Synthesis of poly(vinyl acetate)-b-poly(4-vinylpyridine) block copolymers by a combination of cobalt-mediated radical polymerization and RAFT polymerization and their use in dispersion polymerization under UV radiation

Well-defined poly(vinyl acetate)-block-poly(4-vinylpyridine) (PVAc-b-P4VP) block copolymers were synthesized for the first time by a combination of cobalt-mediated radical polymerization (CMRP) and reversible addition–fragmentation chain transfer (RAFT) polymerization, and were used to prepare PVAc-b-P4VP hairy polystyrene (PSt) particles. PVAc end-capped by a cobalt(II) acetylacetonate complex was first synthesized by the CMRP of vinyl acetate, after which the cobalt complex was modified into a dithiobenzoate group for the RAFT polymerization of 4-vinylpyridine. The hairy PSt particles were synthesized by the dispersion polymerization of St using the PVAc-b-P4VP as both a macro-initiator and a colloidal stabilizer under UV radiation. The average size of PSt particles synthesized with 20 wt.% of PVAc-b-P4VP (M _n = 39,500 g/mol) was 136 nm (CV = 19.2%). Very small Au nanoparticles were successfully immobilized on the surface of the PSt particles.