Advances in RAFT polymerization: the synthesis of polymers with defined end-groups

This paper provides an overview and discusses some recent developments in radical polymerization with reversible addition–fragmentation chain transfer (RAFT polymerization). Guidelines for the selection of RAFT agents are presented. The utility of the RAFT process is then illustrated with several examples of the synthesis of polymers with reactive end-groups. Thus, RAFT polymerization with appropriately designed trithiocarbonate RAFT agents is successfully applied to the synthesis of narrow polydispersity carboxy-functional poly(methyl methacrylate) and primary amino-functional polystyrene. Methods for removing the thiocarbonylthio end-group by aminolysis, reduction and thermal elimination are discussed. It is shown that the thiocarbonylthio end-group can be cleanly cleaved by radical induced reduction with tri-n-butylstannane, to leave a saturated chain end, or by thermolysis, to leave an unsaturated chain end.