Controlled synthesis of industrially important polymers by organometallic-mediated radical polymerization based on cobalt

Reversible deactivation radical polymerization (RDRP) has undergone impressive developments over the last decades and offers today a high level of control of polymer structures. Transition metals have deeply marked the field of RDRP leading to plethora of macromolecules with predictable molar mass, precise topology, specific composition and functionalities. Besides the popular atom transfer radical polymerization, another metal-assisted radical polymerization technique emerged, namely the organometallic-mediated radical polymerization (OMRP). The latter relies on the temporary deactivation of the growing radical chains by a transition metal complex. The OMRP notably stands out for its ability to control the polymerization of challenging ‘Less Activated Monomers’ (LAMs) deprived of radical stabilizing group on their double bond. This presentation aims at describing recent advances in the precision design of polymers by OMRP based on cobalt complexes. Special emphasis will be laid on major industrial polymers including poly(vinyl alcohol), poly(vinyl amine), poly(vinylidene fluoride) but also ethylene-containing polymers. Mechanistic aspects of OMRP will be discussed as well as the synthesis of unique statistical and block copolymers.