End-functional polymers, thiocarbonylthio group removal/transformation and reversible addition-fragmentation-chain transfer (RAFT) polymerization

This review focuses on processes for thiocarbonylthio group removal/transformation of polymers synthesized by radical polymerization with reversible addition-fragmentation-chain transfer (RAFT). A variety of processes have now been reported in this context. These include reactions with nucleophiles, radical-induced reactions, thermolysis, electrocyclic reactions and 'click' processes. We also consider the use of RAFT-synthesized polymers in the construction of block or graft copolymers, functional nanoparticles and biopolymer conjugates where transformation of the thiocarbonylthio group is an integral part of the process. This includes the use of RAFT-synthesized polymers in other forms of radical polymerization such as atom transfer radical polymerization or nitroxide-mediated polymerization, and the 'switching' of thiocarbonylthio groups to enable control over polymerization of a wider range of monomers in the RAFT process. With each process we provide information on the scope and, where known, indicate the mechanism, advantages and limitations. (C) 2011 Society of Chemical Industry