Copolymerization of methyl acrylate with styrene using triphenylstibonium 1,2,3,4-tetraphenylcyclopentadienylide as a novel radical initiator

Abstract

The free-radical copolymerization of methyl acrylate with styrene initiated by triphenylstibonium 1,2,3,4-tetraphenylcyclopentadienylide under nitrogen blanket at (60 ± 0.1)°C in 1,4,dioxane for 2 h has been carried out. The kinetic expression is Rp ∝ [I]0.14 [MA]0.70 [Sty]0.75. The system follows nonideal kinetics due to primary radical termination as well as degradative chain transfer reactions. The overall activation energy is 42 kJ mol−1. The reactivity ratios calculated from Kelen–Tüdos method for r1 (MA) and r2 (Sty) are 0.16 ± 0.01 and 0.028 ± 0.005 respectively. These values suggest the alternating nature of the copolymer. The ylide dissociated to form a phenyl radical, which brings about copolymerization of methyl acrylate with styrene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1731–1736, 2007