LIST OF ABBREVIATIONS: 1. AN-Acrylonitrile 2. AA-Acrylicacid 3. AAm-Acrylamide 4. PAN-Polyacrylonitrile 5. MA-Methylacrylate 6. MMA-Methyl Methacrylate 7. PEG-Polyethylene Glycol 8. NCTB-N-Cetyl-Trimethyl Ammonium Bromide 9.

CTAB-Cetyl-Trimethyl Ammonium Bromide 10. CAN-Ceric Ammonium Nitrate 11. CAS-Ceric Ammonium Sulphate 12. CA-Citric Acid 13. CS-Ceric (IV) Sulphate 14. LA-Lactic Acid 15. CMC-Critical Micelle Concentration 16. SDS-Sodium Dodecyl Sulphate 17. [ ] Concentration 18. I-Ionic Strength 19. C-Temperature In Degree Celcius 20. K-Degrees of Kelvin 21. Rp-Rate of Polymerisation 22. Ri-Rate of Initiation
o

Introduction Macromolecules or polymers are very high molar mass compounds consisting of several structural units inter-connected by covalent bonds. The molar mass of a polymer may vary from 5,000 to several millions. Fundamentals research in polymer chemistry was done from 1920 to 1950 by the German chemist,Hermann Staudinger who won the 1953 chemistry Nobel prize. Karl Ziegler,Giulio Natta and Paul J.Flory also made signifigant contributions to the polymer chemistry. Flory was awarded the 1974 chemistry Nobel prize. P.G.de Gennes, the French physicist was awarded the 1991 physics Nobel Prize for studying polymer liquid crystals and developing the scaling concept in polymer dynamics. A polymer consists of a large number of simple monomeric structural units which are repeated over and over again to form a giant molecule called a macromolecule. The simple unit is called the repeat unit. In the polymers .A-A-A A-A .. and .AB-A-B-A-B.. for instance, the repeat units are A and A-B respectively. A high polymer is one in which the number of repeating units is in excess of about 1000. This number is termed as Degree of polymerization. Polymers find immense use in glass and ceramics industries. They are also being employed for rocket constructions polymer engineering deals with the splitting up of natural high molar mass compounds to produce valuable food stuffs. The hydrolysis industry, for instance,produces ethyl alcohol by hydrolysis of wood.

2. Types of polymer and polymerization One classification based on polymer structure and divides polymers into condensation and addition polymers. The other classification is based on polymerizations mechanism and divides polymerization into step and chain polymerizations. The condensation addition classifications is based on the composition or structure of polymers. The step-chain classification is based on the mechanism of polymerization. Vinyl monomers can be made to react with themselves to form polymers by conversion of their double bonds into saturated linkages. nCH2=CHY ( CH2=CHY )
n

Where Y can be any substituent group such as hydrogen, alkyl, aryl, nitrile, ester, acid, ketone, ether and halogen. Condensation polymer and its synthesis involve the elimination of small molecules, or it contains functional group as part of the polymer chain its repeating units locks certain atoms. That is present in the monomer to which it can be degraded. 2.1 Radical chain polymerization It consisting of a sequence of three steps initiation, propagation, and termination. The homolytic dissociation of an initiator species I to yield a pair of radicals R. Kd I 2 R

Kd rate constants for catalytic dissociation. Then the addition of this radical to the first monomer molecule to produce the chain initiating radical M1. R+ M

K1

M1

M-monomer molecule, k1- rate constant for initiation step. Propagation consist of the growth M1 by successive additions of large number of monomer molecules M1 + M M2 + M Mn + M

Kp Kp Kp

M2 M3 etc. Mn + 1

Kp rate constant for propagation. Termination occurs by a combination of coupling and disproportionation.

Ktc Mn + m Ktc

Mn + Mn

Mn +

Mm

Mn + Mm

Ktc & Ktd are the rate constant for termination by coupling and disproportionation respectively.

2.2 Initiators : The initiation of the polymer chain growth is brought about by free radicals produced by the decomposition of compounds called initiators. The term chain growth represents a process involving a continuous and very rapid addition of the monomer units to form polymer molecules or polymer chains. As more and more monomer units are added, the length of the polymer chains increases continuously and the chain growth rapidly. A variety of initiators system can be used to bring about the polymerization radicals can be produced by a variety of thermal, photochemical & redox methods. [Banford, 1998; Denisova et.al., 2003; Eastmond., 1976 a, b, c; Moad et.al., 2002]1 2.3 Thermal Decomposition of Initiators : Types of Initiators : The thermal, homolytic dissociation of initiator is the most widely used mode of generating radicals to initiate polymerization. Polymerizations initiated in this manner are often referred to as thermal initiated or thermal catalyzed polymerizations. The number of different types of compounds that can be used as thermal initiators is rather limited one is usually limited to compounds with bound dissociation energies in the range 100-170 KJ Mol-1. Compounds with higher or lower dissociation energies will dissociate too slowly or too rapidly. Several different types of peroxy compounds are widely used [Sheppard]2 these are peroxides such as acetyl and benzoyl peroxides.

O 2CH3- C-O ----------------1

CH3-C-O-O-C-CH3

O 2-C-O ----------------2

-C-O-O-C-

The value of decomposition rate constant Kd varies in the range 10-4-10-9 S-1, depending on the initiator temperature [East Mond, 1976, a,b,c]3. Most initiators are used at temperature where Kd is usually 10-4-10-6 S-1. Kd is larger for acetyl peroxides than for alkyl peroxides since the RCOO radical is more stable than the RO radical and for R-N=N-R, Kd increases in the order R=allyl, benzyl > tertiary > secondary > primary [Koenig, 1973]4. The initiators half life (t1/2) defined as the time for the concentration of I to decrease to one half its original value. The rate of initiators disappearance by

-d[I] = dt Which on integration yields, [I] = [I]0 e-kdt Or Kd[I] ------------------ 3

-----------------4

[ I ]0 In = = Kdt [I] Where [I]o is the initiator concentration at the start of polymerization. t1/2 is obtained as 0.693 t1/2 = Kd By setting, [ I ] = [ I ]0/2 2.4 Redox Initiation:Many oxidation reduction reactions produce radicals that can be used to initiate polymerization [Sarac., 1999]5 this type of initiation is referred to as redox initiation, redox catalysis or redox activation. A prime advantage of redox initiation is that radical production occurs at reasonable rates over a very wide range of temperatures depending on the particular redox system, including initiation at moderate temperatures of 0-50C and even lower, some redox polymerizations can be initiated photolytically as well as thermally. 2.5 Types of Redox initiators: Peroxides in combination with a reducing agent are a common source of radicals; for example; The reaction of hydrogen peroxide with ferrous ion H2O2 + Fe2+ HO- + HO + Fe3+. ----------------- 5

Ferrous ion also promotes the decomposition of a variety of other compounds including various types of organic peroxides.

Fe2+ ROOR Fe2+ ROOH

RO- + RO

----------------- 6

HO- + RO

----------------- 7

O Fe ROOCR
2+

O RCO- + RO ----------------- 8

Other reductants such as Cr2+, V2+, Ti3+, Co2+ and Cu2+ can be employed in place of ferrous ion in many instances most of these redox systems are aqueous or emulsion systems. The combination of a variety of inorganic reductants and inorganic oxidants initiates radical polymerization, for example, -O3S-O-O-SO3- + Fe2+ -O3S-O-O-SO3- + S2O32Fe3+ + SO42- + SO4SO42- + SO4- + S2O3-

Other redox systems include reductants such as HSO3-, SO32-, S2O32- in combination with oxidants such as Ag+, Cu2+, Fe3+ ClO3- and H2O2.

Organic Inorganic redox pairs initiate polymerization, usually but not always by oxidation of the organic component, for example for oxidation of an alcohol by Ce4+.
4+

R-CH2-OH + Ce

Ce + H + R-CH-OH
3+ +

(Or)

By V5+, Cr6+, Mn3+ [Fernandez and guzman 1989; Misra and Bajpai, 1982; Nayak and Lenka, 1980]6.

There are some initiator systems in which the monomer itself acts as one component of the redox pair. Examples are thiosulphate plus acrylamide or methacrylic acid and N,N-dimethylaniline plus methylmethacrylate [Manickam et.al., 1978; Tsuda et.al., 1984]7. 2.6 Photochemical initiation: Photochemical or photoinitiated polymerizations occurs when radicals are produced by ultraviolet and visible light irradiation of a reaction system [Oster and yang., 1968; pappas, 1988]8. In general, light absorption results in radical production by either of two pathways; Some compound in the system undergoes excitation by energy absorption and subsequent decomposition into radicals. Some compound undergoes excitation and excited species interacts with a second compound to form radicals derived from the latter and / or former compound.

2.7 Metal ion Oxidants in Redox Initiation: Numerous reduction agents like alcohols, thiols, ketones, aldehydes, acids, amines and amides have been used in combination with oxidizing metal ions to participate in general single electron transfer reaction for free radical polymerization, metal ion used mainly for this purpose are Mn(III) and Mn(VII), Ce(IV), V(V), Co(III), Cr(VI) and Fe(III). 2.8 Cerium (IV) and electro induced polymerization Cerium (IV) ion has been used for the oxidation of many organic compounds, in the form of ceric (IV) ammonium nitrate (CAN), Ceric (IV) ammonium sulphate (CAS), Ceric(IV) Sulphate (CS) and cericperchlorate and the mechanism of such cericperchlorate and the mechanism of such reactions has been well established. Reducing agents, combined with Cerium (IV) and alcohols, aldehydes, acids and amines. The rate of vinyl monomers were in the order of Ceric perchlorate > Ceric nitrate > Ceric sulphate. Which is in the order of oxidation power of mentioned species. Ceric ions forms complexes with amines such as Sulfate, Nitrate and Hydroxyl in aqueous solution whose relative concentrations have been found to be function of hydrogen ion, respective anion concentration and ionic strength. Increase of ligand concentration X = SO42- and NO3- depress the rate of polymerization due to formation of less reactive cerium (IV) species, CeXn than Ce4+ and Ce(OH)n.

The mechanism and kinetics of polymerization involving ceric ion alone [Ananthanarayan and santappa et.al]9 and also in combination with reducing substrates such as alcohols10, diols11, polyols12, aldehydes13, ketones14 and amines15 etc. with different monomers acrylonitrile, acrylamide and methyl methacrylate etc. 2.9 Redox Polymerization: The kinetics of redox polymerization in terms of the propagation and termination steps. Termination is by biomolecular reaction of propagating radicals; The initiation and polymerization rates will be given by the expressions. Ri = Kd [reductant] [Oxidant] -----------------9

Kd [Reductant] [Oxidant] Rp = Kp [M] 2Kt

1/2 ----------10

In the alcohol Ce4+ system termination occurs according to Mn + Ce4+ Ce3+ + H+ dead polymer

------------11

At high ceric ion concentrations. the propagating radical losses a hydrogen to form dead polymer with C=C and group. Ri = Kd [Ce4+] [alcohol] Rt = Kt [Ce4+] [alcohol] --------------12 ---------------13

Steady state assumption (Ri = Rt) one obtains the polymerization rate as

Kd Kp [M] [alcohol] Rp = Kt Rp will show a higher dependence on [M] in these cases then indicated by the equation 2 and 5. The first dependence of Ri on [M] results, in 3/2 and 2-order dependence of Rp on [M] for bimolecular and monomolecular terminations respectively. Organic inorganic redox pair initiate polymerization, usually but not always by the oxidation of organic component. For example : Ce4+, V5+, Cr6+, Mn3+, Ag+, Cu2+ and ----------14

Fe3+ are used as the initiator of the redox systems. There are some initiator systems in which monomer itself act as a one component of redox pair. Examples, thiosulphate plus acrylamide or metharylic acid and N, N- dimethylaniline plus methylmethacrylate. Initiation :

M+ R

K1

M1

---------------15

Propagation :

M1 + M Kp

Kp

M2

----------------16

M n-1 + M

Mn

Termination

Kt

Mn + Ce(IV) Oxidative Termination :

Mn + Ce (III) + H+

---------17

R + Ce(IV)

Ko

oxidation product + Ce (III) + H+

---------18

In the methyl methacrylate polymerization by cerium (IV) (CAN) primary alcohol in nitric acid under nitrogen, by the application of Tafts correlation. It was suggested that the mechanism is free radical mechanism (* =0, P = -0.2). Kd Ce(IV) + R CH2OH (-RCH-OH+ Ce(III) + H+ ----------19

In the polymerization of methyl methacrylate by

Cerium (IV) [CAS]-diol

(propane 1, 2-diol16 and butane 1,4 diol17) system in aqueous sulfuric acid and under nitrogen, for the primary radical production step, complex formation was not reported between cerium (IV)18 and diol. In addition of kinetic results, the infrared spectrum of the isolated polymers showed the presence of hydroxyl group along with those of the homopolymer, indicating that the polymer contains the diol as an end-group which envisages the initiation by primary radicals formed from the reaction of Ceric ion with diol and termination by metal ions.

In the cases rate of polymerization was found to be directly proportional to the concentration of diol and inversely proportional to the ceric ion concentration but shows square dependence to the concentration of monomer. The rate of ceric ion disappearance is directly proportional to the initial concentration of ceric ion and diol. For the polymerization of methyl methacrylate with Cerium (IV) (CAS)- glycerol ion aqueous sulfuric acid the termination step is postulated to mutual at lower concentration of Ce(IV)0.5 where the rate of monomer disappearance was found to be proportional to [Ce(IV)] and [Glycerol]. The termination step for the same system at high concentrations of Ce(IV) termination step was proposed to be linear showing that the rate of polymerization is proportional to [M]2 [Glycerol]. The rate of ceric ion disappearance was found to decrease with increase sulfuric acid concentration and increasing ionic strength by addition of NaHSO4 to constant sulfuric acid concentration. Probably due to formation of neutral disulfate complexes of Ce(IV) [Ce(SO4)2] according to following equilibrium. Ce4+ + HSO4Ce(SO4)2+ + H+

Ce(SO4)2+ + HSO4Ce(SO4)2+ + HSO4-

Ce(SO4)2 + H+ Ce(SO4)32- + H+

In the polymerization methyl methacrylate [MMA] by Ce(IV) benzyl alcohol [BA] system in nitric acid, the first order dependence of Rp on [MMA] observed and the rate of Ce(IV) disappearance was proportional to first powers of [Ce(IV)] and [BA]. The reaction of Ce(IV) benzyl alcohol produces the free radical C6H5CH2OH which may partly be oxidized by [Ce(IV)] to give benzaldehyde. The growing polymer chains get terminated by the mutual annihilation of polymer radicals as evidenced by the dependence of rate of polymerization over square roots of [Ce(IV)] and BA. 2.10 Dependence of polymerization rate on Initiator: The polymerization rate to be dependent on the square root of the initiator concentration. This dependence has been abundantly confirmed for many different monomer initiator concentrations over wide ranges of monomer and initiator concentrations. [East mond, 1976, a,b,c, : Kamatchi et.a;., 1978 : Santee et.al., 1964; Schuez and Blaschke., 1942; V.Ranchan and smets., 1959]19 The order of dependence of Rp on [I] may be observed to be less than one-half at very high initiator concentrations. The termination mode may change from the normal bimolecular termination between propagating radicals to primary termination which involves propagating radicals relating with primary radicals. [Perger et.al., 1977; David et.al; 2001: Ito., 1980]20.

Ktp Mn-R ---------------21

Mn + R

Fig 1. Square root dependence of the polymerization rate Rp on the initiator concentration [1], g1/4 = Methyl methacrylate, benzoyl peroxide, 50oC.

This occurs if primary radicals are produces at too high a concentration and / or in the presence of too low a monomer concentration to be completely and rapidly scavenged by monomer. If termination occurs exclusively by primary termination the polymerization rate is given by Kp Ki [M]2 RP = --------------------Ktp

----------------22

Lower than one-half order dependence of Rp on Ri is also expected if one of the two primary radicals formed by initiator decomposition has low reactivity for in initiation, but is still active in termination of propagating radicals [Kaminsky et.al., 2002]21 2.11 Dependence of Polymerization Rate of Monomer : The initiator rate can be monomer dependent in several ways. The initiator efficiency may vary directly with the monomer concentration. F = f [M] Which would lead to first order dependence of Ri on [M] and 3/2 order dependence of Rp on [M], the equivalent result arises if the second step of the initiation reaction were to become the rate determining step. This occurs when Kd > Ki or when [M] is low. The initiation reaction may be written as, M+I M + R

And results in a 3/2 order dependence of Rp on [M]. This initiation is probably best considered as an example of redox initiation. 2.12 Kinetics of Initiation and Polymerization : The rate of producing primary radicals by thermal homolysis of an initiator Rd and is given by Rd = 2 fKd [I] -------------23

Where, [I] is the concentration of initiators and f is the initiator efficiency. The initiator efficiency is defined as the fraction of radicals produced in the homolysis reaction that initiate polymer chains, the value of f is usually less then unity due to wastage reactions, radicals that initiate polymer chains. The value due to wastage reactions. The normalizes of the initiator is the rate-determining step in the initiation sequence, and the rate of initiation is then given by Ri = 2 fKd [I] -------------24

Substitution of Eq 7 into Rp

fKd [I] Rp = Kp[M] --------------------Kt

1/2 ----------------25

4. REVIEW OF LITERATURE Studies on kinetics of polymerization of methyl methacrylate initiate by Ce(IV) redox systems are available in the literature. Some of them are as follows. M.Palanivelu etal., (2011)22 investigated the kinetics of polymerization of methyl methacrylate initiated by Ce(IV)-Vanillin redox system in aqueous solution of sulfuric acid at 40o C. The rate of polymerization (Rp) and the reaction orders with respect to monomer, initiator and ligand have been determined and found to be 1.5, 0.5 and 0.5 respectively. The effect of concentration of sulfuric acid on the polymerization was also studied. The rate of polymerization was found to increase with increasing temperature 30-60o C and decreases at higher temperature (>600C). The overall activation energy (Ea) was found to be 36.7 KJ/mol. The polymerization of methyl methacrylate initiated by the ceric ammonium nitrate D-glucose redox system has been studied in aqueous nitric acid under nitrogen in the temperature range 20.5 to 35oC.The initial rate of polymerization was determined gravimetrically whereas the initial rate of ceric ion disappearance was determined by titration of ceric ion. The relationships between conversion and D-glucose, Ce(IV), and monomer concentrations were determined. The dependence of the rates on D-glucose, Ce(IV), and monomer concentrations was evaluated. The effect of temperature was studied by M.D.Fernandez etal., (2007)23.

The kinetics of polymerization of methyl methacrylate initiated by cerium (IV)lactic acid redox system was studied in an aqueous medium in the temperature range of 25-50o C. The rate of polymerization (Rp) and the rate of Ce(IV) disappearance have been measured. The effects of some water-miscible organic solvents, cationic, anionic, nonionic surfactants, and complexing agents on the rate of polymerization were investigated. The temperature dependence of the rate was studied, and the activation parameters were computed using the Arhenius and Eyring plots. The effects of inorganic and organic solvents polymerization were also investigated by

Mahadevaiah etal., (2006).24 M.D.Fernandez etal., (2007)25 investigated the polymerization of methyl methacrylate initiated by ceric ammonium nitrate-maltose has been investigated in aqueous nitric acid under nitrogen in the temperature range 20.5-35Co.The dependence of the initial rate of polymerization and the initial rate of ceric ion consumption on maltose, Ce(IV),and monomer concentrations has been determined. The reaction orders were found to depend on ceric ion concentration. At a moderately high Ce(IV) concentration (1X10-3 mol litre-1) the orders were 1/2 and 3/2 with respect to maltose and monomer concentration, respectively and independent of Ce(IV) concentration. But a low Ce(IV) concentration (4X10-4 mol litre-1) the orders with respect to monomer and Ce(IV) changed to 1 and 1/2 respectively. V.S.Jamal Ahmed etal., (2001)26 studied the kinetics of radical free polymerization of methyl methacrylate using potassium peroxomonosulfate as initiator in

the presence of benzyl tributylammonium chloride (BTBAC) as phase transfer catalyst was studied. The polymerization reactions were carried out under nitrogen atmosphere and unstirred conditions at a constant temperature of 60oC in ethyl acetate /water bi-phase system. The rate of concentrations of monomer, initiator, catalyst, temperature, acid and ionic strength on the rate of polymerization (Rp) as certained. The orders with respect to monomer, initiator and phase transfer catalyst were found to be 1.5, 0.5 and 0.5 respectively. The rate of polymerization (Rp) is independent of ionic strength and PH. S.V.Subramanian etal., (2004)27 investigated the polymerization of the monomer, methyl methacrylate (MMA) was carried out in sulfuric acid medium at 15 oC. With the redox initiator system, ceric ammonium sulfate-malonic acid. There was no induction period, and a steady state was attained in a short time. There was found to be no polymerization even after 1hr, in the absence of the reducing agent R. The initiation was by the radical produced from the Ce4+-malonic acid reaction. The rate of monomer disappearance was proportional to [M]1.5,[R]0.5 and [Ce]0.3-0.5, and the rate of ceric disappearance was proportional to [R] and [Ce4+]. Chain lengths of the polymers were directly proportional to [M] and inversely to [R]1/2 and [Ce4+]1/2. M.Dharmendira kumar etal., (2004)28 studied the kinetics of free radical polymerization of methyl methacrylate(MMA) using potassium peroxydisulfafe as initiator in the presence of propiophenonebenzyldimethylammonium chloride as phase transfer catalyst were studied. The reactions were carried out under inert and unstirred conditions at constant temperature of 60oC in cyclohexanone/water biphase media. The

dependence of the rate of polymerization on various experimental conditions, such as different concentrations of monomer, initiator and phase transfer catalyst (PTC) and different ionic strength, temperature and volume fraction of aqueous phase was studied. The order with respect to monomer, initiator and phase transfer catalyst was found to be 1, 0.5 and 0.5 respectively. The rate of polymerization (Rp) is independent of ionic strength and PH. However, an increase in the polarity of solvent and volume fraction of aqueous phase has slightly increased the Rp value. Kavitha sankar etal., (2002)29 investigated the kinetics and mechanism of free radical polymerization of methyl methacrylate(MMA) using water soluble initiator viz., potassium peroxydisulfate(PDS) in the presence of newly synthesized 1,4dihexadecylpyrazine-1,4-diium dibromide as multi-site phase transfer catalyst(MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 50+1oC under nitrogen atmosphere. The effect of variation of [MMA],[PDS],[MPTC] ,and volume of fraction of aqueous phase, solvent polarity and temperature on the rate of polymerization(Rp) was ascertained. The order with respect to monomer, initiator and multi-site phase transfer catalyst were found to be 1.0, 0.5 and 0.5 respectively. The rate of polymerization of is independent of ionic strength and PH. The photo-initiated homo-polymerization of methyl methacrylate (MMA) has been studied at 25oC in the presence of ortho-phosphoric acid as complex former. Post-polymerization accompanied by a molecular weight increase has been found to occur in addition to an increase in reaction rate after ceasing photo-initiation in the

system MMA-H3PO4. The factor responsible for the continuation of the postpolymerisation in such a system has been found to be the macro-radicals whose active life is greatly prolonged in the presence of the complex former. The effects of various factors in the kinetics of the post-illumination process have been studied by Ye.S.Garina etal.,(2005)30 The free radical terpolymerization of indene (In) methyl methacrylate (MMA) and acrylonytrile (AN) has been investigated by Naguib, Hala.F etal., (2009)31. The rate of polymerization of all the binary systems involved dilatometrically for the homogeneous polymerization. The reactivity ratios of the three binary systems were calculated and were found to be equal to 0.031 and 0.397 for In/AN copolymers and 0.02 and 3.82 for In/MMA copolymers and finally 0.152 and 1.20 for AN/MMA copolymers. The rate of terpolymerization in bulk has been measured as well as the relationship between the monomer mixture composition and the obtained terpolymer in order to construct the compositional triangle. Also the effect of initiator concentration on the rate of terpolymerization was investigated. A.K.Srivastava etal., (2003)32 investigated the homopolymerization of methyl methacrylate(MMA) was carried out in the presence of triphenyl stibonium 1,2,3,4- tetraphenyl- cyclopentadienylide as an initiator in dioxane at 65 oC+0.1oC. The system follows non-ideal radical kinetics (Rp [M]1.4[I]0.44) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value of Kp2/Kt were 64 KJ mol-1 and 0.173X10-3/mol-1S-1 respectively.

Novel block copolymers of poly (ethylene glycol) (PEG) with various vinyl monomers namely acrylonitrile (AN), acrylamide (AAm), methyl methacrylate(MMA) and methacrylic acid(MAA) were synthesized using Ce4+-PEG and Mn3+-PEG redox system in aqueous acidic medium. The polymerization proceeded via a macroradical generation, which was substantiated by ESR spectroscopy. This macroradical acted as a redox macroinitiator for the block copolymerization of vinyl monomers. The formation of the block copolymers was confirmed by chemical test and fractional precipitation, as well as by FT-IR, 1H and
13

C FT-NMR spectroscopy. These polymerizations have been

studied by S.Nagarajan etal., (1998)33. R.Chandragandhi etal., (1997)34 was investigating the polymerizations, of methyl methacrylate (MMA) and acrylonitrile (AN) were carried out in aqueous nitric acid at 300C with the redox initiator system ammonium ceric nitrate ethyl cellulose (EC). A short induction period was observed as well as the attainment of a limiting conversion for polymerization reactions. The consumption of ceric ion was first order with respect to CE(IV) concentration in the concentration range (0.2 0.4) x 10-2M, and the points deviations from a linear fit. The plots of the inverse of pseudo first order rate constant for ceric ion consumption, (K1)-1 vs [EC]-1 gave straight lines for both the monomer systems with non zero intercepts supporting complex formation between Ce(IV) and EC. The rate of polymerization increases regularly with [Ce(IV)] upto 0.003M, yielding an order of 0.41, then falls to 0.0055M and again shows a rise at 0.00645M for MMA polymerization for AN polymerization Rp shows a steep rise with

[Ce(IV)] up to 0.001 M and beyond this concentration Rp shows a regular increase with [Ce(IV)], yielding an order of 0.48. In the presence of constant [NO3-] MMA and AN polymerization yield orders of 0.36 and 0.58 for [Ce(IV)] variation respectively. The rate of polymerization increased with an increase in EC and monomer concentration, only at a higher concentration of EC and [0.5M] was a steep fall in Rp observed for both monomer systems. The orders with respect to EC and monomer for MMA polymerization were 0.19 and 1.6 respectively. The orders with respect to EC and monomer for AN polymerization were 0.2 and 1.5, respectively. A kinetic scheme involving oxidation of EC Ce (IV) via complex formation, whose decomposition gives rise to a primary radical initiation, propagation, and termination of the polymeric radicals by biomolecular intervation the polymeric radicals by biomolecular interaction is proposed. An oxidative termination of primary radicals by Ce(IV) is also included. C.Erbil etal.,(1998)35 was synthesized the polyacrylamides (PANMS)

polyacrylonitriles (PANS) and polymethyl methacrylates (PMMAS) by using Ce(NH4)2 (NO3)6, Ce(SO4)2 4H2O and KMno4 in combination with nitrilotriacetic acid (NTA) and diethylenetriamine penta acetic acid (DTPA) which have strong chelating properties, as redox initiations, polymerizations, were carried out in the aqueous acidic solutions at 250C and 550C in the presence of air. The chain structures of the resulting products were studied by fourier transform infrared (FTIR) spectroscopic measurements form the comparison of the spectroscopic results with gravimetric and viscometric data it was concluded that both the difference between he solubility behaviour in aqueous solutions of MMA, AN, AAM, and their polymers and catalyst-

activator-monomer combinations were important parameters effecting the polymerization mechanism, conversions and the structures of the polymers. The FTIR and viscosity results indicated that PAAMS obtained in our experimental conditions formed cross linked structures with sulphated complexes of Ce (III) and Mnso4 produced by the redox reactions between catalyst [Mno4- and Ce(IV)] NTA and AAM. The observed and PAN chains were terminated by hydrated and sulphated complexes of Ce(III) while the termination of PMMA radicals took place by primary radicals because PMMAS were formed by emulsion polymerization kinetics. Sunilkumar Banyal etal., (2011)36 was studied the mulberry silk fibre was graft copolymerized with binary mixtures of acrylic acid, methylacrylates as the principal monomer in aqueous medium by using CAN as redox initiator. The binary vinyl monomers were graft co polymerized by using the grafting conditions like reaction time, temperature, concentration of MMA and CAN as reported earlier for optimum percent grafting (74.40) of MMA alone onto the same backbone. Graft copolymers were

characterized by FTIR, SEM swelling studies, moisture absorbance and chemical resistance in acidic and alkaline medium. Dye uptake (Gention Violet) on graft copolymers were studied photo calorimetrically at 420nm. The dying capabilities of the graft copolymers with binary mixture is more that the reference graft copolymers of methyl methacrylate.

C.M.Patra etal., (1994)37 was investigated the influence of N-acetylglycine on the kinetics of graft copolymerization of acrylonitrile (AN) and methyl methacrylate (MMA) onto chemically modified jute fibers was studied in the temperature range 40600C. The optimum conditions for grafting have been determined by the effects of concentrations of monomers, Ce(IV), and N-acetylglycine on the rate of grafting. The effect of time, temperature, and concentration of the acid, the amount of jute fibers and some organic solvents and inorganic salts on the rate of grafting has been reported. On the basis of experimental results findings out, a kinetic scheme has been proposed. Infrared spectra of chemically modified jute and grafted jute have been investigated. More than 185% graft yield could be achieved with the present system. Grafting has improved the thermal stability of jute fibers. Nesrin Oz etal., (2001)38 was investigating the Ethoxylated nonyl phenols, ethoxylated fatty alcoholos, and ceric ammonium nitrate redox systems were used for the polymerization of vinyl and acrylic monomers such as acrylonitrile, styrene, and acrylic acid. The initiating radical was formed on reducing organic compound which in turn initiated polymerization to give polymers containing chain ends of ethoxylated nonyl phenols and ethoxylated fatty alcohols that showed much higher water absorption. The effects of the concentration of Ce4+ salt, ethoxylated nonyl phenols, and monomers on both the yield and the molecular weight of corresponding polymers were studied.

M.Patra etal., (1996)39 studying the polymerization of acrylonitrile (AN) the Ce(IV) Citric Acid (CA) redox system as an initiator in aqueous nitric acid solution, in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS) has been kinetically reported at a temperature range of 25-450C. The rate of polymerization (Rp) and disappearance of Ce(IV) (-Rce) increase with increasing concentration of SDS above its critical micelle concentration (CMC) when the surfactant molecules are organized, Rp was found to be proportional to [AN]1.5 and [CA]0.5 with other organic substrates Rp follows the increasing order of sorbitol > mannitol > glycerol > CA. It was found to decrease considerably in the presence of cationic surfaetant (CTAB), and nonionic surfactant (Trition - X 100) had no effect on the rate. Rce various linearly with [Ce(IV)] and [CA]. Both Rp and Rce increase with increasing temperature. The overall activation energy was found to be 18.31 and 13.72 k.cal mol in the absence and presence of 0.015 MSDS, respectively. The chain length of the polyacrylonitrile has also increased with increasing SDS concentration. Femeozturk etal., (2007)40 was studying the comprehensive account on the synthesis of block copolymers via redox initiating systems. Redox polymerization systems for the synthesis of block copolymers have been reported. The mechanism of initiation by a radox process is a method which is used to obtain block copolymers by various transition metals, such as Ce(IV), Mn(III), Cu(II), and Fe(III) redox polymerization has found wide applications in initiating polymerization reactions in initiating polymerization reactions and has been specifically of industrial importance. As

it follows from the Contents in addition to the above mentioned metals other redox polymerization systems such as hydrogen peroxide and vanadium are described as well. P.L.Nayak etal., (2011)41 was studying the grafting of acryonitrile onto chitosan was studied using ceric ammonium nitrate as the redox initiation in aqueous media. The percentage of grafting and the efficiency of the process were calculated as function of the concentration of initiator and monomer the reaction time and temperature. The percentage of grafting was found to depend on the relative amount of monomer to chitosan, initiator and volume of the aqueous phase as well as the reaction temperature. By using optimized combinations of the reaction variables a grafting efficiency up 88% and a percentage of grafting of nearly 20% were reached. Evidence of grafting was obtained from comparison of SEM, XRP, and FTIR of the grafting and non-grafted chitosan as well as solubility characteristics of the product. The antibacterial and angifungal activities of the grafted polymer have also been investigated.

EXPERIMENTAL PART Polymerization Reaction Vessel The reaction tubes used for the experiments were pyrex glass tubes closed by B-24 cones in which nitrogen inlet and outlet tubes were fused. The longer tube was used as inlet for puring nitrogen gas through the solution and the shorter one was used as outlet for nitrogen. After passing nitrogen for the specified time, the tubes were sealed with rubber gaskets to ensure maintenance of an inert atmosphere. Thermostat The thermostat used was a rounded vessel with a heater, stirrer and thermometer. The temperature range used for all the experiments reported were 300C and 350C controlled to an accuracy of 0.10C. Deaeration Technique The nitrogen gas used to deaerate the experimental system was free from oxygen by passing through several columns of fisher solution. The gas after passing through fisher solution was free from hydrogen sulphide, sulfur dioxide etc, by passing it through a wash bottle containing saturated lead acetate solution and then washed free of all vapours by passing it through a wash bottle containing double distilled water. Before passing the purified nitrogen through the reaction tube, it was passed through a wash bottle containing the same concentration of monomer solution in order to avoid the loss

of monomer during deaeration. For all the experiments the deaeration time was 20 minutes. Preparation of Fisher Solution Fisher solution was prepared by dissolving 20g of sodium hydroxide in 100ml of water and adding 16g of sodium dithionate (N2S2O4) and 2g of anthroquinone sulphonate (silver salt) to the warm solution. The mixture was stirred well until a clear blood red colour solution was obtained. It was cooled of room temperature and then used. The fisher solution was changed for every ten runs. Reagents All chemicals used were of the purest quality mostly BDH, E.Merck, SDs fine (analar or G.R. Grade), SRL, products. Glasswares and the reaction vessels were cleaned with warm solutions of chromic acid, rinsed frequently with double distilled water and dried in air oven at 900C. Water Water was distilled in all glass cornery vessel, the second distillation being from potassium permanganate and the double distilled water was used throughout the study.

Monomer CH3 Methyl Methacrylate [CH2 = C COOCH3] was recrystallised twice from methanol and dried in vacuo. Reducing Agent The reducing Agent used in the present work is lactic acid Acid All experiments were conducted in sulphuric acid solution. Solution of sulphuric acid were prepared by suitable dilution of concentrated acid with double distilled water and standardized against sodium hydroxide solution. Purification of Reagents To obtain reproducible results and to minimize experimental errors a high degree of purity of the solvents and reagents were used. Therefore only a analytical grade chemicals were used. Commercial sample and laboratory grade reagents were carefully purified by standard procedure and then purity was checked by melting point measurements.

Estimations Initiator Ceric ammonium sulphate was used as initiator. The Ce(IV) ion concentration were determined by cerimetry. For this, an aliquot of Ce(IV) stock solution was run into a known excess of standard ferrous ammonium sulphate solution using ferroin indicator. Ferroin Indicator The ferroin indicator was prepared by dissolving 1.485g of 1,10-phenantheroline monohydrate (C12H8N2H2O) in 100 ml of 0.025 ferrous ammonium sulphate solution. Rate of Polymerization (Rp) The rate of polymerization (Rp) of methyl methacrylate was determined by

Iodimetry. The weight of polymer obtained in each experiment was substituted in the equation given below to get Rp. Rp = (1000 x W) / (V x T x M) Where W = Weight of the polymer T = Temperature V = Total Volume of the reaction mixture. M = Molecular weight of the monomer. R = Reaction time in seconds.

Rate of Ce(IV) Disappearance Rate of Ce(IV) disappearance (-d[Ce(IV)]/dt) was determined as described below. At the end of the reaction time, the reaction was arrested with definite amount of ferrous ammonium sulphate on the excess ferrous ion was determined by cerimetry. From the amount of unreacted ferrous ion, the Ce(IV) consumed was evaluated and hence the rate of Ce (IV) disappearance was computed. Oxidation experiment A typical oxidation experiment is described below. A reaction mixture containing lactic acid, sulphuric acid, sodium bisulphate (to maintain the ionic strength) and water (to maintain total volume constant) were taken in the reaction tube. Nitrogen free from oxygen by passing through fisher solution by bubbled through the solution for 20 minutes and the system was thermostated at the desired temperature. The Ce(IV) stock solution was added and the tube was sealed with rubber gaskets to ensure maintenance of an inert atmosphere. The total volume of the reaction mixture was usually 20ml. At the end of the reaction time (20 min), the reaction was arrested by the addition of a known excess of ferrous ammonium sulphate solution, when the remaining Ce(IV) was instantly reduced to Ce(III) state. The unreacted Fe(II) was estimated by titrating with a standard ceric ammonium sulphate solution using ferroin indicator. The rate of Ce(IV) disappearance was evaluated from the titre value. The rate of Ce(IV) disappearance was followed at different substrate concentration, Ce(IV) concentration and sulphuric acid concentration keeping the constant ionic strength.

Polymerization Experiment In a typical kinetic run, a reaction mixture containing methyl methacrylate, lactic acid, sulphuric acid, sodium bisulphate and water taken in the reaction tube was interposed between the nitrogen cylinder and the reaction tube (to avoid loss of monomer during deaeration) nitrogen, free from oxygen by passing through fisher solution, was bubbled through the solution for 20 minutes and the system was thermostated at the desired temperature. The Ce(IV) stock solution was added and the tube was sealed with rubber gaskets to ensure maintenance of an inert atmosphere. Polymerization started without any induction period. At the end of the reaction time (20 min), the reaction tube was opened and quenched with excess of ferrous ammonium sulphate solution. The polymethyl methacrylate was filtered through a previously weighted sintered glass crucible, washed several times with distilled water and finally washed with distilled ethanol and then dried at 600C to a constant weight. The weight of tye polymer was used to compute the rate of polymerization. The filtrate was analysed by cerimetric using ferroin as indicator. The rate of Ce(IV) disappearance was evaluated from the titre value. REFERENCE : 1. Bamford, CH., G.C.Eastmond and D.Whittle, Polymer, 10,771 (1969b). Denisova, E.T., T.G.Denisova and T.S.Pokidova, Handbook of Free Radical Initiators, Wiley, New York (2003), Moad, G., J. Chiefari, R.T. A. Mayadunne, C.L.Moad, A.Postma, E.Rizzardo, and S.H.Thang, Macromol. Symp., 182, 65 (2002).

2. Sheppard C.S., Peroxy Compounds, pp. 1-21 in Encyclopedia of Polymer Science and Engineering, Vol.11, H.F. Mark, N.M. Bikales, C.G. Overberger, and G.Menges eds., Wiley Interscience, New York, (1988). 3. Eastmond G.C., The Kinetics of Free Radical Polymerization of Vinyl Monomers in Homogeneous Solutions, Chap. 1 in Comprehensive Chemical Kinetics, Vol. 14A, C.H. Bamford and C.F.H. Tipper, eds., American Elsevier, New York, (1976a.) 4. Koenig. T., The Decomposition of Peroxides and Azoalkanes, Chap.3 in Free Radicals, Vol.I, J.K.Kochi, ed., Wiley, New York, (1973). 5. Sarac, A.S., Prog, Polym. Sci., 24, 1149 (1999). 6. Fernandez, M.D. and G.M. Guzman, J.Polym. Sci. Polym. Chem.. Ed., 27, 2427 (1989). Misra, G.S. and U.D.N. Bajpai, Prog. Polym, Sci., 8, 61 (1982). Nayak, P.L. and S.Lenkla, J.Macromol. Sci. Rev. Macromol. Chem., C19, 83 (1980). 7. Manickam, S.P., K.Venkatarao, U.c. Singh, and N.R.Subbaratnam, J.Polym, Sci. Polym. Chem.. Ed., 16, 2701 (1978). 8. Oster, G and N.L. Yang, Chem. Rev., 68, 125, (1968), Pappas, S.P., Photopolymerization, pp 186-212 in Encyclopedia of Polymer Science and Engineering, Vol. 11, H.F. Mark, N.M.Bikales, C.G. Overberger, and G.Menges, eds., Wiley Interscience, New York, (1988).

9. Ananthanarayan V.S. Santappa M.J. Appl Polym Sci; 9:2347 (1969). 10. Hanna SB, Carool WR, Attiga S, Webb WH, Z.Naturforsch, B. Anorg Chem: 30:409, (1975), Renders G, Broze G, Jerome R, Teyssie Ph. J Macromol Sci Chem A : 16 (8) : 1399, (1981). 11. Mohanty N. Pradhan B, Mohanta MC. Eur Polym J; 15:743 (1979). 12. Rout A, Rout Sp, Singh BC, Santappa M. Makromol Chem; 178:639; (1977). 13. Subramanian SV, Santappa M, Makromol Chem : 112: (1968) 14. Subramanian SV, Santappa M, J Polym Sci, Part A-1; 6:493: (1968). 15. Saha SK, Chaudhuri AK, J Polym Sci, Polym Chem Ed : 10:797: (1972). 16. Mohanty N, Pradhan B, Mohanta MC, Eur Polym J : 15:743(1979). 17. S. Mohanty N, Pradhan B, Mohanta MC, J Macromol Sci A : 19(2):283:(1981). 18. Sarac, AS. Int Chem Kinet 1985: 17 : 1333. Sarac AS, Goc, men A.J. Soln Chem : 19:901(1990). 19. Kamatchi M., J Satoh, and S.-I Nozakura, J. Polym, Sci, Polym. Chem. Ed., 16, 1789 (1978); Santee, G.F., R.H.Marchessault, H.G. Clark, J.J. Kearny, and V.Stannett, Makromol. Chem., 73 177 (1964); Schulz, G.V. and F.Blaschke, Z. Physik Chem. (Leipzig), B51, 75 (1942).

20. David G., J.J. Robin, and B.Boutevin, J. Polym. Sci. Polym. Chem. Ed., 39, 2740 (2001); Sarac, A.S., Prog. Polym. Sci., 24, 1149 (1999); Ito, K., J. Polym. Sci. Polym. Chem.. Ed., 18, 701 (1980); Macromolecules, 13, 193, (1980). 21. Kaminsky, V., M.Buback, and M.Egorov, Macromol, Theory Simul., 11, 128 (2002). 22. M.Palanivelu, K.E.N. Nalla Mohamed, T.Hidayathulla Khan and M.Prem Nawaz (2011). 23. M.D. Fernandez, G.M.Guzman : British Polymer Journal 21 (5): 413-419 (2007) 24. Mahadevaian T.Demappa : Journal of Applied Polymer Science,m 103 (6) : 3498 3505(2006). 25. M.D.Fernandez, G.M. Guzman : British Polymer Journal (2007). 26. V.S.Jamal Ahamed, H.Thajudeen, T.K.Shabeer. Eur polym J(2001) 27. S.V.Subramanian, M.Santappa: Journal of Polymer Science, (2004). 28. Dharmendira Kumar, M., ; Konguvel Thehazhnan, P.; Umapathy, M.; Rajendran, M.; International Journal of Polymeric Materials 53,95-103(2004). 29. Kavitha Sankar, Venugopal Rajendran, Journal of Applied Polymer

Science.(2002)

30. Ye.S.Garina, A.V.Olenin, v.P.Zubov, Science.(2005)

V.a.Kabanov;

Journal

of

Polymer

31. Naguib, Hala F.; Makhtar, Samia M.; Khalil, NEsren Z.; Elsabee, Maher Z (2009). 32. A.K.Srivastava and Ajay Kumar Chaurasia : J.Chem Sci., 116, 55-59 (2003). 33. S.Nagarajan, S.Sudhakar, K.S.V. Srinivasan: Pure and Appl. Chem., 70(6), 12451248(1998). 34. Chandraganthi, K.Vasanthi and R.Sriram; J.M.S. Pure Appl. Chem, A32(12), 1997-2015 (1995). 35. E.Erbil : E.Heximaglu, A.S.Sarac; Polymer; 40, 7409-7415 (1998). 36. Sunil Kumar Banyal, Balbir Singh Knith, Rajeev Kr.Sharma; Adv. Appl. Sci. Res. 2(1), 193-207, (2011). 37. C.M.Patra, B.C. Singh : Journal of Applied Polymer Science, 52,1557-1568 (1994). 38. Nesrin OZ; Ahmet Akar; J.Am. Chem. Soc. 82, 301-313 (2001). 39. M.Patra, A.K.Pandigrathi, and B.K.Sinha, Journal of Polymer Science (1996). 40. Temel Ozturk and Ismail Cakmak, Iraniarr Polymer Journal 16 (8), 561-581, (2007).

41. P.L.Nayak, Manojkumar Pati, Advances in Polymer Science and Technology; An International Journal 1(2); 14-21; (2011).

Scope of the present work Metal ions such as Cr6+, V5+, Fe3+, Ce4+, Co3+, Mn3+ etc., coupled with certain have been reported to be useful redox system for initiating vinyl polymerization. For instance CE4+ have been found to be an active oxidant in the vinyl polymerization, hence Ce4+ (Ceric ammonium sulphate) is chosen as the oxidizing agent for the present investigation then also lactic acid (CH3CHOHCOOH) is choosen as the reducing agent for the present work. Detailed survey of literature reveals that an extensive study can be carried out on methyl methacrylate, acrylamide, methyl acrylate, acrylic acid and its derivatives with organic reducing agent like alcohols, aldehydes, ketones, acids, amides, amines etc., which in combination with a oxidizing agent constitute a redox pair to initiate the Vinyl polymerization. Earlier, the redox polymerization of methyl methacryalate initiated by various redox system has been investigated. Based on the kinetic studies of polymerization of methyl methacrylate (MMA) initiated by ceric ammonium sulphte (CAS) lactic acid (LA) redox system have been studied with a suitable experimental methods. Hence the system is choosen for the present work.