Organometallic-mediated radical synthesis of well-defined ethylene-vinyl acetate statistical and block copolymers

The copolymerization of ethylene (E) and vinyl acetate (VAc) is of high interest for polymer industry. Nevertheless, the control of the macromolecular parameters of ethylene-vinyl acetate copolymers (EVAs) is difficult to achieve. Herein, we report the controlled radical copolymerization of these monomers by organometallic-mediated radical polymerization (OMRP) using Co(acac)2 as controlling agent. The ethylene pressure is varied from 10 to 100 bar and we discuss the effect of this parameter on kinetics, level of control and copolymer composition. EVAs are synthetized accordingly with low dispersities and ethylene content reaches up to 57 mol%. The precision design of EVA-containing block copolymers, i.e. PVAc-block-EVA, is also addressed.