Mechanoredox catalyzed cationic RAFT polymerization via perfluorinated anion assistance for the synthesis of high-molecular-weight polymers

Abstract

External-field-regulated cationic reversible addition–fragmentation chain transfer (RAFT) polymerization provides a promising strategy for the precise synthesis of macromolecules. However, achieving high-molecular-weight poly(vinyl ether)s (PVEs) under mild conditions remains challenging due to premature chain termination. In this work, we report a perfluorinated anion-assisted strategy that facilitates mechanochemical cationic RAFT (mechano-cRAFT) polymerization of vinyl ethers under solvent-minimized conditions. The resulting PVEs achieve number average molecular weights exceeding 170 kDa, with high chain-end fidelity for efficient chain-extension. Density functional theory (DFT) calculations revealed enhanced interactions between cationic chain terminals and perfluorinated counterions, which stabilizes propagating species and suppresses chain termination. This methodology offers a robust platform for the synthesis of well-defined high-molecular-weight PVEs under mild conditions.