End group removal and modification of RAFT polymers

Abstract

This paper describes both well-established routes and recent advances in the end group modification of polymers synthesised by reversible addition–fragmentation chain transfer (RAFT) polymerisation. The lability of the thiocarbonylthio group, which facilitates the RAFT mechanism, allows for ready post-polymerisation functionalisation of RAFT polymers by a number of techniques. In particular, end group thermolysis, radical induced reduction, hetero-Diels–Alder reactions and reaction with nucleophiles are discussed as are the applications and limitations of each method. The versatility of RAFT as a polymerisation tool for the synthesis of polymers with functional end groups for a range of applications is demonstrated.