + ktc )[R][Mx ] − kth [C][Mx ]} (8)  
ktrm [M] + ktrs [S]
The overall rate of change of radicals, [R] is sum- − +ktra [A] + ktrc ([Co ] ([Mx ])
mation of all radicals of different chain lengths in the −[Cm ])
medium. In developing Eqs 7 and 8, chain transfer by −{(ktd + ktc )[R][Mx ] − kth ([C0 ]
complexes I and II, regeneration of monomer radical − [Cm ]))([Mx ])} (12)
due to chain transfer and chain transfer by polymer are
neglected.
Assuming that overall rate of change of concentration Using PSSH for radicals [M1 ] and [Mx ], the resultant
of free radicals is constant in a short period of time, equations give rise to many relationships between [Mx ]
and [Mx −1 ]. Hence
∞
d[R]  d[Mx ]  
= = Ri
dt dt Ri /[R] + α
x =1  
[M1 ] = [R]   (13)
∞
 kp [M] + α(ktd + ktc )[R]
− (ktd + ktc )[R] Mx +kth ([C0 ] − [Cm ])
x =1
 
∞
  kp [M] 
[Mx ] = [Mx −1 ]   (14)
− kth [C] Mx = 0 (9) kp [M] + α + (ktd + ktc )
x =1 [R] + kth ([C0 ] − [Cm ])
−kth [C]
i.e., [R] = where α = ktrm [M] + ktrs [S] + ktra [A] + ktrc ([C0 ]−
2(ktd + ktc )
 1/2 [Cm ]).
kth2 [C]2 Ri The above equations reduce to the following from
± + (10) which concentration of radicals of different chain length
4(ktd + ktc ) 2 (ktd + ktc )
are obtained.
When CCl4 does not participate in termination (kth =
0), Eq. 10 reduces to an equation similar to that for [M1 ] = [R] (1 − β)γ (15)
thermal- or peroxide-initiated free radical polymeriza- x −1
[Mx ] = [Mx −1 ] β = [R] (1 − β) γ β (16)
tion except for the definition of Ri .[23]
When the concentration of CCl4 is less than a
minimum, the rate of propagation depends on the where
concentration of CCl4 because the rate of initiation
is a function of concentration of CCl4 . In such a kp [M]
β= and
case, the available CCl4 will be used up in radical kp [M] + α + (ktd + ktc )[R]
initiation rather than radical termination. But when the +kth ([C0 ] − [Cm ])
concentration of CCl4 is in excess over and above Ri /[R] + α
γ = (17)
the minimum required for complex formation, it takes α + (ktd + ktc )[R] + kth ([C0 ]
part in radical termination also. If [C0 ] and [Cm ] are −[Cm ])
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

Concentration of monomer ∞
  t
(α + kth {[C0 ] − [Cm ]})γ [R](1 + β)
The rate of monomer consumption or polymerization x 2 Px =
x =1 0 (1 − β)2
rate is as follows:

d[M]
t
2ktd [R]2 γ (1 + β)
− = Ri + {(kp + ktrm )[M0 ][R]} (18) dt + dt
dt 0 (1 − β)2
 t
ktc [R]2 γ 2 (2 + β)
In the above equation, substituting the appropriate + dt (24)
equation for Ri (depending on [C]/[A] ratio, Eq. 6) and 0 (1 − β)2
concentration of radicals, the monomer concentration is
obtained. Accordingly
The number and weight average molecular weights
if [C]/[A] ≤ 1, [M] = [M0 ] are estimated by the following equations:
 t
 
exp − (kp + ktrm )[R]dt (19) ∞ ∞
0  
xPx x 2 Px
i f [C]/[A]  1, [M] = [M0 ]
 t  t Mn =
x =1
and Mw =
x =1
(25)
  ∞ ∞
exp − (kp + ktrm )[R]dt + k1 [A]dt (20)
0 0
Px Px
x =1 x =1
Concentration of dead polymer of chain length
x Evaluation of kinetic constants
The rate of formation of dead polymer of chain length The overall kinetics, initiation, propagation, chain trans-
x is as follows: fer and termination constants are evaluated following
d[Px ] the procedure described below using experimental data
= {ktrm [M] + ktrs [S] + ktra [A] of the present study.
dt
+ ktrc ([C0 ] − [Cm ])}[Mx ]
kth ([C0 ] − [Cm ])[Mx ] Overall kinetic constants
The overall rate of polymerization, Rp , as proposed by
x −1
 Sen and Dass[5] is as follows:
+ 2ktd [R][Mx ] + ktc [M][Mx −n ]
n=1
 1/2
= α[R](1 − β)γβ x −1
+ kth ([C0 ] δk1 k2 [A][M][C]
 
kp k−1 + k2 [C]
Rp = 1/2 [M] (26)
− [Cm ])[R](1 − β)γβ x −1 kt  + (1 − δ)k3 k4 [A][M][C] 
k−3 + k4 [M]
+2ktd [R]2 (1 − β)γβ x −1
+ ktc [R]2 (x − 1)(1 − β)2 γβ x −2 (21)
When [C]/[A] ≤ 1, δ = 0 and since k4 [M]  k−3 ,
Rp = K1 [M] [A]1/2 [C]1/2 where the overall constant
This equation is integrated and summed over all the
K1 = kp k3 1/2 /kt 1/2 .
species to get
When [C]/[A] > 1, δ = 1 and since k2 [C]  k−1 ,
∞
  t Rp = K2 [M]3/2 [A]1/2 where the overall rate constant
Px = (α + kth {[C0 ] − [Cm ]})γ [R] dt K2 = kp k1 1/2 /kt 1/2 .
x =1 0 From a plot of Rp as a function of [M] at fixed
 t  concentrations of amine and CCl4 (Fig. 10), K1 , the
+ 2ktd γ [R]2 dt + ktc γ 2 [R]2 dt (22) overall rate constant when [C]/[A] ≤ 1, is evaluated.
0 Similarly, from the plot of Rp as a function of log
[M] at fixed concentration of amine (Fig. 11), K2 , the
Similarly overall rate constant when [C]/[A] > 1, is evaluated.
∞  K1 and K2 thus obtained at different temperatures are
 t
(α + kth {[C0 ] − [Cm ]})γ [R] reported in Table 5. These constants are in the same
xPx = dt
x =1 0 (1 − β) range of magnitude as that reported by Gogo and Dass[4]
  t for a similar system. Whereas theses authors did not
t
2ktd γ [R]2 ktc γ 2 [R]2 notice any variation between these constants, the present
+ dt + dt (23)
0 (1 − β) 0 (1 − β) study indicated a variation for [C]/[A] ≤ and >1.
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE

2 In charge transfer polymerization mechanism, as

303 K proposed in the present study, the complex agents CCl4
1.8 313 K
Log Rp x 106 323 K and amine also participate in chain transfer mechanism.
1.6 333 K Hence the Eq. 27 is modified as follows:
1.4
Rp
1.2 xn = (28)
Ri + ktrm [M][Mx ] + ktrs [S][Mx ]
1 +ktrc [C][Mx ] + ktra [A][Mx ]
0.8
0 0.1 0.2 0.3 0.4 0.5 0.6 Rearranging the above equation after including Rp =
Log [MMA] kp [M] [Mx ]

Figure 10. Variation in rate of polymerization 1 Ri ktrm ktrs [S] ktrc [C] ktra [A]
with [MMA] when [C]/[A] > 1. = + + + + (29)
xn Rp kp kp [M] kp [M] kp [M]

In this equation, appropriate expressions for Ri are

120
T = 313 substituted depending on whether [C]/[A] ≤ 1 (Eq. 3)
[M] = 2.50 or >1 (Eq. 4) and becomes linear at fixed concentra-
100 [A] = 1.87 tions of solvent, monomer and amine. Accordingly,
[C] = 1.45
80 [S] = 4.20 experimental
% conversion

Predicted kth ≠ 0 1 k3 [A][C ]

when [C ]/[A] ≤ 1, = + Z1 (30)
60 Predicted kth = 0 xn kp
1
40 and when [C]/[A]  1,
xn
20 k1 [M][A]
= + Z2 (31)
kp
0
0 5 10 15 20 25
Time, h
where Z1 and Z2 are constants. From experimental data
of 1/Rp versus 1/xx , initiation constants k1 and k2 are
Figure 11. Comparison of experimental and predicted evaluated. These values at different temperatures are
conversions when [C]/[A] ≤ 1. listed in Table 5.

Propagation constants
This confirms the difference in rate of polymerization In the expression for overall kinetic constants K1 and
between them. K2 , initiation constants k1 and k2 are known and both kp
and kt are unknown. While rate of propagation is depen-
Initiation constants dent on rate of initiation and termination, the rate of
In thermal or peroxide initiated polymerization, the termination due to combination and disproportionation
degree of polymerization is as follows: is assumed to be the same as that obtained in thermal-
or peroxide-initiated polymerization. Hence a reported
Rp a value[6,17,18] of 9.8 × 107 e−(352.8/T) is assigned to kt
xn = (27) and kp values calculated both when [C]/[A] ≤ 1 and >1
Ri + ktrm [M] [Mx ] + ktrs [S] [Mx ]

Table 5. Details of kinetic constants obtained in the present study.

[C]/[A] ≤ 1 Temperature (K) [C]/[A] > 1 Temperature (K)

303 313 323 333 303 313 323 333
Overall constant × 10 (m /mol.s) 6 3
4.831 4.628 6.722 8.789 6.967 8.498 11.299 13.654
Initiation constant × 108 0.118 0.153 0.289 0.222 0.144 0.223 0.666 0.187
Propagation constant × 104 0.485 0.550 0.618 0.690 0.110 0.128 0.147 0.169
Chain transfer constant 0.120 0.095 0.213 0.208 0.027 0.221 0.051 0.051
ktrs × 102 0.115 0.340 0.253 0.127 0.026 0.079 0.060 0.031
ktra × 102 0.080 0.126 0.077 0.478 0.018 0.029 0.018 0.117
ktrc × 102
Termination constant × 102 0.036 0.160 0.143 0.280 0.103 0.015 0.106 0.174

 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

at different temperatures are reported in Table 5. The technique. The kth values so obtained at different tem-
value of kp /kt 1/2 obtained in present study is compared peratures are reported in Table 5.
to that reported by Gogoi and Dass[5] for a similar sys-
tem when [C]/[A] > 1. But the value when [C]/[A] ≤ 1
Activation energies
is not reported in the literature.
Following Arrhenius type of dependence of temperature
on kinetic constants, activation energies for initiation,
Chain transfer constants propagation, chain transfer and termination steps are
If ratios of [C]/[M] and [A]/[M] are fixed, Eq. 29 calculated and reported in Table 6. The overall activa-
reduces as follows: tion energy for polymerization reaction is determined
1 ktrs [S] by the following equation:
= + Z3 (32)
xn kp [M]
Eki + Ekt − Ekth
where Z3 is a constant. From experimental data of Eoverall = Ep + (35)
2
inverse degree of polymerization at various [S]/[M]
ratios, the constants ktrs /kp are evaluated. Since kp is
The value obtained is 3.75 kcal/mol, which is much
known, ktrs is calculated. Similarly by fixing [S]/[M]
less than 6.7 kcal/mol as reported in literature[1] for a
and [C]/[M], ktra is evaluated by varying [A]/[M].
system similar to that of the present study but acceler-
Likewise ktrc is also evaluated by fixing [S]/[M] and
ated by metal complex. This confirms the advantage of
[A]/[M] and varying [C]/[M]. The chain transfer con-
charge transfer polymerization over other methods.
stants thus estimated at different temperatures both
when [C]/[A] ≤ 1 and >1 are reported in Table 5. An
analysis of these constants indicates that the predomi-
nance of chain transfer agents follow the order: amine
Model simulation and verification
> CCl4 > solvent.

Termination constants The mathematical model developed in the present study

As per the mechanism proposed in the present study,
termination of free radical chain length takes place
due to combination, disproportionation and/or due to
CCl4 participation. The mechanism of termination due
to combination and disproportionation is similar to that
of thermal or peroxide initiated free radical polymer-
ization. Hence, the constants reported in literature[6,7,17]
for kt and ktc are used in the present study. The reported
values are kt = 9.8 × 107 exp(−352.8/T) and ktc /ktd =
3.95 × 10−4 exp(−4090/T). Termination constant due
to CCl4 is estimated in the present study as detailed
below:
The equations derived in the present study for con-
centration of monomer as given by Eqs 19 and 20 for
[C]/[A] ≤ 1 and >1 respectively, are simplified as fol-
lows:
 
[M] = [M0 ] exp −{kp + ktrm }[R] (33)
 
[M] = [M0 ] exp −{kp + ktrm }[R] − k1 [A] (34)
for predicting monomer concentration and molecular
weights of polymer is validated with kinetic constants
obtained in the present study and compared with
experimental data. The values of kp , ktrm and K1 are
used for predicting monomer concentration, whereas
all kinetic constants are used for predicting molecular
weights. The experimental data used for comparison
with the model was obtained independently.
Prediction of monomer conversion
A typical comparison of experimental and predicted
monomer conversions when [C]/[A] ≤ 1 and >1 are
respectively shown in Figs 11 and 12. The monomer
conversion predicted by assuming that CCl4 does not
Table 6. Details of activation energy obtained in
present study.
Activation energy (kCal/mol)

The experimental data of time versus MMA con- Reaction step [C]/[A] ≤ 1 [C]/[A] > 1
centration when [C]/[A] ≤ 1 and >1 is respectively Overall 6.65 4.62
subjected to Eqs 33 and 34 and the value in parenthe- Initiation 4.19 9.28
sis of exponential terms are obtained. In these values, Propagation 2.36 2.87
all the terms except concentration of radical are known. Chain transfer
Solvent 8.37 8.70
The radical concentration, [R], and CCl4 termination Amine 7.82 8.33
constant, kth , are related by Eq. 10. By substituting val- CCl4 12.13 12.64
ues of ktd , ktc , [C] and [R] for conditions [C]/[A] ≤ 1 Termination 12.20 1.79
and >1, kth is evaluated by employing Regula–Falsi
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE

100 80

Number Average Molecular

T = 313 Experimental 333 K Experimental
323 K Experimental
Predicted kth ≠ 0

Weight (Thousnads)
[M] = 2.50 313 K Experimnetal
80 [A] = 1.87 Predicted kth = 0 333 K predicted
60
323 K predicted
[C] = 2.45 313 K predicted
% Conversion

60 [S] = 4.20
40

40

20
0 10 20 30 40 50 60 70
20
Time, h

0 Figure 13. Comparison of experimental and predicted

0 10 20 30 40 number average molecular weight when [C]/[A] ≤ 1.
Time, h

Figure 12. Comparison of experimental and predicted

conversions when [C]/[A] > 1. 70
[M] = 2.50

Number average molecular

60 [A] = 1.87
[C] = 2.48

participate in termination step (i.e., kth = 0) is also
shown in these figures.
The model predictions are satisfactory at temperatures
between 303 and 323 K. At 333 K, the model predicted
lower conversions than experimental ones during initial
stages of reaction. This is because thermal polymeriza-
tion taking place at 333 K was not considered in the
present model.
The improvement in predictions with inclusion of
kth is evident in all these cases, since the model pre-
dicted higher conversions than experimental when kth
is neglected. The effect of temperature on monomer
conversion is significant when [C]/[A] ≤ 1, whereas it
increases with increase in temperature when
[C]/[A] > 1.
At the same temperature, the monomer conversion is
more when [C]/[A] ≤ 1 than when [C]/[A] > 1 at any
time. This is because of excess CCl4 present in latter
case terminates polymerization faster. This supports
the present hypothesis that termination by excess CCl4
is taking place. The trend predicted by the present
model for conversions when kth = 0 is similar to that
of thermal- or peroxide-initiated polymerization.
Prediction of molecular weights
The variation of number and weight molecular weights
with time is predicted by the present model at different
temperatures when [C]/[A] ≤ 1 and >1 and are respec-
tively compared in Figs 13 and 14. The number average
molecular weight decreases with time and at any par-
ticular time and increases with increase in temperature.
The trends are similar when [C]/[A] ≤ 1 and >1. The
predictions are satisfactory at higher temperatures than
at lower temperatures.
The weight average molecular weight decreases with
time and at any particular time it decreases with increase
in temperature. The latter observation is in contrast with
that observed for number average molecular weight.
 2009 Curtin University of Technology and John Wiley & Sons, Ltd.
weight (thousands)
50 [S] = 4.20
40
30
333 K experimental
20
323 K experimental
10 333 K predicted
323 K predicted
0
0 10 20 30 40 50
Time, h
Figure 14. Comparison of experimental and predicted
number average molecular weight when [C]/[A] > 1.
Due to this, the polydispersity is more at lower tem-
peratures.
Effect of parameter ‘δ’ on conversion
The overall rate of initiation due to complexes I and
II is given by Eq. 6. When [C]/[A] ≤ 1, ‘δ’ assumes a
value zero indicating that complex I initiates reaction
and assumes a value 1 when [C]/[A] > 1 indicating
that the complex II initiates reaction. The possibility
of complex I initiating when [C]/[A] > 1 or complex
II when [C]/[A] ≤ 1 is examined by varying ‘δ’ from
1 to 0 progressively in model equation for conversion.
The results are plotted, typically, in Figs 15 and 16 for
[C]/[A] ≤ 1 and >1 respectively.
These results indicate that at lower temperatures, pre-
diction by either mechanism is satisfactory during the
initial period of reaction. At higher temperatures, pre-
diction of conversion based on either mechanism is
satisfactory for respective cases as there is no signif-
icant change for intermediate values of ‘δ’. Thus initia-
tion mechanism depends on temperature in addition to
[C]/[A] ratio. For [C]/[A] > 1, complex I predominates
at all temperatures and for [C]/[A] ≤ 1, complex II pre-
dominates depending on temperature and [C]/[A] value.
Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
P. G. RAO ET AL. Asia-Pacific Journal of Chemical Engineering

25 into account the initiation mechanism of charge transfer

δ = 1.0
δ = 0.8
complex, participation of CCl4 , nBA in chain trans-
20 δ = 0.6 fer mechanism and participation of CCl4 in termination
δ = 0.4 step. The model is validated with kinetic constants of
% conversion

δ = 0.2 present study and compared satisfactorily with experi-

15
δ=0
Experimnetal mental data.
10
T = 323
[M] = 2.50
5 [A] = 1.87
[C] = 2.48 NOMENCLATURE
[S] = 4.20
0
0 5 10 15 20 25 30
Time, h A1 Amine radical
C1 Carbon tetrachloride radical
Figure 15. Effect of parameter ‘δ’ on conversion when [i] Concentration of i (mol/m3 )
[C]/[A] ≤ 1. K1 , K2 Overall rate constants
k1 , k−1 , k2
k3 , k−3 , k4 Rate constants for initiation
25 kp Rate constant for propagation
δ = 1.0
δ = 0.8 kth Rate constant for termination
20 δ = 0.6 ktc Rate constant for termination by combina-
δ = 0.4
δ = 0.2 tion
% conversion

15 δ=0 ktd Rate constant for termination by dispropor-

Experimnetal
tionation
10 ktra Rate constant for transfer to amine
T = 323
[M] = 2.50 ktrc Rate constant for transfer to CCl4
5 [A] = 1.87 ktrm Rate constant for transfer to monomer
[C] = 2.48 ktrs Rate constant for transfer to solvent
[S] = 4.20
M0 Initial monomer concentration (mol/m3 )
0
0 5 10 15 20 25 30 Mx Polymer radical with x monomer units
Time, h Mn Number average molecular weight
Mw Weight average molecular weight
Figure 16. Effect of parameter ‘δ’ on conversion when Px Polymer with x monomer units
[C]/[A] > 1. R Radical
Ri Rate of initiation
Ri ,I Rate of initiation by charge transfer com-
CONCLUSIONS plex I
Ri ,II Rate of initiation by charge transfer com-
The charge transfer polymerization of methyl methacry- plex II
late in presence of n-butyl amine and carbon tetrachlo- Rp Rate of polymerization (m3 /m.s)
ride with dimethyl sulfoxide as solvent is investigated. S1 Solvent radical
Different limiting conversions are reached at different t Time of reaction (s)
temperatures and more prominent when [C]/[A] ≤ 1. T Temperature (K)
An increase in the concentration of MMA increases con- x Number of monomer units
version at and above 323 K, while it decreases at and α Constant as in Eq. 15
below 313 K. This is prominent when [C]/[A] ≤ 1. An β Constant as in Eq. 15
increase in concentration of DMSO or decrease in con- γ Constant as in Eq. 15
centration of CCl4 increases the conversion of MMA, δ Fraction of amine used for formation of
while nBA has no significant effect. The polymer gen- complex I
erated has higher polydispersity compared to the one O Initial
generated by peroxide-initiated polymerization. m Minimum
A reaction mechanism that includes participation of x Number of monomer units
CCl4 in the termination step is proposed and the over-
all kinetics, initiation, propagation, chain transfer and
termination constants are evaluated at different tem-
REFERENCES
peratures. The overall activation energy for the reac-
tion is 3.75 kcal/mol. A model for predicting monomer [1] M. Matsuda, Y.J. Ishiroshi. Polym. Sci., Part A, 1970; 1,
conversion and molecular weights is developed taking 387–397.
 2009 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering CHARGE TRANSFER POLYMERIZATION OF METHYL METHACRYLATE
[2] S. Gupta, U. Nandi. Polym. Sci., 1970; 8, 1493–1501.
[3] S. Hussain, S.D. Baruah, N.N. Dass. J. Polym. Chem., 1978;
16, 167–171.
[4] A.K. Gogoi, N.N. Dass. J. Polym. Sci., Polym. Chem., 1983;
21, 3517–3524.
[5] S.R. Sen, N.N. Dass. Eur. Polym. J., 1982; 18, 477–480.
[6] A.D. Schmidt, W.H. Ray. Chem. Eng. Sci., 1981; 36,
1401–1410.
[7] P.E. Baillagou, D.S. Soong. Chem. Eng. Sci., 1985; 40,
75–86.
[8] S.D. Barauh, N.N. Dass. Macromol. Chem., 1979; 180,
1351–1358.
[9] A. Penlidis, S.R. Ponnusamy, C. Kiparissidas, K.F. O’Driscoll.
Chem. Eng. J., 1992; 50, 95–107.
[10] S. Hussain, N.N. Dass. J. Polym. Sci., Polym. Chem., 1982;
20, 3181–3187.
[11] D.A. Seanor, in Polymer Science (Ed.: A.D. Jenkins), North
Holland Publishing Company: Amsterdam, 1972; p.1247.
[12] S.D. Baruah, B. Subrahmanyam. J. Macromol. Sci., Chem.,
1990; A27, 237–243.
[13] S.D. Baruah, N.N. Dass. Eur. Polym. J., 1980; 16, 11–14.
[14] S.K. Saha, A.K. Choudhuri. J. Polym. Sci., Polym. Chem.,
1988; 26, 901–911.
 2009 Curtin University of Technology and John Wiley & Sons, Ltd.
[15] R. Vijayaraghavan, D.R. MacFarlane. Eur. Polym. J., 2006;
42, 1830–1835.
[16] F. Jahanzada, S. Sajjadib, M. Yianneskisb, B.W. Brooksa.
Chem. Eng. Sci., 2008; 63, 4412–4417.
[17] B.M. Louie, G.M. Carratt, D.S. Soong. J. Appl. Polym. Sci.,
1985; 30, 3825–3840.
[18] B.M. Louie, G.M. Carratt, D.S. Soong. J. Appl. Polym. Sci.,
1985; 30, 3985–4012.
[19] T.C. Takeichiro, S. Shioya, Y. Okada. Ind. Eng. Chem. Res.,
1988; 27, 93–99.
[20] S.R. Ponnusamy, A. Penlidis. Chem. Eng. J., 1988; 39,
175–183.
[21] M.H. Srour, V.G. Gomes, I.S. Altarawneh. Chem. Eng. Sci.,
2008; 63, 4257–4268.
[22] N.N. Dass. Prog. Polym. Sci., 1984; 10, 51–85.
[23] L.A. Cutter, T.D. Drexler. Comput. Appl. Polym. Sci., 1982;
13–16.
[24] S. Hussain, N.N. Dass. Eur. Polym. J., 1982; 18, 795–798.
[25] S.S. Begum, N.N. Dass. Eur. Polym. J., 1982; 18, 1033–1035.
[26] S.S. Begum, N.N. Dass. J. Polym. Sci., Polym. Chem., 1985;
23, 2561–2565.
[27] N.N. Dass, A.K. Gogoi. J. Polym. Mater., 1984; 1, 183–188.
Asia-Pac. J. Chem. Eng. (2009)
DOI: 10.1002/apj