Synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP)

The synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) (PVAc-b-PVC) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP) is investigated for the first time in this paper. A PVAc–Co(acac)2 macroinitiator is prepared by CMRP using the V-70/Co(acac)2 binary system or a preformed alkylcobalt(III) compound. Then, the block copolymerization occurs in the bulk at 40 °C by the addition of VC. The addition of water to the polymerization medium or the slow generation of alkyl radicals during the whole polymerization is beneficial to the process by consuming part of the excess of deactivator (Co(acac)2) that blocks the polymer chains into the dormant form. Dynamic light scattering (DLS) measurements and AFM analyses evidence that the PVAc-b-PVC forms core–shell micelles in a selective solvent of the PVAc block, i.e. methanol, evidencing the blocky structure of the copolymer. PVAc-b-P(VC-co-VAc) copolymers are also successfully prepared by initiating the radical copolymerization of VC and VAc at 40 °C from a PVAc–Co(acac)2 macroinitiator.