Redox‐Initiated RAFT Polymerization and (Electro)chemical Activation of RAFT Agents

Redox chemical and electrochemical approaches to initiating and externally controlling reversible addition–fragmentation chain transfer (RAFT) polymerization enable the preparation of well-defined and complex polymeric architectures under mild conditions. Redox pairs and electrochemical currents/potentials were used to generate radicals at room temperature, replacing conventional thermal radical initiators and minimizing the generation of new chains during polymerization. Moreover, redox-initiated RAFT polymerizations, including Fenton-RAFT polymerizations, could be coupled with enzymatic degassing. Alternatively, transition metal complexes were used to activate RAFT agents, eliminating the need of radical initiators. Electrochemically mediated RAFT ( e RAFT) polymerization was developed by using electrochemical stimuli to activate RAFT agents and control the polymerization.