CHAPTER I

1.1. GENERAL ASPECTS

A large number of smaller molecules unite to form a

macromolecule or polymer. This chemical process is called

polymerization reaction. A monomer is defined as a chemical

compound containing one or more polymerizable structural units1-5.

The macromolecules consisting of identical monomers are called

homopolymers. When different types of monomers are used, the

resulting polymer is called copolymer or mixed polymer. The

polymerization reactions are broadly classified into two types, namely

condensation polymerization and addition polymerization. In

condensation polymerization, the polymer formation is in general

accompanied by the elimination of smaller molecules such as water and

methanol. But in addition polymerization, which is confined to a

particular type of unsaturated compounds namely olefins and their

derivatives, the polymer is formed without the elimination of simple

molecule.

Addition polymerization is further classified into two categories

namely ionic polymerization and free-radical polymerization. The ionic

polymerization proceeds through the formation of carbonium ion,

whereas the free-radical polymerization proceeds through the formation

of active free-radicals.

1
 The free-radical polymerization involves a chain reaction,

proceeding in three steps namely (1) activation or initiation (2)

propagation and (3) termination. It is observed that the addition of

small amount of foreign substances like oxygen, iodine and quinone

suppresses the rate of polymerization due to quenching of free radicals.

The active radicals generated in the initiation step successively

combine with monomer molecules to give a long chain active radical.

kp
RM1 + M RM2
kp
RM2 + M RM3
kp
RM3 + M RM4

The rate of propagation in each step is assumed to be the same.

In the final step the growing polymer radicals lose their activity and

become an inactive polymer. The termination may proceed through the

following reactions:

(i) By recombination

kt
R-CH2-CHX + XCH- CH2-R R- CH2-CHX-XHC-CH2R

(ii) By disproportionation

kt
R-CH2-CHX + XCH-CH2-R R-CH2-CH2X + R-CH=CH-X

2
(iii) By metal

kt
R-CH2-CHX + Metal ion Polymer + Reduced metal ion

(iv) By primary radical

kt
R-CH2-CHX + R R- CH2-CHXR

The retarders like nitrobenzene reduce the rate of polymerization

while the inhibitors like benzoquinone, almost completely inhibit the

reaction. A well known and an effective inhibitor for vinyl polymerization

is molecular oxygen. The stable free radical diphenylpicrylhydrazyl

(DPPH) is also an effective inhibitor for polymerization.

The polymerization reaction can be initiated by various systems

such as organic substances, inorganic salts, metal ions and metal ion

complexes of organic ligands and metal ion complexes of inorganic

ligands in aqueous medium.

1.2 METALLIC REDOX SYSTEMS AS INITIATORS

Redox polymerization of vinyl monomers, initiated by transition

metal ions in their higher oxidation states in aqueous medium, can

provide valuable information. Among the metals, the transition metal

ions are most widely used to initiate polymerization in aqueous

solutions. Transition metal ions are easily reducible to the lower valency

state resulting in the formation of free-radicals of the reducing agent.

The metal ions can be used to initiate polymerization as its simple salt

3
or in combination with complexing ligands. A survey of the available

literature on the polymerization of vinyl monomers using the metal ion

redox initiating systems has been given.

Viswanathan and Santappa6 have shown that in the presence of

reducing agents such as n-butanol, ethylene glycol, cyclohexanone and

acetaldehyde, Cr(VI) is capable of initiating vinyl polymerization. It was

found that the rate of polymerization decreased with increasing [Cr(VI)]

and was proportional to [H+] indicating the involvement of Cr(VI) in the

termination step and also the importance of protonated species in the

reaction. Similar cases of metal ion termination were reported in the

polymerization of AN initiated by Cr(VI) thiourea7, and Cr(VI)-glycerol

redox systems8.

Wang9 reported the polymerization of N-vinyl carbazole and

4-vinyl pyridine initiated by copper(II) nitrate. Tazuke and Gkamura10

reported that the polymerization of 4-vinylpyridine was initiated by an

one electron transfer from monomer to the copper(II) acetate in a

complex.

Inove and Yamuchi11 reported the rapid polymerization of MMA

by a combination of organic acids and copper powder or cuprous

chloride. Guchi Tatsuro et al.12 observed that the high concentration of

Cu2+ inhibited the polymerization of MMA initiated by urea-CuCl2 redox

system. Yinghai et al.13 investigated the polymerization of AN initiated

by Cu(II) and urea in alkaline medium.

4
 It is well known that vanadium(V) by itself does not initiate

polymerization but does so only in the presence of suitable reducing

agents. Santappa et al. were the first to make a systematic study of the

polymerization of vinyl monomers using V(V) in combination with

reducing agents. They used cyelohexanol14, lactic acid15 and pinacol16 in

the presence of V(V) for the polymerization of AN. In these systems, Rp

showed a second order dependence on (monomer), a first order

dependence on reductant and inverse first order dependence on V(V).

The termination of growing polymer chain was found to occur by the

reaction with V(V). Mutual terminations as well as termination by

primary radicals were considered to be unimportant in these systems.

Click and Senwar17 studied the polymerization of AN using

V(V) malic acid system in sulphuric acid medium. The Rp was

proportional to [malic acid] and [monomer]2. Nayak et al. used

thiourea18, tartaric acid19, cyclohexanone20, propane-1,2-diol21 and

ethylene glycol22 as reducing agents in combination with V(V) for the

polymerization of AN. The V(V)cyclohexanone23 redox system was also

used for the polymerization of MA and MMA. The results were

consistent with the formation of an intermediate complex between the

ketone and the metal ion, the decomposition of which leads to initiating

radicals.

Anuradha et al. studied the polymerization of AN by using

V(V) glycerol24 redox system and proposed linear termination of

5
polymer chains. Das et al. reported the polymerization of AN and MMA

using V(V) ascorbic acid25 and V(V) thioacetamide26 systems. The

kinetics and mechanisms of retardation of V(V) -cyclohexanone initiated

polymerization of AN by phenol were discussed by Jena et al27. The

polymerization of AN initiated by V(V) thiourea redox systems was

reported by Jinynan et al28. Srinivas et al.29 reported the polymerization

of AN initiated by pervanadic acid (PVA). If the concentration of PVA is

greater than 5x10-3 M, there is no induction period. The rate of AN

disappearance was proportional to [AN]2, [PVA]10 and decreased with

increase in [V5+] at high concentration.

Hussain and Dass30 reported the polymerization of MMA initiated

by a mixture of urea and CCl4 and accelerated by Fe(III) complex

namely hexakis (dimethyl sulfoxide) iron(III) perchlorate. The maximum

rate of polymerization was reduced, when a 6:1 molar ratio of urea to

Fe(III) complex was achieved. Dass and Baruah31 noticed the

accelerated rate of polymerization of MMA in the presence of hexahis

(dimethyl sulfoxide) iron(III) perchlorate in DMSO, even in the absence

of reducing agent at 60C. Arai Yoshio et al.32 investigated the

polymerization of MMA by iron(III) nitrate in aqueous solution

containing a non-ionic surfactant. The polymerization was hindered by

the addition of 2-phenyl-1,1-picryl-hydrozyl-1,4-benzoquinone. The

enhanced rate of polymerization of MMA, initiated by semicarbazide

complex of Fe(III) and CCl4 in DMF, was reported by Dass et al.33

6
 The polymerization of MMA in CCl4 medium with ferric laurate, a

metal soap in combination with n-hexylamine as the initiator system

was studied by Saha and Chaudhuri34. The rate of polymerization was

found to be linear with the monomer concentration and proportional to

the square root of both ferric ion and amine concentration. In the

absence of amines there was no polymerization even after 2 hours.

Jayasubramanian et al.35 reported the vinyl polymerization by

thallium(III) acetate. Like this thallium(III) sulphate36 was also found to

initiate polymerization of MMA.

Bamford and Lind37,38 studied the polymerization of vinyl

monomers initiated by manganese(III) triacetonylacetonate. Nikolaev39

showed that the introduction of a carboxylate group into the above

ligand increased the rate of polymerization. In the study of the

polymerization of AAM and methacrylamide (MAA) initiated by

manganese(III) acetate, Santappa et al.40-42 proposed that the

termination was by mutual combination for the first two monomers

while termination was by Mn(III) ions for AA. The permanganate ion in

combination with organic acids such as oxalic acid,43-50 ascorbic acid,51

tartaric acid,52 malic acid,53 thioglycollic acid,54-55 and citric acid56 had

been used to initiate vinyl polymerization.

Ganga Devi and Mahadevan57 studied the polymerization of AN

using Mn(III) and reducing agents such as diacetone alcohol and

malonic acid. No polymer was formed in the absence of a reducing

7
agent showing that there was no reaction between monomer and

Mn(III). Complex formation between Mn(III) and reducing agent and its

decomposition to produce the initiating free-radicals were proposed in

the mechanism. During the polymerization of AN and MMA using

Mn(III)-malonic acid58 redox system, the polymerization was found to

get terminated by mutual combination of growing chains.

In the polymerization of AAM using Mn(III)-pinacol59 redox

system, the rate of polymerization was proportional to [AAM] and

[Pinacol] and was independent of [Mn(III)]. Jayakrishnan and

Mahadevan60 investigated the polymerization of AN initiated by Mn(III)-

cyanoacetic acid and Mn(III)-2-butanone redox systems and suggested

that the initiation was through the complex formed between Mn(III) and

reducing agent and termination by the mutual combination of growing

chains. Though the above authors suggested the complex formation,

the complex formation constant had not been evaluated.

Nayak et al.61 investigated the polymerization of AN with a series

of organic acids as reducing agents and found that the order of

reactivity varied as citric > tartaric > ascorbic > oxalic > succinic >

glutaric > adipic acid. Similarly in the polymerization of MMA, initiated

by Mn(III)-alcohol redox systems62, the reactivity of alcohols was found

to vary in the order : 1-propanol > glycerol > ethylene glycol > isobutyl

alcohol > 1-butanol > 1,2-propanediol > cycloheptanol > cyclohexanol >

cyclopentanol. The kinetics of polymerization of AN, initiated by Mn(III)

8
with a series of amides redox systems, was investigated by Samal et

al.63 It was reported that under identical conditions, the order of

reactivity of the amides was, thioacetamide > succinamide > acetamide

> formamide, the order of reactivity of the amides was explained by

considering the existence of resonance and hyperconjugation effects.

In the polymerization of AN, initiated by Mn(III)-glycerol and

Mn(III)-allyl alcohol64 systems, oxidation of both glycerol and allyl

alcohol proceeded through an intermediate metal complex.

Senapathy et al.65, who studied the polymerization of AN initiated

by Mn(III)-glycerol system in aqueous acetic acid, reported a decrease in

the rate of polymerization with an increase in the acetic acid

concentration. Further, an increase in the concentration of H2SO4

caused an increase in the reaction rate initially but at higher acid

concentrations, the rate again decreased. Jeyakrishnan et al.66 studied

the polymerization of AN and MMA initiated by Mn(III)-propanedinitrile

redox system in aqueous H2SO4, DMF and glacial acetic acid. Mutual

termination was found to occur in all these systems. Elayaperumal

et al.67 studied the kinetics of polymerization of AN and AAM initiated

by Mn(III)-diglycollic acid system. The rate coefficients were related to

reactivities of monomer and polymer radicals.

Balakrishnan and Subbu68 investigated the polymerization of

acrylamide initiated by manganese(III)-acetate-ethoxyacetic acid (EAA)

redox system in aqueous H2SO4. The polymerization process was

9
initiated by the free-radical arising from the oxidation of EAA by Mn(III)

and terminated by mutual combination of growing polymer radicals.

They also found that the disappearance of Mn(III) followed a first order

reaction.

Kunyan et al.69 investigated the reactivity of a series of

substituted carboxylic acids in combination with Mn(III) during vinyl

polymerization and reported the following order of reactivity : citric acid

> lactic acid > glycine > n-butyric acid > methacrylic acid.

From the foregoing survey, it becomes evident that the

reactivity of the reducing agents depended on the resonance and

hyper conjugation effect. In most of the above reactions, the rate of

disappearance of metal ions followed the first order reaction during

polymerization. It was noticed that the formation of polymer was

terminated by mutual combination of growing chains. Further it was

reported that the rate of polymerization increased upto certain acid

concentrations but above which the rate of polymerization decreased.

1.3 CHEMISTRY OF CERIUM

Cerium belongs to the group of inner transition elements with the

incompletely filled 4f level. Ce(IV) (4f05s26p6) and Ce(III) (4f15s26p6) are

the two important oxidation states of cerium. Ce(IV) compounds are

more acidic, more easily hydrolysed and more susceptible to

complexation than Ce(III). The salts of quadrivalent cerium are noted for

10
their strong oxidizing power and are largely used in analysis and

synthesis. Oxidation of a substrate by Ce(IV) occurs through transfer of

a single electron from the substrate to the oxidant

Ce(IV) + e- Ce(III)

For this reason, the mechanism of oxidation by Ce(IV) in many

cases is simpler than similar oxidations with chromate and manganate.

Moreover, the oxidation potential of Ce(IV)-Ce(III) couple is higher than

many of the common oxidizing agents. The oxidation potential of Ce(IV)

in an acid medium varies from 1.28-1.87 V depending on the nature

and concentration of the acid used. The ceric salts exist as different

ionic species in different acid media depending on the pH of the

solution. In perchloric acid medium, ceric salt exists as Ce(OH)3+ and

Ce(OH)22+ as observed by Sherill et al. 70

Ce(OH)3+ + H2O Ce(OH)22+ + H+

The value of the above equilibrium constant K was proposed as

0.6. Heidt and Smith71 who studied the photochemical oxidation of

water by Ce(IV) in perchloric acid medium concluded that Ce(IV) forms a

dimeric species in 1 M perchloric acid.

In sulphuric acid medium, Moore and Anderson72 observed a

complex containing one Ce(IV) and one sulphate ion as the predominant

11
species upto a concentration of 0.01M H2SO4. Hardwick and

Robertson73 have studied the association of ceric ions with sulphate ion

spectrophotometrically and proposed the existence of complexes of the

type Ce(SO4)2+, Ce(SO4)2 and (Ce(SO4)3)2- In nitric acid medium

Blaustein and Gryder74 identified the existence of the following dimers

and

2 Ce(IV) (Ce(IV))2

Ce(IV) + Ce(III) (Ce(IV) Ce(III))

the association constants for these dimers were also reported.

Ceric salts were found to oxidise different kinds of organic

compounds. The oxidation of a number of aliphatic ketones and

aldehydes was studied by Shorter and Hinshelwood75 who correlated

their structures and enolisation constants with reactivity. The kinetic

study of the oxidation of acetone with ceric ammonium nitrate was

made by Shorter.76 Enol form of acetone and Ce(OH)3+ were proposed as

the reactive species. The oxidation was inhibited by bromine which

removed the enol form as it was formed. Venkatakrishnan and

Santappa77 also reported that the enol forms of aliphatic ketones were

reactive towards ceric ions. The studies on the kinetics of oxidation of

methanol,78 ethanol,79 2,3-butanediol,80 glycol,81 pinacol82 and benzyl

alcohol83 by Ce(IV) have been reported. The mechanism of oxidation of

12
the above organic substrates by Ce(IV) in perchloric or nitric acid

medium involved the complex formation between the substrate(s) and

Ce(IV) and then the decomposition of the complex to give a radical (R)

which subsequently reacted to yield the products.

K kd
S + Ce(IV) Complex R + Ce(III) + H+

fast

R + Ce(IV) products + Ce(III) + H+

Yadah and Bhagat84 studied the kinetics of oxidation of malonic

acid by ceric sulphate and observed a first order dependence with

respect to each reactant. Therefore, in the following section, the

literature on cerium ion as initator has been reviewed.

1.4. CERIC ION AS AN INITIATOR OF VINYL POLYMERISATION

At first Bacon85 reported the initiation of vinyl polymerization by

Ce(IV). A qualitative study of the initiation capacities of ceric ions in

different acid media was made by Saldick86 in 1956. Later

Venkatakrishnan and Santappa87 studied to some extent the kinetics of

ceric ion initiated polymerization. Ananthanarayanan and Santappa88

made a more comprehensive kinetic study on vinyl polymerization. The

rate of polymerizations was found to increase in the order HClO4 >

HNO3 > H2SO4 media. Ceric ions initiated as well as terminated the

polymerization. The rate of polymerization was found to bear a square

dependence on monomer concentration and be independent of Ce(IV)

13
concentration, confirming both the initiation and termination by ceric

ions.

Narita et al.89 proposed a mechanism for the polymerization of

AAM by ceric ammonium nitrate, wherein AAM formed a complex with

ceric ion which yielded the initiating species through the abstraction of

H from the amide group of the monomer. Karpenko et al.90 reported the

isothermal polymerization of AN in the presence of Ce(IV).

Pramanick and Sarkar91 discussed the mode of initiation by ceric

salt in the polymerization of MMA. It was found that the basic reaction

for the generation of initiating radicals was strongly dependent on the

acidity of the medium and independent of the nature of the anion. In a

moderately acidic medium, the primary reaction was the formation of

hydroxyl radicals from the oxidation of water by ceric ion. These

hydroxyl radicals initiated polymerization and appeared as end-groups

in the polymer. When ammonium ions were also present as in the case

of ceric ammonium sulphate, some of the hydroxyl radicals reacted with

ammonium ions producing ammonium radicals and hence polymers

with both hydroxyl and amine end groups were formed. In a strongly

acidic medium, no specific end groups could be identified in the

polymer.

Dainton92 pointed out the advantages of a redox system for the

initiation of vinyl polymerization. There was a decrease in activation

energy by about 80 kJ/mol for the radical production in a redox system

14
when compared to a non-redox system. This would permit

polymerization at a lower temperature, uncomplicated by side reactions.

Mino et al.93 investigated and found that the ceric salts such as ceric

ammonium nitrate and ceric ammonium sulphate were capable of

forming effective redox systems in the presence of organic reducing

agents such as alcohols, thiols, aldehydes and amines. They carried out

the polymerization of AAM initiated by ceric nitrate3-chloro-1-

propanol redox system and found that at constant hydrogen ion

concentration, the rate of polymerization was independent of ceric ion

concentration.

Subramaniam and Santappa94 carried out the polymerization of

AN, MA and MMA in perchloric acid medium using ceric perchlorate-

formaldehyde [F] redox couple. The rate of polymerization was found to

be proportional to [M]2 [F] for all the systems. The rate was found to be

independent of [Ce(IV)] for the systems with MA or AN but inversely

proportional to [Ce(IV)] with MMA as the monomer. The rate of ceric ion

disappearance was directly proportional to [Ce(IV)], [F] and [M].

Termination of the polymer chain radical was reported to occur by

reaction with metal ions. The same authors also studied the

polymerization of MA and MMA initiated by ceric ammonium sulphate-

malonic acid95 redox systems in sulphuric acid medium and reported

that the initiation was by the primary radical of malonic acid and

15
termination occurred by the mutual interaction between growing

radicals.

Saha and Chaudri96 reported the polymerization of AN by ceric

ion-triethylamine system. They97 also found out the effect of various

amines on the ceric ion initiated polymerization of vinyl monomers.

They explained that a redox reaction between ceric ions and the amines

was dependent on the electron donating ability of the substituents.

Narita et al.98 reported the polymerization of MMA using Ce(IV)

pinacol redox system. They found that Ce(IV) was just an initiator at

lower concentrations and acted also as a terminator at higher

concentrations. Anuradha et al. studied the polymerization of AN using

Ce(IV) glycerol99 and Ce(IV) acetophenone100 redox systems. Both the

systems followed similar kinetics with the rate of monomer

disappearance being proportional to [AN]1.5, [Ce(IV)]0.5 and [reductant]0.5

and the rate of disappearance of Ce(IV) being proportional to [Ce(IV)]

and [reductant]. The results were explained by assuming the production

of initiating radicals by the oxidation of substrate by Ce[IV] and

termination by the mutual combination of growing polymer chains. The

above mentioned authors101 also reported in the polymerization of AN by

Ce(IV)-thiourea redox system that the rate of monomer disappearance

was directly proportional to [thiourea] and the square of [monomer] and

inversely proportional to [Ce(IV)]. The rate of Ce(IV) disappearance was

proportional to [Ce(IV)] and [thiourea] being independent of [monomer].

16
A kinetic scheme was given, suggesting the production of initiating

radicals from the oxidation of thiourea by Ce(IV) and termination by the

interaction of the chain radicals with Ce(IV).

The aqueous polymerization of AN by Ce(IV)- acetaldehyde redox

system at 25C was reported by Riaz Ahamed et al.102 The results

obtained were found to be identical to those obtained for Ce(IV)

glycerol and Ce(IV) acetophenone systems. The activation energy for

the overall rate of polymerization was 67.0 kJ/mol and the value of the

rate constant was 2.48 mol dm-3s-1

Mohanty et al.103 investigated the polymerization of AN using

Ce(IV)-propane 1,2-diol (PDL) system in aqueous sulphuric acid

medium. The polymerization rate was proportional to [Ce(IV)], [PDL] and

to the square of [AN]. The polymerization of AN initiated by Ce(IV)

mannitol104 redox system was also studied by the same authors. At low

ceric ion concentration, mutual termination was important whereas at

higher concentrations, linear termination was the exclusive step.

Misra et al.105 reported the homogenous polymerization of AAM

initiated by ceric ammonium sulphate citric acid system. The rate of

monomer disappearance was found to be proportional to [monomer] and

[Ce(IV)]0.58 and independent of [citric acid]. The independence of the rate

of polymerization on [citric acid] might be due to the balance that exists

between the generation and consumption of the free-radicals in the side

17
reactions. The rate of ceric ion disappearance was directly proportional

to [ceric ion] but independent of [monomer].

Polymerization of AN, initiated by Ce(IV)- thioacetamide redox

system, was investigated by Samal et al.106 The rate of polymerization

and the rate of Ce(IV) disappearance were measured. The effect of

certain compounds on the rate of polymerization was also studied.

Termination o the polymer chain was found to occur by the reaction

with metal ions.

The polymerization of AN, initiated by ceric ion organic sulphur

compound redox systems, was studied by Lenka and Nayak.107 The

reactivities of organic sulphur compounds used with ceric ammonium

sulphate to initiate the polymerization of AN decreased in the order :

cysteine > thiourea > 2- aminoethanethiol > thioglycollic acid. The rate

of polymerization and the chain length of polyacrylonitrile increased

with increasing monomer concentration while the latter alone decreased

with increasing ceric ion concentration.

Misra and Bhattacharya108 found out the polymerization of AAM

(M) initiated by ceric ammonium sulphate-thiourea (TU) system. The

polymerization rate depended on [M]1,2, [Ce(IV)]0.5 and [TU]0.5. The

activation energy was reported to be 24 kJ/mol.

Misra and Khatib109 repoted the polymerization of AAM initiated

by Ce(IV)-lactic acid redox system. The rate of monomer disappearance

18
increased with increasing [lactic acid], [AAM] and reaction temperature.

It decreased with increasing [H2SO4] and [catalyst]. The termination

was, however, found to occur by the mutual combination of growing

chains.

The polymerization of AN by Ce(IV)-glucose system was studied by

Padhi and Singh110. The rate of polymerisation was proportional to

[monomer]2, [glucose] and [Ce(VI)]-l. A mechanism involving termination

by Ce(IV) was proposed. Nageswar Rao et al. pointed out the

polymerization of AN using Ce(IV)-diacetone alcohol111, Ce(IV)-malic

acid112 and Ce(IV)-ethyl methyl ketone113 redox systems. In all the

three systems, the rate of polymerization was proportional to

[monomer]1.5Ce(IV)]0.5 and [reductant]. A mechanism involving primary

radical initiation and mutual termination was proposed.

Pramanick and Chakraborthy114 studied the polymerization of

MMA, MA, AAM and AN using Ce(IV)-sulphamic acid redox system.

The rate of polymerization of MMA increased with [ceric ion] upto

0.7X10-3 M and then decreased. The kinetics of polymerization of AN by

ceric ion butane 1,4-diol system was studied by Mohanty et al115. There

was no evidence for the formation of a complex between the diol and the

oxidant. The results were consistent with a linear mode of termination.

The polymerization of AN initiated by Ce(IV)-dimethyl sulphoxide

(DMSO) system in perchloric acid was studied by Nageswar Rao et al.116

19
The rate of polymerization was proportional to [monomer]2 and [DMSO]

while being independent of [Ce(IV)]. Termination was found to occur

exclusively by the interaction of chain radicals with cerium (IV) ions.

Padhi and Singh117 investigated the polymerization of AN by

using Ce(IV) sucrose redox system and reported that the rate of

polymerization was proportional to [AN]1.5 and the rate of Ce(IV)

disappearance was almost independent of [AN).

The kinetics of the aqueous polymerization of MMA, initiated by

Ce(IV)-thiourea(TU) system in 1 M H2SO4, was studied by Pramanick

and Chatterjee.118 It was found that the Ce(IV) and thiourea initially

formed 1:1 complex which then reacted with uncomplexed ceric ion. In

the presence of excess of Ce(IV)-TU complex, the polymerization of MMA

was initiated by TU radicals whereas the slight excess of TU was found

not to influence the rate of polymerization. The overall activation energy

for the polymerization reaction was determined, in the temperature

between 15C and 25C, as 42.65 kJ/mol.

Fernandez et al.119 reported the results of the polymerization of

MMA in aqueous nitric acid with ceric ammonium nitrate-2- butanol

(IBA) redox system. The rate of polymerization was proportional to

[monomer]1.5 and [IBA]0.5. The rate of ceric ion disappearance was Rce

directly proportional to [Ce(IV)]. The polymerization rate was found to

have increased with [Ce(IV)] from 1.0 x 10-3 to 3.0 x 10-3M. From [Ce(IV)]

=3.0 x 10-3 to 1.5 x 10-2 M, the rate became independent of [Ce(IV)] but

20
beyond this concentration, the rate was found to have decreased. The

half order on the [IBA] and 3/2 order on the [MMA] suggested the

mutual termination of growing polymeric radicals.

Fernanda et al.120 investigated the polymerization of MMA,

initiated by ceric ammonium nitrate-methanol redox system, in

aqueous nitric acid medium. The concentration of nitric acid in the

reaction medium was varied from 1.0 x 10-3 N to 1.0 N. An increase in

the acid concentration from 1 x 10-3 N to 9 x 10-2 N caused an

increase in the rate of polymerization, but for acid concentrations

above 9x10-2N the Rp values decreased progressively. At the high

concentration of nitric acid, the protonation of methanol did not favour

the complex formation between ceric ion and methanol.

Fernandez and Guzman121 reported the effects of nitric acid and

nitrate ion concentration on the polymerization of MMA initiated by

ceric ammonium nitate-2-propanol and 2-butanol redox systems. In

these systems, the Rp values initially increased rapidly on increasing the

nitric acid concentration upto 0.1 M and then decreased with further

increase of acid concentration. It was shown that ceric ions in acid

solution consist of different species such as Ce4+, Ce(OH)3+ and

(Ce-O-Ce)6+, whose relative amounts depend on the acid concentration,

according to the equilibria (1) and (2).

21
 Ce4+ + H2O (CeOH)3+ + H+ (1)

2(CeOH)3+ (Ce-O-Ce)6+ + H2O (2)

Abdulkadir et al.122 studied the polymerization of acrylamide

initiated by Ce(IV)-tartaric acid redox system in sulphuric acid and

perchloric acid media. They found the first order dependence with

respect to [Ce(IV)]. Dong Jianhua et al.123 reported the polymerization

of AAM initiated by Ce(IV)-aceto acetanilide redox system. The rate of

polymerization was 170 times faster for the above system than with

Ce(IV) only. Pojman et al.124 studied the polymerization of AN by

Ce(IV)-bromoderivatives of malonic acid systems. During

polymerization, the Ce(III) was reoxidised in an autocatalytic process

involving HBrO2 and the radical BrO2. The BrO2 radical was involved

in termination of polymer chains through disproportionation.

Wen-Cheng et al125 investigated the polymerization of acrylamide

by Ce(IV)-EDTA redox system in aqueous medium through

spectrophotometric process. The radicals which initiated the

polymerization were found as

K
Ce(IV) + EDTA Ce(IV) - EDTA
Complex C
kd
Ce(IV) EDTA EDTA + Ce(III) + H+
Complex C R

22
 The concentration of Ce(IV) decayed exponentially with reaction

time, following the first order kinetics. The complex formation constant

of the above system was larger than those obtained from other Ce(IV)-

alcohol complex systems. The enhanced stability of Ce(IV)-EDTA

complex indicated that a strong chelated complex occurred. The

complex formation constant (K) and disproportionation constant (kd)

of Ce(IV)-EDTA chelated complex were reported as 1.67 x 104 and

3.77 x 10-3 respectively. The rate dependence of polymerization on [M]

and [EDTA] both followed a second order reaction when the monomer

concentration was lower. The activation energy was found to be

62 kJ/mol.

The polymerization of acrylamide and acrylonitrile using ceric ion

as initiator can be promoted greatly by the tartaric acid, The kinetic

equation and overall activation energy of the polymerization of

acrylamide initiated by ceric ion/tartaric acid have been obtained126.

Aqueous polymerization of methyl methacrylate initiated by ceric

ion reducing agent systems in sulphuric acid medium was studied by

Venkataramana Reddy et a1.127 Polymerization of methacrylate (MMA)

was carried out in aqueous sulphuric acid medium at 30C using

ammonium ceric sulphate (ACS) / methyl ethyl ketone (MEK) and

ammonium ceric sulphate / acetone as redox initiator systems. A short

induction period was observed with both the initiator systems, as well

as the attainment of limiting conversion for polymerization reactions.

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The rate of ceric ion consumption RCe was first order with respect to

Ce(IV) concentration in the concentration range (0.5 - 5.5) x 10-3 M and

0.5 order with respect to reducing agent concentration in the

concentration ranges (0.0480 - 0.2967 M) and (0.0500 - 03912 M) for

Ce(IV) - MEK and Ce(lV)-acetone initiator systems respectively.

Nalla Mohamed128 has studied the polymerization of acrylamide

initiated by Ce(IV) -iminodiacetic acid (IDA) redox system in aqueous

solution. Polymerisation behaviour as a function of the concentration of

Ce(IV), IDA and acrylamide as well as temperature has been studied.

The rate of polymerization has been found to be first order with respect

to the concentration of monomer. The complex formation constant (K)

and disproportionation constant (kd) of Ce(lV) IDA complex were

evaluated. The effect of excess of Ce(IV), mineral acid and

complex (initiator) concentrations was studied. Evaluation of

complex formation during polymerization of acrylamide initiated by

Ce(IV)-aminopolycarboxylate ligands has been done by the same author.

Radical polymerization of acrylamide initiated by ceric ammonium

nitrate-methionine redox initiator system was studied by Betuldince

et al.129 The polymerization of acrylamide, initiated by [Ce(IV)]

ammonium nitrate-methionine redox initiator system was carried out in

an aqueous solution at different reaction conditions.

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 The kinetics of polymerization of acrylonitrite (AN), initiated by a

V(V)-cyclohexanone redox system in the presence of a surfactant, was

studied over a temperature range of 30C-50C in acidic medium by

Manabendra Patra et al.130

Nanda and Kishore131 have studied catalytic oxidative

polymerization of vinyl monomer using cobalt phthalocyanine complex

and an exploratory investigation on the polymerization of vinyl acetate

has also been done.

A kinetic study has been done on the polymerization of

acrylonitrile initiated by the Cerium (IV) Glutamine132 redox system.

Redox polymerization of acrylonitrile, initiated by the system

Tristrinitratocerium(IV)paraperiodate-propane-l,2-diol133, has been

studied in aqueous sulphuric acid under nitrogen in the temperature

range 30C - 40C. The relation between the rate of polymerization and

[M]2 or [R] is linear.

The polymerization of acrylamide, acrylic acid and methyl

acrylate, initiated by Mn(III) -aspartic acid redox system in aqueous

sulphuric acid, has been studied by Shanmuga Sundari and Subbu134.

Rajendran and Subbu have studied the polymerization of

methylacrylate and acrylamide initiated by the redox system

Mn(III)- tartaric acid in aqueous sulphuric acid medium at 15C135.

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