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Electrochemically Mediated Reversible Addition–Fragmentation Chain-Transfer Polymerization
- Wang, Yi, Fantin, Marco, Park, Sangwoo, Gottlieb, Eric, Fu, Liye, Matyjaszewski, Krzysztof
- Macromolecules 2017 v.50 no.20 pp. 7872-7879
- acrylates, composite polymers, electrochemistry, electrodes, free radicals, polymerization
- An electrochemically mediated reversible addition–fragmentation chain-transfer polymerization (eRAFT) of (meth)acrylates was successfully carried out via electroreduction of either benzoyl peroxide (BPO) or 4-bromobenzenediazonium tetrafluoroborate (BrPhN₂⁺) which formed aryl radicals, acting as initiators for RAFT polymerization. Direct electroreduction of chain transfer agents was unsuccessful since it resulted in the formation of carbanions by a two-electron-transfer process. Reduction of BrPhN₂⁺ under a fixed potential showed acceptable control but limited conversion due to the generation of a passivating organic layer grafted on the working electrode surface. However, by use of fixed current conditions, easier to implement than fixed potential conditions, conversions >80% were achieved. Well-defined homopolymers and block copolymers with a broad range of targeted degrees of polymerization were prepared.