Indian Journal of Chemical Technology

Vol. 25, March 2018, pp. 150-157

Phase transfer catalysis: Effect of cationic surfactants on the free radical

polymerization of methylmethacrylate

E Murugan* & D Geethalakshmi

Department of Physical Chemistry, School of Chemical Sciences, University of Madras,

Guindy Campus, Guindy, Chennai 600 025, Tamilnadu, India

E-mail: dr.e.murugan@gmail.com, murugan_e68@yahoo.com

Received 23 January 2018; accepted 28 February 2018

The effect of cationic surfactants, decyltrimethylammonium bromide (DTAB), dodecyltrimethylammonium bromide

(DDTAB) and tetradecyltrimethylammonium bromide (TDTAB), has been studied as phase transfer catalysts (PTCs) on the

free radical polymerization of methylmethacrylate (MMA) using potassium peroxydisulfate (PDS, K2S2O8) in toluene-water

biphase system. Of the three PTCs in their respective critical micellar concentration (CMC) and in common concentration,

the TDTAB show comparatively high rate of polymerization (Rp), 7.76 × 10-5 mol.L-1.S-1, at the lowest reaction time of 30

min in its concentration of 2 × 10-2 mol.L-1. Detailed kinetic study of polymerization of MMA has been carried out using

TDTAB at a fixed time of 30 min by varying [MMA], [K2S2O8], [TDTAB] and temperature. Based on the kinetic results,

the free energy of activation has been calculated, and a suitable mechanism and rate law has been proposed.

Keywords: Phase transfer catalyst, Cationic surfactants, Free radical polymerization, Methylmethacrylate: Peroxydisulphate

It is of high focus to develop new polymerization

process that can provide access to new polymeric

structures and lead to useful applications. One of the

most important polymerization processes which is

commercially benefitable is free radical polymerization,

because of its extensive scope over appropriate

monomers and the simple reaction conditions to conduct

polymerization1. On comparing the conventional free

radical polymerization method, the PTC assisted free

radical polymerization using PDS as a water soluble

initiator has been an interesting area of research, since

under mild reaction condition a high yield with high

molecular weight polymers can be achieved. Persulfate

(S2O82-) is a quite good initiator of free radical

polymerization2, but for organic monomers, it is not

convenient due to its low solubility in organic solutions.

The extraction (phase transfer) of peroxydisulphate ion

into organic phase is rather difficult compared to

nucleophilic anions used in the organic synthesis. On the

other hand the rate of free radical PTC polymerization is

similar to that of solution polymerization, because of the

fast and irreversible initiation of radical processes. So,

this mutual insolubility of nonpolar and ionic

compounds is overcome using PTC, emerged in 19713.

It is capable of carrying the reactant from the aqueous

phase to the organic phase in order to make it available

completely for the substrate to react. It is a novel and

versatile technique and has received widespread

attention and attracted considerable scientific and

practical interest. It is a convenient and highly useful

synthetic tool in all branches of chemistry4 particularly

in organic chemistry5,6

and in polymer chemistry7-9

because of its simplicity, high conversion, high

selectivity and very mild reaction condition, safety and

in environmental concern10,11

. Quaternary phosphonium

and ammonium salts are the most commonly used PTCs

because of their easy availability and reduced cost12

comparatively and apart from these salts, macrocyclic

poly ethers13,14

(crown ethers and cryptands), polypode

molecule15

, polymer supported PTC16

, polymeric

analogs of dipolar aprotic solvents17

, cyclodextrins18

,

arquad19

were also used as PTCs in the free radical

polymerization of various monomers.

Inspite of various salts used as PTC, cationic

surfactants, when employed along with PDS in free

radical polymerization, play a significant role. They

increase the solubility of the persulfate and catalyze the

polymerization easily. Few of these catalysts that were

employed for free radical polymerization are

summarized here, 1-hexadecylpyridinium chloride20

was

reported by A Jayakrishnan and D O Shah for the

kinetics of free radical polymerisation of MMA using

ammonium peroxy disulphate (NH4)2S2O8 in

ethylacetate-water diphase system. The same PTC

MURUGAN & GEETHALAKHSMI: PHASE TRANSFER CATALYSIS

151

1-hexadecylpyridinium chloride21

was also reported by J

K Rasmussen and H K Smith II in free radical

polymerization of butylacrylate by K2S2O8 in

ethylacetate- water system. A Ramu and G Thangaraj

used hexadecyltrimethylammonium chloride22

as PTC in

free radical polymerization of butylmethacrylate using

peroxydiphosphate in ethylacetate-water diphase

medium. Kinetics of polymerization of MMA using

cetyltrimethylammonium chloride (II)23

coupled with

PDS under benzene-water media was published by V

Bulacovschi, C Mihailescu, S Ioan and B C Simionescu.

From our research group, E Murugan, A Rubavathy

Jaya Priya and P Amirthalingam reported a work on

acrylonitrile employing CTAB24

and CTAB stabilized

by three different metal nanoparticles as PTC using

K2S2O8 initiating system. In our present work, DTAB,

DDTAB and TDTAB were used as PTC along with

PDS as the free radical initiator, and this work has not

been attempted. This study could be useful to establish

the effect of systematic increase of alkyl chain length on

their catalytic property.

MMA25

is a common, important monomer for

radical polymerisation, because of its biocompatibility,

good mechanical and thermo-chemical properties,

excellent weather ability and unique transparency.

MMA has a polar group that plays significant role in

chain propagation as well as in side reaction during the

polymerisation.

For many years commercially available single site

PTC26-29

, multisite PTC30

, polymer supported PTC16

have been used as catalyst. Recently ultrasonification31

and nanocatalyst24

based free radical polymerization

have been carried out in our research. In this study the

effect of cationic surfactants in their CMC and

common concentration in PDS for free radical

polymerization of MMA has been carried out. This is,

infact, attempted for the first time in this reaction.

Moreover no report is available for these cationic

surfactants as PTC for free radical polymerization

under their CMC.

Experimental Section Decyltrimethylammonium bromide (Lancaster),

dodecyltrimethylammonium bromide (Lancaster),

tetradecyltrimethylammonium bromide (Lancaster)

were used without further purification. Potassium

peroxydisulphate (PDS,K2S2O8) (Merck), was

recrystalized twice from distilled-deionized water and

dried under vacuum prior to use. Methylmethacrylate

(MMA), (SRL) was distilled to remove the inhibitor,

hydroquinone and used. K2CO3 (Lancaster) was dried

at 120°C for 24 h and used. Sodium chloride (SRL),

potassium hydroxide (SRL), sodium dithionate

(Merck), sodium salt of anthraquinone-2-sulfonic acid

(Merck), hypovanadous chloride (Merck), ammonium

metavandate (Merck), hydrochloric acid (SRL) and

amalgamated zinc (Merck) were used without further

purification. Solvents like toluene (SRL), methanol

(AR, Qualigens), ethanol (SRL) were purified

according to the literature. Anhydrous dimethyl

formamide (Lancaster) and dichloromethane (SRL)

were used as received. The distilled water obtained

from still was distilled over alkaline KMnO4 in an all

glass quick-fit set up and this double distilled water

was used for the preparation of solutions employed in

the polymerization.

Deaeration technique

The nitrogen gas was used for the purpose of

deaeration and freed from the traces of oxygen and

other impurities by passing through four vertical glass

tubes containing separately (i) Fieser’s solution (ii)

hypovanadous chloride solution (iii) potassium

hydroxide (KOH) solution and (iv) double distilled

water. The Fieser’s solution and hypovanadous

chloride were prepared according to the literature. For

all experiments, the deaeration time was fixed as 30

min unless otherwise mentioned.

Polymerization procedure

The polymerization experiments were conducted in

the long pyrex glass polymerization tubes [4 cm × 20

cm] of about 80 mL capacity with B -24 quick fit socket

fitted with B-24 cone with a provision for inlet and

outlet terminals to pass nitrogen and thermostated at 50

(±) 0.1°C without stirring. Each 10 mL of aqueous phase

containing phase transfer catalyst, and organic phase

containing monomer in toluene were taken in a

polymerization tube and flushed with purified nitrogen

gas for 30 min to ensure inert atmosphere. The

calculated amount of deaerated PDS solution, thermo

stated at experimental temperature, was added to the

polymerization tube and simultaneously started a stop

watch. The polymerization tube was then carefully

sealed by a rubber gasket. PMMA was precipitated

continuously during the polymerization. At the end of

the predetermined reaction time, the polymerization was

arrested by pouring the reaction mixture into ice cold

methanol-water mixture containing traces of

hydroquinone. The precipitated polymer was filtered

through sintered glass crucible (G.4), washed with water

and methanol, and dried in a vacuum oven at 60(±)

0.1°C to attain the constant weight. Temperature

INDIAN J. CHEM. TECHNOL., MARCH 2018

152

variations (in the range, 40- 60°C) for the experiments

were also carried out, to evaluate the thermodynamic

parameters. The rate of polymerization (Rp) was

calculated from the weight of the polymer obtained by

using the following.

Rp = 1000 × W / V.t.M ... (1)

where, Rp = rate of polymerization in mol.L-1

.S-1

,

W = weight of polymer in grams, V= total volume of

the polymerization mixture in mL, t = Reaction time

in seconds and M = molecular weight of the

monomer.

Results and Discussion Employing cationic surfactants as PTC in their CMC

and at a fixed common concentration along with PDS to

initiate free radical polymerization is relatively a new

approach. The present investigation deals with the

kinetics and mechanism of the above said three different

cationic surfactants of varying alkyl chain length as

phase transfer catalysts in the free radical polymerization

of MMA. The reactions were carried out in toluene-

water two phase systems in nitrogen atmosphere under

unstirred condition at 60°C. The dependence of rate of

polymerization, Rp, on various experimental parameters

[MMA], [TDTAB], [K2S208] and temperature was

studied. Many researchers have attempted to enhance

the solubility of PDS in water with various PTC to carry

out free radical polymerization reactions in water and

toluene media. To fix the optimum concentration of the

catalyst and reaction time to follow kinetics, all the three

cationic surfactants under fixed concentration and in

their respective CMC were employed separately. The

[MMA], [K2S2O8] and amount of toluene were kept

constant for all the six reactions at ±60°C. The observed

Rp values for the three PTCs in their respective CMC’s

and in common concentrations are shown in Table 1.

The high Rp value was obtained TDTAB compared to

others at the lowest reaction time of 30 min at a

concentration of 2 ×10-2

mol.L-1. Then, the detailed

kinetic study of free radical polymerization of MMA

was carried out using TDTAB at the fixed time of 30

min by varying the experimental parameters viz.,

[MMA], [K2S2O8], [TDTAB] and temperature. Based on

the kinetic results and the activation parameters, a

suitable mechanism was proposed.

Steady state rate of polymerization

Polymerization reactions were carried out at

different time intervals at fixed concentrations of

MMA, TDTAB, K2S2O8 and temperature to arrive

steady state rate of polymerization. The steady state

rate for polymerization of MMA, derived by carrying

out the polymerization experiments at regular intervals

of time, confirms absence of induction period. During

polymerization the rate increased sharply at first, then

decreased slowly, and finally attained a constant value.

For all the six reactions with the three cationic

surfactants at their respective CMC and in common

concentration of 2 ×10-2

mol.L-1

, the steady state rate of

polymerization attained after 30 min (Fig. 1). Hence,

the concentration of TDTAB was fixed at 2 ×10-2

mol.L-1

and the time at 30 min to carry out the

experiments to study variation in other parameters

Table 1 — Comparative steady state rate of polymerization (Rp)

Surfactant

At Critical micellar concentration At fixed concentration (2×10-2 mol.l1)

Name of the

surfactant

CMC of the surfactant

× 102 mol.l-1

Steady state

time, min

Rate of

polymerization × 104

Name of the

catalyst

Steady state time,

min

Rate of polymerization

× 105

DTAB 5.4 40 2.66 DTAB 40 1.94

DDTAB 1.5 40 4.18 DDTAB 40 5.20

TDTAB 0.3 30 5.99 TDTAB 30 7.76

Experimental condition: [MMA] = 2.0 mol.l-1, [K2S2O8] = 2.0 ×10-2 mol.l-1, Temp = 60 ± 1°C

Fig. 1 — Steady state rate of Polymerization

MURUGAN & GEETHALAKHSMI: PHASE TRANSFER CATALYSIS

153

Effect of [monomer] on the rate of polymerization (Rp)

To assess the effect of [MMA] on the rate of

polymerization (Rp), it was varied in the range 1.4 to

2.6 mol.L-1

, keeping the other parameters constant. The

rate of polymerization increased with the increase in

[monomer]. The plot of 1+ log [MMA] versus 4+ log

Rp was linear with the slope of 1.1 [Fig. 2(a)]. The

order of the reaction with respect to monomer

concentration was unity. This indicates that the

polymerization reaction proceeds with 1.1 order

dependence of Rp on [MMA]. The plot of [MMA]1.1

versus Rp was linear and passed through the origin

[Fig. 2(b)]. Hence, it confirms the first-order with

respect to [MMA]. Generally, in most free radical

polymerization of vinyl monomers, the order with

respect to monomer is always unity. As the

polymerization was performed at 60°C, the incidence

of occlusion is negligible32

and the order with respect to

monomer is unity. The half order with respect to

initiator instead of zero order ruled out the possibility

of primary radical termination, which further confirms

monomer order unity. Similar order of unity was

reported by A Ramu and G Thangaraj22

and V

Selvaraj33

, P Sakthivel and V Rajendran have reported

monomer order unity. T Balakrishnan and S Damodar

Kumar29

in the kinetics of butyl methacrylate using

PDS coupled with tetrabutylphosphonium chloride

have also reported monomer order unity.

Effect of [initiator] on the rate of polymerization (Rp)

To study the effect of concentration of K2S2O8 on

the Rp of MMA, the [monomer], [catalyst], and

temperature were kept constant, and the concentration

of K2S2O8 was varied from 0.8 × 10-2

to 3.2 × 10-2

mol.L-1

. The Rp increased linearly with the increase in

concentration of PDS. A bilogarithmic plot of

2+log[K2S2O8] versus 5 + log Rp was linear with a

slope of 0.51 [Fig. 3(a)]. This indicates that the

Fig. 2(a) — Effect of [Monomer] on Rp; 2(b) — Effect of

[Monomer] on Rp

Fig. 3(a) — Effect of [Initiator] on Rp; 3(b) — Effect of [Initiator]

on Rp

INDIAN J. CHEM. TECHNOL., MARCH 2018

154

polymerization proceeds with 0.51 order. Similar results

were also reported 21

. A plot of [K2S2O8]0.51

versus Rp

was also linear with the line passing through the origin,

thus supporting the above order [Fig. 3(b)]. The order

with respect to initiator is 0.51, only when termination is

bimolecular in the free radical polymerization process. It

also suggests that the monomer-induced decomposition

of Q2S2O8 is absent, where Q2S2O8 is the complex

formed between the PTC (Q+) and the initiator

peroxydisulfate (S2O82-). Generally, the rate of

polymerization is proportional to the square root of

[initiator] at a condition that the termination is

bimolecular. However, in this study, the initiator

exponent was found to be 0.51 for the catalyst TDTAB

at 2 × 10-2

mol.L-1. A square-root relationship between

Rp and [K2S2O8] was also observed by K Y Choi and C

Y Lee13,

Similarly, T Balakrishnan30

, N Jaya

chandramani and T Balakrishnan34

, S Damodar kumar

also observed similar order with respect to [initiator] in

PTC-assisted free radical polymerization of MMA and

acrylonitrile, respectively. R Sakthivel35

, G Arumugam

and T K Shabeer observed similar order with respect to

[initiator] in cetylpyridinium chloride-assisted free

radical polymerization of MMA under PDS system. A V

S Jamal36

, H. Thajudeen, and T K Shabeer demonstrated

MMA kinetics by free radical polymerization under

potassium peroxomonosulphate coupled with

benzyltributylammonium chlorides. E Murugan31

and G

Tamizharasu reported order equal to 0.5 with respect to

initiator in their work of ultra sound assisted free radical

polymerization.

Effect of [catalyst] on the rate of polymerization (Rp)

The effect of concentration of TDTAB on the rate of

polymerization of MMA was studied by varying the

concentration from 0.8 × 10-2 to 3.2 × 10

-2 mol.L

-1

keeping the rest of the parameters constant. The results

showed that the Rp was linearly proportional to the

[TDTAB]. A bilogarithmic plot of 2+ log [TDTAB]

versus 5 + log Rp gave a linear plot with the slope of

0.52 [Fig. 4(a)]. From the slope value, it is inferred half-

order dependence on [TDTAB]. Also, the plot of

[TDTAB] versus Rp passed through the origin

confirming the above observation with respect to

concentration of catalyst [Fig. 4(b)]. C K Y. Choi and C

Y. Lee13

also reported Rp proportional to the square root

of the catalyst in the polymerization of MMA using

K2S2O8-18-crown-6 system. The observed order for

TDTAB catalyst equal to 0.52 is a common one, as

similar inference was demonstrated by T Balakrishnan30

and N Jayachandramani. T. Balakrishnan34

and S.

Damodar kumar in the polymerization of MMA in

toluene/water media using K2S2O8/TEBA system, and in

the free radical polymerization of acrylonitrile using

potassium peroxomonosulphate/TBPC system in ethyl

acetate–water biphasic. V Selvaraj33

, P Sakthivel and V

Rajendran, and A V S Jamal36

, H Thajudeen, and T K

Shabeer, and S Savitha37

and M J Umapathy, in their

polymerization reaction reported 0.5 order for catalyst. T

Balakrishnan38

and S Damodar Kumar reported similar

order in the kinetics of ethyl and methyl acrylates using

oxone as initiator. In this study we have demonstrated

free radical polymerisation using three catalysts with

different chain length such as DTAB, DDTAB and

TDTAB at their CMC and fixed concentration of 2×10-2

mol.L-1, and the results obtained on steady state Rp for

all six concentrations are presented in the Table 1. The

Rps obtained for the catalysts under their CMC were

2.6676 × 10-4, 4.1876 × 10

-4 and 5.9976 × 10

-4 mol.L

-1.S

-1

for DTAB, DDTAB and TDTAB, respectively. The Rp

of TDTAB was higher than that of DTAB and DDTAB.

Fig. 4(a) Effect of [Catalyst] on Rp; 4(a) — Effect of [Catalyst]

on Rp

MURUGAN & GEETHALAKHSMI: PHASE TRANSFER CATALYSIS

155

While comparing the steady state Rp for all the

concentrations, the TDTAB showed higher Rp,

7.76 × 10-5

mol.L-1S

-1 at 2×10

-2mol.L

-1. The increase in

the Rp is attributed to the influence of CMC of the

catalyst39

. Since, the concentration used in this study (2 ×

10-2

mol.L-1) was above CMC for TDTAB and DDTAB,

they can act as micellar reactors and hold a higher number

of initiator molecules in their respective micelles.

However, for DTAB it fell below CMC and so not

favourable for micellization. Hence the Rp was less than

the other two catalysts even at higher reaction time. As a

result, compared to DTAB, the other two catalysts such as

DDTAB and TDTAB required low concentration and

lowest possible reaction time. So, TDTAB showed higher

Rp under lowest reaction time (30 min) for the effective

free radical polymerization. Hence for TDTAB the

reaction time of 30 min at 2 × 10-2

mol.L-1 was fixed for

all the reactions.

Effect of temperature on Rp

Similarly, the effect of temperature on the rate of

polymerization of MMA was studied at five different

temperatures viz., 313, 323, 333, 343 and 353 K with the

catalyst, TDTAB, keeping the other experimental

parameters constant. The Rp increased with increase in

temperature31

. At higher temperature, the rate of initiator

decomposition increased yielding more radicals which in

turn accelerates the rate of polymerization. From the

Arrhenius plot of log Rp versus 1/T (Fig. 5), the overall

activation energy (Ea) for the polymerization reaction,

and the other thermodynamic parameters such as entropy

of activation (∆S#), enthalpy of activation (∆H

#), and free

energy of activation (∆G#) were calculated, and they are

presented in Table 2.

The kinetic features observed in the polymerization of

MMA initiated by K2S2O8 and catalysed by TDTAB

system are as follows. The rate of polymerization

displayed, the following results:

(i) the order with respect to [MMA] = 1.1,

(ii) the order with respect to [K2S2O8] = 0.51,

(ii) the order with respect to [TDTAB] = 0.52 and

(iii) the rate of polymerization is dependent on the

temperature.

General mechanism and rate law

(a) Phase Transfer

K2 2

( ) 2 8 ( ) 2 2 8 (O)2Q S O (Q ) S Ow w

+ − + −→← ... (2)

[Ionic pair (or)complex]

(b) Initiation

dK2

2 2 8 (O) 4 (O)(Q ) S O 2Q+SO −•+ −→ ... (3)

iK

4 (O) 1 3 (O)2Q M M (M-O-SO Q)SO −• •+ + → − ... (4)

(c) Propagation

pK

1 2M M M• •+ → … (5)

. .

. . .

pK

n-1 nM M M• •+ → ... (6)

(d) Termination

tK

n nM M Polymer• •+ →

where K is the equilibrium constant, kd is the reaction

rate constant of decomposition, ki is the rate constant

of initiation, kp is the rate constant of propagation, and

kt is the rate constant of termination. The subscripts

(w) and (o) refer to water phase and organic phase,

respectively. Q+

refers to the catalyst. This mechanism

involves the formation of a neutral quaternary

potassium peroxydisulfate complex [(Q+)2S2O8

2-] in

the aqueous phase, which is then transferred to the

organic phase. The decomposition of this ion-pair

takes place in the organic phase leading to the

formation of 2Q+SO4

•-.

Applying the general principles of free radical

polymerization and steady-state hypothesis to the

Fig. 5 — Arrhenius plot

Table 2 — Thermodynamic parameter

Ea k.J.mol-1 ∆H≠ J.K-1.mol-1 ∆S≠ kJ.mol-1 ∆G≠ kJ.mol-1

21.56 90.06 -184.90 61.66

INDIAN J. CHEM. TECHNOL., MARCH 2018

156

radicals formed, the rate law for this mechanism was

derived as follows:

Rp = kp (kdK)0.5⁄(kt)

0.5 [M]

2[S2O8

2-]w

0.5[Q

+]total⁄1+K[Q

+]

w[S2O82-

]w

where,

[Q+]total = [Q

+]w + [(Q

+)2S2O8

2-]o

This kinetic expression satisfactorily explains all

the experimental results and observations. The net

reaction of the MMA was given in the Scheme 1.

Significance of Ea and other thermodynamic parameters

The Ea is the excess energy required by the reactant

molecules in order to cross the energy barrier to form

the products. A reaction that has lower Ea will proceed

at a faster rate at a given temperature. In the present

study, Ea for the overall rate of polymerization was

equal to 21.56 kJ mol-1

. T Balakrishnan38

and S

Damodar Kumar, reported Ea equal to 40.5 kJmol-1

for

the polymerization of MMA using KHSO5-

tetrabutylphosphonium Chloride which is slightly

higher than the Ea of the present study. J Y Tarng40

and

J S Shih reported the apparent activation energy of 72.9

kJmol-1

for the polymerization of acrylonitrile using

crown ether as PTC which shows higher value than the

present study. In our study, the ∆H# =90.06 kJ.mol

-1

indicates that the reaction is endothermic i.e. the energy

will be absorbed from the surroundings. Higher ∆H#

leads to increase in free energy change ∆G#. Entropy is

regarded as a measure of the disorder of a system.

Negative value of ∆S#-184.90 kJ.mol

-1 in this study

indicates lower disorder at the activated complex. As

the activated complex involves bonding of monomer,

PTC and the initiator together, the entropy decreased,

and hence ∆S# is negative. As ∆S

# is negative -T∆S

#

becomes positive. So, the reaction is expected to

produce at lower rate. It determines the feasibility of

the reaction. In the present study, the ∆G#

has positive

value (61.66 kJ.mol-1

) because both the energy factor

∆H#, entropy factor, T∆S

#, are positive and hence the

reaction can proceed at a higher rate with an increase in

temperature, it is also verified from Fig.5.

Conclusion In this paper, cationic surfactants have been

employed as PTC to study the kinetics and mechanism

of the free radical polymerization of MMA. The

reactions have been carried out under inert and

unstirred conditions at constant temperature (60°C) in

toluene/water biphase media using K2S2O8 as the

water-soluble initiator. First the steady state of

polymerization is ascertained by employing the 3

different cationic surfactants under their respective

CMC and in common concentration. On comparing the

six steady state rate of polymerization of the cationic

surfactants in their respective CMC’s and in common

concentration, the TDTAB is verified to yield higher

Rp of 7.76 × 10-5

mol.L-1

.S-1

than others at the lowest

reaction time of 30 min at its concentration 2 × 10-2

mol.L-1

. The dependence of the rate of polymerization

on various experimental conditions such as different

concentrations of monomers, initiator, catalyst and

temperature has been discussed. The order with respect

to monomer, initiator, and catalyst is 1.1, 0.51 and

0.52, respectively. The activation energy and the other

thermodynamic parameters of the polymerization of

MMA are calculated from the slope of log Rp versus

1/T in the temperature range 40-80°C. So, cationic

surfactants can also be simple, competitive PTC for the

free radical polymerization of MMA. Based on the

kinetic results, suitable mechanism has been proposed.

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K2S2O8/Q+X-

Methylmethacrylate polymethylmethacrylate

Scheme-1 Net reaction of MMA

CH3

O

O

H2C

CH3

CH3

O

O

CH3

n

MURUGAN & GEETHALAKHSMI: PHASE TRANSFER CATALYSIS

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