Kinetics and mechanism of RAFT polymerization

RAFT polymerization has emerged as one of the more versatile methods of living radical polymerization. In this paper aspects of the kinetics and mechanism of RAFT polymerization are discussed with a view to pointing out some of the advantages and limitations of various RAFT agents and providing some guidance on how to select a RAFT agent for a particular polymerization. Factors discussed include: transfer constants (C-tr, C-tr) of RAFT agents - (measurement, substituent effects, prediction with MO calculations, reversibility), retardation (examples, dependence on RAFT agent and monomer, possible mechanisms) and formation of multimodal distributions (examples, contributing mechanisms).