Mechanism of dithiobenzoate-mediated RAFT polymerization: A missing reaction step

Abstract

The debate on the mechanism of dithiobenzoate-mediated RAFT polymerization may be resolved by including the reaction between a propagating radical and the star-shaped combination product from irreversible termination into the kinetic scheme. By this step, a highly reactive propagating radical and a not overly stable three-arm star species are transformed into the resonance-stabilized RAFT intermediate radical and a very stable polymer molecule. The time evolution of concentration is discussed for the main-equilibrium range of CDB-mediated methyl acrylate polymerization.