Hybridization of CMRP and ATRP: A Direct Living Chain Extension from Poly(vinyl acetate) to Poly(methyl methacrylate) and Polystyrene

Abstract

Cobalt-mediated radical polymerization (CMRP) was used to prepare well-defined poly(vinyl acetate) (PVAc) as the macroinitiator in the reverse atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and styrene (Sty) for the synthesis of block copolymers of PVAc-b-PMMA and PVAc-b-PSty with linearly increased molecular weight and smoothly shifted gel permeation chromatography (GPC) traces. The chain extension from PVAc to PMMA or PSty via the hybridization of CMRP and ATRP required neither a difunctional initiator nor further chain-end modification and was as simple as regular chain extension in the reverse ATRP process. Because the cobalt complex bonded to the chain end of PVAc was dissociated during the ATRP process, this method also efficiently solved the issue of metal removal in the CMRP process.