A Quantum-Chemical Approach to Understanding Reversible Addition Fragmentation Chain-Transfer Polymerization

Abstract

This article highlights some of the recent contributions that computational quantum chemistry has made to the understanding of the reversible addition fragmentation chain transfer (RAFT) polymerization process. These include recent studies of rate retardation in cumyl dithiobenzoate mediated polymerization of styrene and methyl acrylate and the xanthate mediated polymerization of vinyl acetate, and studies of the effects of substituents on the addition and fragmentation reactions in prototypical systems and polymer-related systems. The accuracy and applicability of theoretical procedures for studying free-radical polymerization are also discussed, and the methodology is evaluated using the homopropagation rate coefficient of methyl acrylate as a test case. The review concludes with a brief discussion of possible future developments in the field.