Synthesis of double-bond-containing diblock copolymers via RAFT polymerization

Abstract

Polyallenes that have internal double bonds are attractive platforms for the development of diverse functional materials. However, the controlled block copolymerization of allene derivatives with a precise structure and designable architecture is still challenging. Herein, we report the preparation of double bond-containing poly(phenoxyallene) (PPOA) copolymers with a tunable structure through reversible addition–fragmentation chain transfer (RAFT) polymerization. RAFT homopolymerization of phenoxyallene (POA) was firstly performed as a typical reaction to optimize the polymerization conditions. A kinetic study quantitatively confirmed the good livingness under the optimized polymerization conditions as the M_n of the obtained polymer increased linearly with the monomer conversion. The versatility of this approach is demonstrated by the preparation of PPOA homopolymers, poly(phenoxyallene)-b-poly(methyl acrylate) (PPOA-b-PMA) and poly(ethylene glycol)-b-poly(phenoxyallene) (PEG-b-PPOA) diblock copolymers.