Macromolecular design via reversible addition–fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization

TLDR

RAFT and MADIX polymerizations are among the most versatile living radical polymerization techniques, offering broad monomer scope, functional tolerance, and diverse polymer architectures. The review surveys progress in RAFT/MADIX polymerization since 1998, outlining future challenges and its expanding role as a synthetic tool for functional macromolecules and materials. It details the mechanism and kinetics of RAFT/MADIX, discusses chain‑transfer agent synthesis, polymerization conditions, and catalogs the monomers and architectures successfully produced. The review identifies future challenges for RAFT/MADIX and highlights its growing adoption as a versatile tool for creating functional macromolecules and materials. © 2005 Wiley Periodicals, Inc., J.

Abstract

Abstract Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl‐thio compounds used as chain‐transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005