Polymerization of methyl acrylate with triphenylbismuthonium 1,2,3,4‐tetraphenylcyclopentadienylide as a new radical initiator

Abstract

AbstractTriphenylbismuthonium 1,2,3,4‐tetraphenylcyclopentadienylide in 1,4‐dioxan initiated radical polymerization of methyl acrylate to ∼30% conversion without gelation because of autoacceleration. The polymer had a viscosity‐average molecular weight of 200,000. The kinetic expression was Rpα[I]0.3[M]1.16, that is, the system followed nonideal kinetics because of primary radical termination and degradative chain‐transfer reactions. The values of kkt and the energy of activation were computed as 3.12 × 10−5 Lmol−1s−1 and 28 kJ/mol, respectively. The ylide dissociated to form a phenyl radical, which brought about polymerization of methyl acrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2060–2065, 2004