Ring opening polymerization of 2-aminothiazole with iron(III) chloride

Poly(2-aminothiazole), PAT, was synthesized by the chemical polymerization of 2-aminothiazole, AT, with FeCl₃·6H₂O in 1,4-dioxane. The effect of temperature, monomer, and initiator concentration and polymerization time on the rate of polymerization was studied. The structural analysis of the polymer was carried out by elemental analysis and ¹H-NMR, FTIR, and UV–VIS spectroscopies. Thermal properties were studied by DSC and TGA. Conductivity measurements were carried out by four-probe technique and the number average molecular weight, M _n, of the polymer was determined by cryoscopy.     

Chemical synthesis and characterization of soluble conducting poly(2-aminothiazole)

Poly(2-aminothiazole), (P-2AT), was synthesized by chemical polymerization method using 2-aminothiazole as the monomer. Structural characterizations were carried out by Fourier transform infrared, nuclear magnetic resonance, UV-vis spectroscopy, elemental analysis and scanning electron microscopy techniques. Thermal characterizations were carried out by thermogravimetric analysis and differential scanning calorimetry techniques. The number average molecular weight, M_n, of the polymer was determined by gel permeation chromatography. The effects of monomer and initiator concentration and polymerization time on the polymer yield were also studied. The solubility of the P-2AT was tested in common organic solvents as well as in acidic and basic solutions. P-2AT was soluble in DMSO, THF and DMF and its conductivity value measured 3 × 10^?6 S/cm.     

Electroinitiated polymerization of 2-allylphenol

Summary Redox behaviour of 2-allylphenol (2APhOH) was studied by using cyclic voltammetry (CV) and electroinitiated polymerization was conducted at the measured peak potentials. Constant potential electrolysis (CPE) of the monomer was carried out in acetonitrile-sodium perchlorate, solvent-electrolyte couple, at room temperature. Polymerization of the monomer yielded insoluble polymer films on the surface of the electrode together with the low molecular weight polymers in the bulk of the solution. The structural analysis of the polymers were carried by ¹H-NMR and FTIR spectroscopy. Molecular weight of the soluble polymer was determined by GPC. Thermal properties of the polymer film and soluble polymer were studied by DSC. The course of electroinitiated polymerization was monitored by in-situ UV-VIS spectroscopy. Received: 10 April 2000/Revised version: 21 June 2000/Accepted: 5 July 2000     

Polymerization of N‐phenylmaleimide with a rare‐earth coordination catalyst

The polymerization of N‐phenylmaleimide was carried out with the binary rare‐earth coordination catalyst lanthanum phosphonate [La(P₅₀₇)]–trisobutyl aluminum [Al(i‐Bu)₃] in toluene at 60°C. The dependence of the polymerization on the polymerization time, the molar ratio of Al(i‐Bu)₃ to La(P₅₀₇), and the concentration of the catalyst were studied. The structures of the resultant polymer were characterized with ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectrophotometry, and the thermal properties of the polymer were measured with thermogravimetric analysis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 979–982, 2005     

Preparation and performance study on P(St‐MMA)‐SiO2 doped P(VDF‐HFP) based composite polymer electrolyte

The organic–inorganic hybrid material poly(styrene‐methyl methacrylate)‐silica (P(St‐MMA )‐SiO₂) was successfully prepared by in situ polymerization confirmed by Fourier transform infrared spectroscopy and was employed to fabricate poly(vinylidene fluoride‐hexafluoropropylene) (P(VDF‐HFP )) based composite polymer electrolyte (CPE ) membrane. Desirable CPEs can be obtained by immersing the CPE membranes into 1.0 mol L^?1 LiPF₆‐EC /DMC /EMC (LiPF₆ ethylene carbonate + dimethyl carbonate + ethylmethyl carbonate) liquid electrolyte for about 0.5 h for activation. The corresponding physicochemical properties were characterized by SEM , XRD , electrochemical impedance spectroscopy and charge–discharge cycle testing measurements. The results indicate that the as‐prepared CPEs have excellent properties when the mass ratio of the hybrid P(St‐MMA )‐SiO ₂ particles to polymer matrix P(VDF‐HFP ) reaches 1:10, at which point the SEM analyses show that the as‐prepared P(St‐MMA )‐SiO ₂ particles are uniformly dispersed in the membrane and the CPE membrane presents a homogeneous surface with abundant interconnected micropores. The XRD results show that there may exist interaction forces between the P(St‐MMA )‐SiO ₂ particles and the polymer matrix, which can obviously decrease the crystallinity of the composite membrane. Moreover, the ionic conductivity at room temperature and the electrochemical working window of the CPE membrane can reach 3.146 mS cm^?1 and 4.7 V, respectively. The assembled LiCoO₂/CPE /Li coin cell with the CPE presents excellent charge–discharge and C ‐rate performance, which indicates that P(St‐MMA )‐SiO ₂ hybrid material is a promising additive for the P(VDF‐HFP ) based CPE of the lithium ion battery. © 2016 Society of Chemical Industry     

Studies on the preparation of branched polymers from styrene and divinylbenzene

The self‐condensing vinyl polymerization of styrene and an inimer formed in situ by atom transfer radical addition from divinylbenzene and 2‐bromoisobutyl‐tert‐butyrate using atom transfer radical polymerization technique was studied. To study the polymerization mechanism and achieve high molecular weight polymer in a high polymer yield, the polymerization was carried out in bulk at 80°C. Proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and gel permeation chromatography (GPC) coupled with multiangle laser light scattering (MALLS) were used to monitor the polymerization process and characterize the solid polymers. It is proved that the polymerization shows a “living” polymerization behavior and the crosslinking reaction has been restrained effectively due to the introduction of styrene. Polymers with high molecular weight (M_w.MALLS > 10⁵) can be prepared in high yield (near 80%). Comparison of the apparent molecular weights measured by GPC with the absolute values measured by MALLS indicates the existence of branched structures in the prepared polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of glucose-substituted poly(<Emphasis Type="Italic">p</Emphasis>-phenylene)s with twisted main-chain in one direction due to induced axial chirality

Summary The peracetylated and free glucose-substituted poly(p-phenylene)s were synthesized by the coupling polymerization of a dibromobenzene monomer using Ni complex and the subsequent deacetylation by hydrazine monohydrate. The polymerization was carried out using bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)₂) as a coupling agent with 2,2’-bipyridyl (bpy) and 1,5-cyclooctadiene (COD) in a mixed solvent of DMF and toluene. The structure of the product was confirmed by ¹H and ¹³C NMR measurements to be the poly(p-phenylene) having peracetylated glucose residues. The M_n values were estimated by GPC analysis with DMF as eluent to be 7300–9800. The fluorescence analysis of the polymer was carried out in comparison with that of the dimeric model compound. The CD spectrum of the polymer indicated that the main-chain was twisted and immobilized in one direction due to the chirality and bulkily of the peracetylated glucose residues. The deacetylation using hydrazine monohydrate completely took place to give the free glucose-substituted poly(p-phenylene).     

Kinetic studies of the chemical polymerization of substituted aniline in aqueous solutions and characterization of the polymer obtained Part 1. 3‐Chloroaniline

Aqueous polymerization of 3‐chloroaniline (mCA) was studied using sodium dichromate as oxidant in the presence of hydrochloric acid. The effect of hydrochloric acid, sodium dichromate and monomer concentration on the polymerization rate, specific viscosity of the obtained polymer and ac conductivity was investigated. The initial and overall reaction rates increase with increasing hydrochloric acid concentration or sodium dichromate concentration, but decrease with increasing monomer concentration. The specific viscosity values (η_sp) increase with increasing hydrochloric acid concentration or monomer concentration, which means that the molecular weight of the polymer samples increases accordingly. On the contrary, the molecular weight decreases with increasing sodium dichromate concentration. The highest ac conductivity value of the obtained polymer was found for 0.0255 mol l⁻¹ of Na₂Cr₂O₇, 0.8 mol l⁻¹ HCl and 0.0956 mol l⁻¹ monomer concentration in the reaction medium. The order of the polymerization reaction with respect to hydrochloric acid, Na₂Cr₂O₇ and monomer concentration was found to be 1.0, 0.9 and 0.75, respectively. The apparent activation energy (E_a) for this polymerization system was found to be 13.674 × 10⁴ mol⁻¹. The obtained poly(3‐chloroaniline) was characterized by UV–visible, IR and ¹H NMR spectroscopy. X‐ray diffraction analysis and electron microscopy studies were carried out. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) results were used to confirm the structure. © 2001 Society of Chemical Industry     

Direct Controlled Polymerization of Ionic Monomers by Surface-Initiated ATRP Using a Fluoroalcohol and Ionic Liquids

Surface-initiated atom transfer radical polymerization (ATRP) of (2-methacryloyloxyethyl)trimethylammonium chloride (MTAC), 3-(N-2-methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate) (MAPS), and 2-methacryloyloxyethyl phosphorylcholine (MPC) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3-methylimidazolium chloride at 60 °C to produce well-defined ionic polymer brushes and the corresponding free polymers with predictable number-average molecular weight (M_n, 1×10⁴−3×10⁵ g mol⁻¹) and narrow molecular weight dispersity (M_w/M_n<1.2). A first-order kinetic plot for ATRP of MTAC and MAPS revealed a linear relationship between the monomer conversion index (ln([M]₀/[M])) and polymerization time. Reduction in polymerization rates was observed with an increase in ionic liquid concentration. The M_n of both poly(MTAC) and poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the M_n of the polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated.     

Preparation of bimodal polypropylene in two‐step polymerization

Polymerization of propylene was carried out by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system in n‐heptane, where MgCl₂, EtOH, TiCl₄, DIBP (diisobutyl phthalate), TEA (triethyl aluminum), and cHMDMS (cyclohexyl methyl dimethoxy silane) were support, ethanol for alcoholation, catalyst, external donor, cocatalyst (activator), and internal donor, respectively. The catalyst activity and polymer isotacticity were studied by measuring the produced polymer and its solubility in boiling n‐heptane, respectively. The molecular weight and molecular weight distribution of the polymers were evaluated by gel permeation chromatography. Hydrogen was used for controlling the molecular weight. For producing the bimodal polypropylene, the polymerization was carried out in two steps (i.e., in the presence and absence of hydrogen). It was found that the catalyst showed high activity and stereoselectivity, on the other hand, bimodal polymer could simply be produced in two‐step polymerization by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system. Meanwhile, the effect of the step of the hydrogen adding on propylene polymerization was investigated. It was shown that the addition of hydrogen in the second step was more suitable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1456–1462, 2006     

Electrochemical behaviour and electrochemical polymerization of fluoro‐substituted anilines

The electrochemical behaviour of three fluoro‐substituted aniline monomers, 2‐fluoroaniline (2FAN), 3‐fluoroaniline (3FAN) and 4‐fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile–water mixture (1:1 by volume) using NaClO₄ as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin resonance (ESR) and in situ UV–VIS spectroscopic techniques for one of the monomers (4FAN). Both CV and in situ UV–VIS measurements indicated that the polymers obtained are in the emeraldine base form. In situ ESR studies indicated that electrochemical polymerization involves a radical‐cation as an intermediate. Characterization of polymer products have been carried out using FTIR and NMR spectroscopic techniques, and thermal behaviour was studied using differential scanning calorimetry (DSC). It was found that conductivity can be imparted to as‐synthesized polyfluoroanilines via iodine doping. © 2002 Society of Chemical Industry     

No2–initiated polymerization of acrylamide in dimethylsulfoxide

NO₂-initiated polymerization of acrylamide in dimethylsulfoxide was carried out. The dependence of monomer, initiator concentrations, and temperature on polymer yield and initial rate of polymerization was studied. The overall activation energy of polymerization was calculated to be about 15 kcal mol^?1. The copolymerization of acrylamide with methyl methacrylate was also studied. The kinetic mechanism of polymerization was proposed.     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (R_p) was found to be R_p = k[AIBN]^0.5[ 1 ]^1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol^?1. The monomer reactivity ratios in copolymerization with styrene were r ₁ = 2.65 and r_st = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry     

Solubility parameters of two chlorinated polyethylene polymers

An equation that appears adequate for the calculation of the solubility parameter of random copolymers was tested with two nonrandom copolymers, chlorinated polyethylene (CPE) AK 227 and AK 243, containing 27.8% and 42.1% chlorine, respectively. Flory's equation relating the energy of interaction between polymer and diluent to the depression of the melting point of the pure polymer was used to estimate the solubility parameter of the polymers from solution temperature studies in chlorobenzene, toluene, o-xylene, and p-xylene. Using data obtained on PE as a criterion, agreement within 3% was obtained between the reported δ-value and that estimated from solution temperature studies when toluene, o-xylene, and p-xylene were used as diluents. In the case of the two CPE polymers, values for the gas constant and for the heat of fusion in units of cal/cm³ polymer °K and cal/cm³ polymer, respectively, were obtained by solving simultaneous equations. From the derived gas constant values, the weight of an average repeating unit of CPE polymer was obtained, 39.38 for AK 227 and 46.95 for AK 243, which compares favorably with values obtained using the expression n₁M₁ + n₂M₂ = M_x. For ΔH, the results showed that in going from PE to CPE, a reversal in the sign of ΔH occurs indicating that, in the diluents studied, the value of χ is positive in the case of PE and negative for the CPE polymers. Taking this into account, agreement between calculated δ-values and those estimated from solution temperature studies is within 2% for AK 227 (toluene, o-xylene, p-xylene) and within 1% for AK 243 when toluene and o-xylene were used as diluents. Anomalous results were obtained in the latter case when p-xylene and chlorobenzene were used as diluents and from solution temperature studies of PE in chlorobenzene. The results do indicate that the equation used to calculate the solubility parameter of random copolymers may also be used for nonrandom copolymers such as CPE.     

Chain walking copolymerization of ethylene with cyclopentene - Effect of ring incorporation on polymer chain topology

Chain walking ethylene copolymerizations with cyclopentene (CPE) as the ring-forming comonomer were carried out in this study to investigate the tuning of polyethylene chain topology via the unique strategy of ring incorporation. Four sets of polymers containing five-membered rings on the polymer backbone at various low contents (in the range of 0-7.5 mol%) were synthesized by controlling CPE feed concentration at four different ethylene pressure/temperature combinations (1 atm/15 °C, 1 atm/25 °C, 1 atm/35 °C, and 6 atm/25 °C, respectively) using a Pd-diimine catalyst, [(ArNC(Me)-(Me)CNAr)Pd(CH₃)(NCMe)]⁺SbF₆⁻ (Ar = 2,6-(iPr)₂C₆H₃). The polymers were characterized extensively using ¹³C nuclear magnetic resonance (NMR) spectroscopy, triple-detection gel permeation chromatography (GPC), and rheometry to elucidate the chain microstructures and study the effect of ring incorporation on polymer chain topology. It was found that CPE was incorporated in the copolymers primarily in the form of isolated cis-1,3 ring units, along with a small fraction in the form of isolated cis-1,2 ring units. Significant linearization of polymer chain topology was achieved with ring incorporation in each of the three sets of polymers synthesized at 1 atm on the basis of the incrementally raised intrinsic viscosity curves in the Mark-Houwink plot and the significantly enhanced zero-shear viscosity of the polymer melts with the increase of ring content despite the decreasing polymer molecular weight. For the set of polymers synthesized at 6 atm/25 °C, the effect of ring incorporation on polymer chain topology was negligible or weaker due to their linear chain topology resulting at this polymerization condition. The results obtained in this study support the proposed blocking effect of backbone-incorporated rings on catalyst chain walking, and demonstrate that effective tuning of polyethylene chain topology from hyperbranched to linear can be conveniently achieved via CPE incorporation while without changing ethylene pressure or polymerization temperature.     

Controlled/‘living’ radical polymerization of methyl methacrylate with p-TsCl/CuBr/BPY initiating system under microwave irradiation

Atom-transfer radical polymerization of methyl methacrylate under microwave irradiation (MI) using p-TsCl/CuBr/BPY as the initiating system was successfully carried out. The polymerization of methyl methacrylate under MI shows linear first-order rate plots, a linear increase in the number-average molecular weight with conversion and low polydispersities, 1.1 < M_w/M_n < 1.3. The influence of polymerization time, temperature and monomer/initiator ratio on the conversion, molecular weight and polymer distribution were studied using the MI process, and compared with that obtained by the corresponding conventional heating (CH) process. The MI process not only increases the rate of polymerization, but also narrows the polydispersity index of polymers. The apparent rate constant, , under MI is 6–8 times higher than that under CH with an identical initiating system and polymerization temperature. The effect of MI on the stereoregularity and T_g of PMMA were investigated by ¹³C NMR spectroscopy and DSC, respectively. Copyright © 2004 Society of Chemical Industry     

Grafting of poly-β-alanine onto carbon black: The hydrogen transfer polymerization of acrylamide catalyzed by n-butyllithium in the presence of carbon black

The hydrogen transfer polymerization of acrylamide (AAm) catalyzed by n-butyllithium in the presence of carbon black was carried out at 80–100°C and the grafting of poly-β-alanine (nylon 3) was investigated. It was suggested that the growing polymer anion was captured by the quinonic oxygen group on the surface of carbon black. Furthermore, the growing polymer anion reacted with the phenolic hydroxyl group on the surface to give ungrafted polymer and the lithium phenolate (? O^?Li⁺) group (chain transfer to phenolic hydroxyl group). The ? O^?Li⁺ group formed was considered to be capable of initiating the hydrogen transfer polymerization of AAm. Accordingly, during the hydrogen transfer polymerization in the presence of carbon black, poly-β-alanine was effectively grafted by the termination of growing polymer anion and the propagation of the polymer from the ? O^?Li⁺ group on the surface. The grafting ratio was determined to be 60–80%. The carbon black obtained from the polymerization gave a stable colloidal dispersion in water, N,N-dimethylformamide, and formic acid. Furthermore, it was found that the ratio of hydrogen transfer polymerization to normal vinyl polymerization (T ratio) increased with an increase in polymerization temperature.     

Microemulsion polymerization of styrene using developed redox initiation system and study of rheological properties of obtained latices

Microemulsion polymerization of styrene was kinetically studied using a potassium persulfate (KPS)/P‐methyl benzaldehyde sodium bisulfite (MeBSBS) adduct as the developed redox pair initiation system. The rate of microemulsion polymerization of styrene was found to be dependent on the initiator, emulsifier, and monomer to the powers of 1.4, −0.77, and 0.83, respectively. The apparent Arrhenius activation energy (E_a) estimated for the microemulsion polymerization system was 6.5 × 10⁴ J/mol. Also, the morphological parameters were studied at different initiator concentrations. The rheological measurements for the prepared microemulsions were carried out to investigate the effect of the preparation parameters on the rheological behavior of the polystyrene microemulsions. The rheological flow curves of the polystyrene microemulsion latices prepared at different temperatures were carried out, and we found that the plastic viscosity and Bingham yield values of the flow curves increased with an increasing reaction temperature. That may be due to the cage effect of the prepared polymer particles, which trapped the medium molecules. The plastic viscosity increased with increasing emulsifier concentration while the Bingham yield value decreased. For the polystyrene microemulsion prepared in the presence of different initiator concentrations, the plastic viscosity and Bingham yield increased with increasing initiator concentration. This trend was found to be the same for the microemulsion latices prepared in the presence of different monomer concentrations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1240–1249, 2000     

Formation of monodisperse polyacrylamide particles by radiation‐induced dispersion polymerization. I. Synthesis and polymerization kinetics

Highly monodisperse polyacrylamide (PAM) microparticles were directly prepared by radiation‐induced dispersion polymerization at room temperature in an aqueous alcohol media using poly(N‐vinylpyrrolidone) (PVP) as a steric stabilizer. Monomer conversion was studied dilatometrically and polymer molecular weight was determined viscometrically. The gel effect was found evidently from the polymerization kinetics curves. The influence of the dose rate, monomer concentration, stabilizer content, medium polarity, polymerization temperature on the polymerization rate, and the molecular weight of the polymer was examined. The polymerization rate (Rp) can be represented by Rp ∝ D^0.15[M]^0.86[S]^0.47[A/W]^0.64 and the molecular weight of the polymer can be represented by M_w ∝ D^?0.19 [M]^1.71[S]^0.43[A/W]^0.14 at a definite experimental variation range. The overall activation energy for the rate of polymerization is 10.57 kJ/mol (20–35°C). Based on these experimental results, the polymerization mechanisms were discussed primarily. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2567–2573, 2002