Well-defined poly(vinyl acetate)-block-polystyrene (PVAc-b-PSt) block copolymers were successfully synthesized by a combination of cobalt-mediated radical polymerization (CMRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. PVAc and PVAc-b-PSt (with an average PSt repeating unit of 2 or 6) were first synthesized via CMRP with cobalt(II) acetylacetonate as a regulating agent.The cobalt complexes attached to their ? chain ends were modified into a phenyl dithioester group by reacting with bis(thiobenzoyl) disulfide, producing PVAc and PVAc-b-PSt macro-chain-transfer agents (PVAc-CTA and PVAc-PSt-CTA), respectively. The RAFT polymerization of styrene with PVAc-CTA or PVAc-PSt-CTA was conducted in N,N-dimethylformamide at 80 oC. PVAc-b-PSt block copolymers synthesized with PVAc-PSt6-CTA (with an average PSt repeating unit of 6) exhibited narrowest molecular weight distributions (Mw/Mn = 1.28-1.30) even at high conversions.

Synthesis of poly(vinyl acetate)-<i>b</i>-polystyrene copolymers by a combination of cobalt-mediated radical polymerization and RAFT polymerization

240th National Meeting (2010)

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Synthesis of poly(vinyl acetate)-b-polystyrene copolymers by a combination of cobalt-mediated radical polymerization and RAFT polymerization