New just accepted paper in Macromolecules with our longtime collaborator Christophe Detrembleur from the University of Liege.
The synthesis of ethylene-based block copolymers by a single radical polymerization technique remains a great challenge. The main difficulty relates to the difference in reactivity between ethylene and the comonomer, especially if polar vinyl monomers are considered. In order to overcome this limitation, in the present work, the controlled radical homopolymerization of ethylene via organometallic-mediated radical polymerization (OMRP) using a cobalt complex as controlling agent was investigated. For the first time, block copolymers composed of ethylene and polar vinyl monomers, e.g. poly(vinyl acetate)-b-polyethylene (PVAc-b-PE) and poly(ethylene vinyl acetate)-b-polyethylene (EVA-b-PE) were prepared. Although a minor population corresponding to the triblock copolymers formed by radical coupling reactions was observed, this strategy is straightforward for preparing PE-based copolymers without the need to change the polymerization mechanism between each block. The synthesis and the post-polymerization modification of α-functional polyethylene (PE) was also demonstrated.