• copolymerization;
  • differential scanning calorimetry (DSC);
  • ESR/EPR;
  • FT-IR;
  • radical polymerization


The free-radical copolymerization of 4-vinyl pyridine (4-VP) with methyl acrylate (MA) initiated by p-acetylbenzylidene triphenylarsonium ylide at 60 ± 0.1°C with dioxane as an inert solvent yielded random copolymers. The kinetic equation was Rp ∝ [Ylide]0.83[4-VP]0.33 [MA]0.40 (where Rp is the rate of polymerization); in other words, the system followed nonideal kinetics. The values of the energy of activation and kp2/kt (where kp is the rate constant of propagation and kt is the rate constant of termination) were 23.21 kJ/mol and 1.212 × 10−5 mol L−1 s−1, respectively. The reactivity ratios calculated with the Kelen–Tüdos method were 0.14 ± 0.0075 for 4-VP and 0.56 ± 0.0078 for MA. The copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, differential scanning calorimetry, and electron spin resonance methods. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009