Abstract
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 ω 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 °C. 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. The PVAc-b-PSt block copolymer (Mn(GPC) = 21 000 g/mol, M...
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