Kelen-Tudos Method Research Articles

An efficient way to tune grafting density of well-defined copolymers via an unusual Br-containing acrylate monomer

A series of well-defined amphiphilic graft copolymers, containing hydrophilic poly(acrylic acid) backbone and hydrophobic poly(butyl acrylate) side chains, were synthesized by sequential reversible addition fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) without any postpolymerization functionality modification followed by selective acidic hydrolysis of poly(tert-butyl acrylate) backbone. tert-Butyl 2-((2-bromopropanoyloxy)methyl)-acrylate was first homopolymerized or copolymerized with tert-butyl acrylate by RAFT in a controlled way to give ATRP-initiation-group-containing homopolymers and copolymers with narrow molecular weight distributions (Mw/Mn < 1.20) and their reactivity ratios were determined by Fineman-Ross and Kelen-Tudos methods, respectively. The density of ATRP initiation group can be regulated by the feed ratio of the comonomers. Next, ATRP of butyl acrylate was directly initiated by these macroinitiators to synthesize well-defined poly(tert-butyl acrylate)-g-poly(butyl acrylate) graft copolymers with controlled grafting densities via the grafting-from strategy. PtBA-based backbone was selectively hydrolyzed in acidic environment without affecting PBA side chains to provide poly(acrylic acid)-g-poly(butyl acrylate) amphiphilic graft copolymers. Fluorescence probe technique was used to determine the critical micelle concentrations in aqueous media and micellar morphologies are found to be spheres visualized by TEM. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2622–2630, 2010

New functional copolymers of N-acryloyl-N′-methyl piperazine and 2-hydroxyethyl methacrylate: synthesis, determination of reactivity ratios and swelling characteristics of gels

Copolymers of N-acryloyl-N′-methylpiperazine (AcrNMP) and 2-hydroxyethyl methacrylate (HEMA) were synthesized by free radical solution polymerization in dioxane at 70 ± 1 °C, using 2,2′-azobisisobutyronitrile (AIBN) as initiator. The copolymer compositions were analyzed by the methods of FTIR spectroscopy and elemental analysis. Both the method of analysis yielded results that agreed reasonably well. The monomer reactivity ratios of the copolymerization were determined by the linearization methods of Finemann–Ross (FR) and Kelen–Tudos (KT). The reactivity parameter results derived using FTIR analysis showed that the copolymerization yielded mainly alternating structure with reactivity ratios, r1(AcrNMP) = 0.263 ± 0.011 and r2(HEMA) = 0.615 ± 0.097 by F–R method and r1 = 0.227 ± 0.074 and r2 = 0.53 ± 0.15 by KT method. Microstructure data calculated by the method of Igarashi also supports the alternating structure (tendency) of the copolymer. Crosslinked polymer gels of this system exhibited remarkably high swelling of more than 500% in water at ambient temperature.

Monomer reactivity ratio and thermal performance of α-methyl styrene and glycidyl methacrylate copolymers

Synthesis and characterization of the copolymers (PAG) of α-methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H-NMR) and thermogravimetery (TG). Based on the copolymer compositions determined by 1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 ± 0.012 and 0.883 ± 0.046 respectively by Kelen-Tudos method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.

Copolymers of bulky fumarate: synthesis and their properties

The free radical copolymerization of di-n-docosyl fumarate with vinyl acetate and n-alkyl (meth)acrylates was carried out in toluene at 70°C using benzoyl peroxide as an initiator. 1H NMR and carbon analysis was used to determine the copolymer compositions. Monomer reactivity ratios for high conversion polymerization were calculated by Fineman-Ross, Kelen-Tudos and conversion extension Kelen-Tudos methods. Gel permeation chromatography was used to determine the molecular weights and polydispersity indexes. In order to determine the stability of polymers against thermal degradation, the kinetics and mechanism of the thermal degradation of copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis techniques. The energy of activation of the degradation process was determined by several thermogravimetric analysis models.

Ultrasonic degradation of poly (styrene- co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene- co-methyl methacrylate) (SMMA), poly (styrene- co-ethyl methacrylate) (SEMA) and poly (styrene- co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen–Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA > SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation.

HYDROGELS FROM ACRYLIC ACID WITH N,N-DIMETHYLACRYLAMIDE: SYNTHESIS, CHARACTERIZATION, AND WATER ABSORPTION PROPERTIES

Copolymer hydrogels of acrylic acid (AA) with N,N-dimethylacrylamide (NNDMAAm) were synthesized by solution free radical polymerization at different feed mol monomer ratios. The monomer reactivity ratios were determined by Kelen-Tudos method. According to that, the monomer reactivity ratios for poly(AA-co-NNDMAAm) were r1 = 0.650 (M1=AA) and r2= 1.160 (M2=NNDMAAm), (r1 x r2= 0.753). The effect of reaction parameters including: the concentration of cross-linking reagent, monomer concentration, pH, temperature, salt solutions, and solvent polarity on the water absorption have been studied. The hydrogels achieved water-absorption values of 544 g water/ g xerogel for the copolymer poly(AA-co-NNDMAAm) 3:1 atpH 5. Low critieal solution temperature (LCST) values of hydrogels, showed an increase whenthe hydrophilic AA moiety eontent increased in the copolymers.

Chiral copolymers of (R)‐N‐(1‐phenylethyl) methacrylamide and 2‐hydroxyethyl methacrylate: copolymerization characteristics and chiroptical properties

AbstractThe aim of this investigation was the copolymerization of a chiral monomer, (R)‐N‐(1‐phenylethyl) methacrylamide, with an achiral monomer, 2‐hydroxyethyl methacrylate (HEMA). The copolymerization characteristics as well as the chiroptical properties (optical rotation and circular dichroism) and their variation with copolymer composition and temperature are discussed. The copolymers are statistical and enriched in HEMA. The monomer reactivity ratio of the chiral monomer (r1) is 0.133 whereas that of HEMA (r2) is 1.042 based on the Kelen–Tudos method. The sequence of consecutive chiral monomer units predominates for a feed composition between 0.5 and 0.9 (mole fraction). On the other hand, the sequence of HEMA is uniform and it predominates for a feed composition of around 0.5 (mole fraction). The chiroptical properties of the copolymers do not vary linearly with the content of chiral units in the copolymers. The optical rotation and circular dichroism attain optimum values above 30–40 mol% of chiral monomer units in the copolymers. However, the circular dichroism of the copolymers varies linearly with the temperature. The chiral monomer being a more bulky structure is less reactive than HEMA. The nonlinear variation of chiroptical properties of the copolymers with the content of chiral units may be due to the secondary interaction in the copolymers associated with the hydrogen bonding involving the amide linkage (CONH) present in the pendant chromophore of the chiral monomer as well as the hydroxyl pendant group of HEMA and also the aromatic π–π interaction. Copyright © 2009 Society of Chemical Industry

Copolymerization ofN-vinyl pyrrolidone with functionalized vinyl monomers: Synthesis, characterization and reactivity relationships

Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobi- sisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, H NMR and C NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composi- tion was determined by H NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copoly- mers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

Convenient Synthesis of PtBA-g-PMA Well-Defined Graft Copolymer with Tunable Grafting Density

A series of well-defined graft copolymers, consisting of poly(tert-butyl acrylate) backbone and poly(methyl acrylate) side chains, were synthesized by the combination of reversible addition-fragmen- tation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). A new acrylate monomer containing ATRP initiation group,tert-butyl 2-((2-bromopropanoyloxy)methyl)acrylate, was first prepared, which can be homopolymerized or copolymerized with tert-butyl acrylate by RAFT in a controlled way to obtain well-defined homopolymers and copolymers with narrow molecular weight distributions (Mw/Mn< 1.18). The reactivity ratios were determined by Fineman-Ross and Kelen-Tudos methods, respectively. The density of ATRP initiating groups can be tuned by the feed ratio of the comonomers. These polymers directly initiated ATRP of methyl acrylate to synthesize well-defined poly- (tert-butyl acrylate)-g-poly(methyl acrylate) graft copolymers (Mw/Mn< 1.28) with controllable grafting densities via the grafting-from strategy without any polymeric functional group transformation. Finally, the poly(tert-butyl acrylate) backbone was selectively hydrolyzed in acidic environment without affecting the poly(methyl acrylate) side chains to give poly(acrylic acid)-g-poly(methyl acrylate) amphiphilic graft copolymers.

Synthesis and characterization of new polymethacrylates bearing perfluorocyclobutyl and sulfonyl units

A new methacrylate monomer containing perfluorocyclobutyl and sulfonyl units, p-(2-(p-(benzenesulfonyl)phenoxy)perfluorocyclobutoxy)phenyl methacrylate, was synthesized from commercially available reagents in good yield and this kind of methacrylate can be homopolymerized by free radical polymerization using 2,2′-azobis(isobutyronitrile) as initiator or atom transfer radical polymerization using methyl 2-bromopropionate as initiator and CuBr/PMDETA as catalytic system. The reactivity ratios for BSPPFCBPMA and MMA were found to be r1=1.2436 and r2=0.8171 determined by Fineman–Ross method, and r1=1.2279 and r2=0.8023 by Kelen–Tudos method respectively. The resultant polymethacrylates bearing perfluorocyclobutyl and sulfonyl functionalities exhibit excellent thermal stability as evidenced from thermogravimetric analysis and the decomposition temperature rose dramatically with the increasing of molecular weights. Random copolymers of BSPPFCBPMA and methyl methacrylate were obtained by free radical copolymerization and their thermo-stabilities increase while raising the contents of BSPPFCBPMA.

Ambient temperature Atom Transfer Radical copolymerization of tetrahydrofurfuryl methacrylate and methyl methacrylate: Reactivity ratio determination

Tetrahydrofurfuryl methacrylate (THFMA), a heterocyclic monomer was polymerized by ambient temperature Atom Transfer Radical Polymerization (AT ATRP) using CuX/PMDETA/EBiB system. THFMA was found to undergo very rapid polymerization, in bulk. For a target DP > 200, bulk polymerization results in cross-linking as evidenced by (CH 2) n ,wag peaks (IR spectroscopy). Atom Transfer Radical copolymerization (ATRcP) of THFMA with MMA was performed and the reactivity ratios were calculated from the copolymer composition, as determined by 1H NMR, using Fineman–Ross and Kelen–Tudos methods. The reactivity ratios determined for ATRP were found to be significantly different from the literature values for conventional free radical polymerization (CFRP). This may be due to the coordination of copper catalytic system with the oxygen atom of the tetrahydrofurfuryl group that could lead to the variation in reactivity ratios. 1H NMR evidence for catalyst–monomer interaction is also provided.

Swelling behavior and metal ion retention from aqueous solution of hydrogels based onN-1-vinyl-2-pyrrolidone andN-hydroxymethylacrylamide

Hydrophilic copolymer gels were prepared by free-radical copolymerization of 1-vinyl-2-pyrrolidone (NVP) and N-hydroxymethyl acrylamide (HMAm). The ratios of both monomers and crosslinker agent (CA) were varied, and the effect of external stimuli such as pH of the swelling media and inorganic ion interaction were investigated. The gels showed a pH-responsive behavior. The interactions of inorganic ions with the hydrophilic hydrogels were determined as a function of pH, copolymer composition, and variation of the composition crosslinking degree. Additionally, a decrease of the pH of the solution caused a decrease in the equilibrium degree of swelling of the copolymer gels. The capacity to remove several metal ions such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Cd(II), and Fe(III) in the aqueous phase was determined by using the liquid-phase polymer-based retention (LPR) technique. In addition, the copolymers and their complexes with transition metal ions were characterized by the monomer reactivity ratios by using the Kelen-Tudos method, elemental analysis, FTIR and 1H-NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Based on the results of swelling and retention capacity of metal ions of poly(NVP-co-HMAm), it was concluded that the swelling and retention capacity properties of the hydrogels depends on the reaction environment's pH. This is regarded as a functional hydrogel, which could be employed as biodegradable materials for applications in agriculture chemicals and as drug delivery systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Synthesis, characterization and thermal properties of homo and copolymers of 3,5-dimethoxyphenyl methacrylate with glycidyl methacrylate: Determination of monomer reactivity ratios

The new methacrylic monomer, 3,5-dimethoxyphenyl methacrylate (DMOPM) was synthesized by reacting 3,5-dimethoxyphenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in presence of triethylamine as a catalyst. The homopolymer and copolymers of DMOPM with glycidyl methacrylate (GMA) were synthesized by free radical polymerization in EMK solution at 70 ± 1 °C using benzoyl peroxide as a free radical initiator. The copolymerization behaviour was studied in a wide composition interval with the mole fractions of DMOPM ranging from 0.15 to 0.9 in the feed. The homopolymer and the copolymers were characterized by FT-IR, 1H NMR and 13C NMR spectroscopic techniques. The solubility was tested in various polar and non-polar solvents. The molecular weight and polydispersity indices of the polymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in DMOPM content. The thermogravimetric analysis of the polymers showed that the thermal stability of the copolymer increases with DMOPM content. The copolymer composition was determined using 1H NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman–Ross ( r 1 = 0.520, r 2 = 2.521), Kelen–Tudos ( r 1 = 0.629, r 2 = 2.554) and extended Kelen–Tudos methods ( r 1 = 0.600, r 2 = 2.502).

Effect of nanoclay and macroinitiator on the kinetics of atom transfer radical homo- and copolymerization of styrene and methyl methacrylate initiated with CCl 3-terminated poly (vinyl acetate) macroinitiator

Effect of nanoclay on the kinetics of atom transfer radical bulk homo- and copolymerization of styrene (St) and methyl methacrylate (MMA) initiated with CCl 3-terminated poly (vinyl acetate) macroinitiator at 90 °C was investigated. CuCl/PMDETA was used as a catalyst system. Results showed that nanoclay significantly enhances the homopolymerization rate of MMA. It was attributed to the activated conjugated C C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al O H) of nanoclay as well as to the effect of nanoclay on the dynamic equilibrium between the active (macro)radicals and dormant species. Homopolymerization rate of St (a noncoordinative monomer with nanoclay) decreased slightly in the presence of nanoclay. It could be explained by inserting of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. Controlled/living characteristic of all the reactions were confirmed by GPC results. More reliable reactivity ratios of the St and MMA in the presence of nanoclay were calculated by using the cumulative average copolymer composition at the moderate to high conversion to be r St = 0.290 ± 0.082, r MMA = 0.443 ± 0.093 (extended Kelen–Tudos method) and r St = 0.293 ± 0.071, r MMA = 0.447 ± 0.080 (Mao–Huglin method). Results indicated that the rate of incorporation of MMA comonomer into the copolymer increases in the presence of nanoclay, verifying the existence of interaction between the carbonyl group of MMA comonomer and the hydroxyl moiety of nanoclay. It was found that in the presence of nanoclay, tendency of the random copolymerization of St and MMA toward an alternating copolymerization increases.

Synthesis of Degradable Materials Based on Caprolactone and Vinyl Acetate Units Using Radical Chemistry

Present studies are carried out with an aim to make degradable materials based on caprolactone and vinyl acetate units using radical chemistry. Radical ring-opening copolymerization of 2-methylene-l,3-dioxepane (MDO) with vinyl acetate in presence of AIBN initiator at 70 °C was carried out to achieve the aim. The copolymerization introduced degradable PCL repeat units onto the C-C backbone of poly(vinyl acetate). Microstructure analysis of the copolymers is done using different ID and 2D NMR techniques. Complete ring-opening polymerization of MDO to give ester units was observed during copolymerizations. Reactivity ratios were found out by Kelen Tudos method and were rVAc = 1.53 and rMDO = 0.47 leading to statistical introduction of ester linkages onto the polymer backbone. The materials showed varied glass transition temperatures (from 37 to −44°C) depending upon the amount of ester linkages and very high elongations. The hydrolysis products were also tested for cytotoxicity studies in L929 cells and compared with that of known and accepted standard materials like poly(ethyleneimine). The hydrolysed products were non toxic and showed a cell viability > 95%. Keeping in view the combined properties like degradability, non-toxicity and low glass transition temperatures, the resulting materials could therefore be proposed for different applications like degradable gums, coatings etc.

ANTIMICROBIAL ACTIVITY OF COPOLYMERS OF 2,4-DICHLOROPHENYL ACRYLATE WITH STYRENE: SYNTHESIS, CHARACTERIZATION AND REACTIVITY RATIOS

Some copolymers of 2,4-dichlorophenyl acrylate (2,4-DCPA) with styrene (St) of different feed compositions were prepared by free radical polymerization technique using 2,2′-azobisisobutyronitrile (AIBN) as an initiator, and the copolymers were characterized by IR spectroscopy. The copolymer composition obtained by UV-spectra led to determination of reactivity ratio by employing Fineman-Ross (F-R) and Kelen-Tudos (K-T) methods. Average molecular weight, as well as intrinsic viscosity, was obtained by vapor pressure osmometry (VPO) and Ubbleholde viscometer. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) of copolymers were carried out under nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated against various microorganisms such as bacteria, fungi and yeasts.

Hydrogels from 2-(dimethylamino)ethylacrylate with 2-acrylamido-2-methyl-1-propanesulfonic acid: synthesis, characterization, and water-sorption properties

A novel series of copolymer hydrogels of 2-(dimethylamino)ethylacrylate (DMAEA)/2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) were prepared by solution free radical polymerization at different feed monomer mol ratios. The monomer reactivity ratios were determined by Kelen–Tudos method. According to that, the monomer reactivity ratios for poly(DMAEA-co-AMPS) were r1 = 0.125 and r2 = 2.85, (r1 × r2 = 0.356). The effect of reaction parameters, including the concentration of cross-linking reagent N,N′-methylene-bis-acrylamide (MBA) and initiator ammonium persulfate (APS), the monomer concentration, pH, temperature, salt solutions, and solvent polarity on the water absorption have been also studied. The hydrogels achieved water-absorption values of 430 g of water/g of xerogel for the copolymer 1:2 richest in AMPS moiety. This copolymer is also very stable to the temperature effect. The optimum pH for the copolymers is 7. Aqueous solutions of the copolymers showed lower critical solution temperature behaviour (LCST). The phase transition temperatures of aqueous solutions of these copolymer increased with increasing of hydrophilic AMPS unit content in the copolymers. The glass transition temperature (Tg) of hydrogels showed a decrease by increasing of comonomer DMAEA content.

Study on monomer reactivity ratios of acrylonitrile/itaconic acid in aqueous deposited copolymerization system initiated by ammonium persulfate

A single water-soluble initiator-ammonium persulfate (APS), not containing alkali metal ions, was first utilized to initiate copolymerization of acrylonitrile (AN)/itaconic acid (IA) in aqueous deposited copolymerization system. Monomer reactivity ratios of this polymerization system were investigated using element analysis method and Q–e schemes. It was found that the monomer reactivity ratios of AN/IA calculated from Q–e schemes are 0.505 (rAN) and 1.928 (rIA), while the monomer reactivity ratios of AN/IA in aqueous deposited copolymerization system at 60 °C are 0.64 (rAN) and 1.37 (rIA) calculated from Kelen–Tudos method, 0.61 (rAN) and 1.47 (rIA) from Fineman–Ross method. The three pairs of monomer reactivity ratios are in good agreement. With the increase of the polymerization temperature, the monomer reactivity ratios of AN and IA approach to unity, indicating that the aqueous deposited copolymerization of AN/IA has a tendency to ideal copolymerization. At lower polymerization conversion, the monomer reactivity ratios of AN and IA have hardly any changes. When the polymerization conversion is more than 5%, the monomer reactivity ratio of AN increases, while that of IA decreases.

A study on the copolymerization kinetics of phenylethyl acrylate and phenylethyl methacrylate

Copolymers of phenyl alkyl acrylates/methacrylates are used clinically as soft materials for the foldable intraocular lens (IOL) to treat cataracts. In this study, copolymers of 2-phenylethyl acrylate (PEA) and 2-phenylethyl methacrylate (PEMA) of various compositions were prepared using free radical polymerization in solution. The composition of the copolymers was determined by1H-NMR analysis. The reactivity ratios of the monomers were calculated using the conventional Fineman-Ross or Kelen-Tudos method. The reactivity ratio of PEA (r1) and PEMA (r2) were estimated to be 0.280 and 2.085 using the Kelen-Tudos method, respectively. These values suggest that PEMA is more reactive in copolymerization than PEA, and the copolymers will have a higher content of PEMA units. The glass transition temperature (Tg) of the copolymers increased with increasing PEMA content. The molecular weight and polydispersity indices (Mw/Mn) of the polymers were determined by GPC. Overall, these results are expected to be quite useful in applications to foldable soft IOL materials.

Copolymerization of 4-cyanophenyl acrylate with methyl methacrylate: synthesis, characterization and determination of monomer reactivity ratios

A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using 1H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r1=2.524±0.038, r2=0.502±0.015), Kelen-Tudos (r1=2.562±0.173, r2=0.487±0.005) and extended Kelen-Tudos methods (r1=2.735±0.128, r2=0.4915±0.007).