The influence of cobalt-coordination on cobalt-mediated radical polymerization of vinyl monomers

Nowadays, polymers are a part of everyday life. Researchers encouraged by growing need in high performance polymers develop new synthesis tools to manage the molecular architecture and thus the polymer properties. In this context, CRP (Controlled Radical Polymerization) techniques have been developed to obtain well-defined architectures and to control polymer parameters. Among these systems is Cobalt-Mediated Radical Polymerization (CMRP), which is based on the reversible deactivation of the growing radical chains with a cobalt complex, the cobalt (II) bis-acetylacetonate. The interest of this system is not only due to its ability to control the polymerization of very reactive monomers such as vinyl acetate (VAc) and N-vinylpyrrolidone (NVP), but also its peculiar mechanism which exhibits two pathways depending on the polymerization conditions; a reversible termination process and a degenerative chain transfer mechanism. Furthermore, it has been showed that the Co-C strength and thus the polymerization are strongly influenced by the use of some additives, such as water, dimethylformamide, dimethylsulfoxide and pyridine, which coordinate the cobalt free site.
In this presentation we report the use of a preformed alkyl-cobalt(III) adduct as initiator for the polymerization of acrylonitrile (AN) and the use of these ligands in the CMRP system to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) block copolymers.
As a conclusion, cobalt-coordination appears today as a unique opportunity to adjust the Co-C bond strength and to push back the bounds of possibilities in terms of macromolecular engineering assisted by CMRP.