Controlled Synthesis of Ethylene-Vinyl Acetate Based Copolymers by Organometallic Mediated Radical Polymerization

The controlled radical copolymerization of ethylene (E) and vinyl acetate (VAc) is further investigated by organometallic-mediated radical polymerization (OMRP) using Co(acac)(2) as controlling agent at ethylene pressure up to 100 bar. The effect of ethylene pressure on kinetics, level of control and copolymer composition, is discussed. Ethylene-Vinyl Acetate copolymers (EVAs) with low dispersities and ethylene content reaching 57 mol% are notably reported. This work also successfully addresses the precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA. In this case, the order of the synthesis of the blocks is a key parameter. The "PVAc-first" strategy is by far more practical and efficient.