Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer Polymerization. 2017

Yi Wang, and Marco Fantin, and Sangwoo Park, and Eric Gottlieb, and Liye Fu, and Krzysztof Matyjaszewski
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213.

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, using 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.

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