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Updated: Feb 8, 2026

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
Published on: February 18, 2022
Electrochemically Mediated Reversible Addition-Fragmentation Chain-Transfer Polymerization
Yi Wang1, Marco Fantin1, Sangwoo Park1
1Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213.
Abstract:
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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