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Macromolecular Rapid Communications, Vol.27, No.16, 1299-1305, 2006
Mechanism of dithiobenzoate-mediated RAFT polymerization: A missing reaction step
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.
Keywords:controlled living radical polymerization;kinetics (polym.);polymerization mechanism;rate retardation;reversible addition-fragmentation chain transfer (RAFT)