Retardation in RAFT Polymerization: Does Cross-Termination Occur with Short Radicals Only?

The recently proposed model by Perrier and co-workers [J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 3455] to account for retardation effects in dithiobenzoate-mediated reversible addition fragmentation chain transfer (RAFT) polymerization of styrene has been tested experimentally. According to this model, retardation is caused by cross-termination of very short radicals only. Polymerizations were conducted employing a macroazoinitiator and a polymeric RAFT agent based on cumyl dithiobenzoate, thereby effectively eliminating all short radicals from the system. The results show, in basic agreement with the model, that there is very little, if any, retardation in dithiobenzoate-mediated RAFT polymerization of styrene in the absence of short radicals.