Diphenylselenonium 2,3,4,5-tetraphenylcyclopentadienylide-initiated polymerization of styrene and acrylonitrile: Synthesis, characterization, reactivity ratios, and thermal properties



Solution copolymerization of styrene (Sty) and acrylonitrile (AN) was carried out in dioxane at 60 ± 1°C for 90 min using diphenylselenonium 2,3,4,5-tetraphenylcyclopentadienylide (selenonium ylide) as radical initiator. The kinetic expression is as follows: Rp ∼ [Ylide]0.5 [Sty]1.0 [AN]1.0. The overall activation energy is 28.72 kJ mol−1. The composition of copolymer calculated from 1H-NMR and elemental analysis was used to evaluate reactivity ratio as r1 (Sty) = 0.351 and r2 (AN) = 0.0185, using kelen-Tudos method. It confirmed the alternating nature of the copolymer. The copolymer was characterized using Fourier transform infrared (FTIR) spectroscopy, 1H-NMR, 13C-NMR, differential scanning calorimetry, and thermal gravimetric analysis. Electron spin resonance spectroscopy confirmed the presence of the phenyl radical responsible for initiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011