Experimental requirements for an efficient control of free-radical polymerizations via the reversible addition-fragmentation chain transfer (RAFT) process

Reversible addition-fragmentation chain transfer (RAFT) polymerization is a recent and very versatile controlled radical polymerization technique that has enabled the synthesis of a wide range of macromolecules with well-defined structures, compositions, and functionalities. The RAFT process is based on a reversible addition-fragmentation reaction mediated by thiocarbonylthio compounds used as chain transfer agents (CTAs). A great variety of CTAs have been designed and synthesized so far with different kinds of substituents. In this review, all of the CTAs encountered in the literature from 1998 to date are reported and classified according to several criteria : i) the structure of their substituents, ii) the various monomers that they have been polymerized with, and iii) the type of polymerization that has been performed (solution. dispersed media. surface initiated, and copolymerization). Moreover, the influence of various parameters is discussed, especially the CTA structure relative to the monomer and the experimental conditions (temperature, pressure, initiation, CTA/initiator ratio, concentration), in order to optimise the kinetics and the efficiency of the molecular-weight-distribution control.