Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Abstract

Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.