Organometallic-mediated radical polymerization of methylene heterocycles and ethylene

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. In particular, the organometallic-mediated radical polymerization (OMRP),[1,2] which relies on the temporary deactivation of the growing radical chains by a transition metal complex, 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 ethylene-based polymers. The organometallic-mediated radical homopolymerization of ethylene and the ethylene/vinyl acetate copolymerization will be discussed. Unique linear and macrocyclic ethylene-containing architectures will be described. [3,4] Finally, we will present the controlled radical (co)polymerization of methylene heterocycles, like vinyl carbonates produced by carboxylative cyclization of propargyl alcohol with carbon dioxide, as well as the thermal and the solution properties of the copolymers resulting therefrom. [5] [1] Debuigne, A.; Jerome, C.; Detrembleur, C. Polymer 2017, 115, 285–307. [2] Demarteau, J.; Debuigne, A.; Detrembleur, C. Chem. Rev. 2019, 119 (12), 6906-6955. [3] Demarteau, J., De Winter, J., Detrembleur, C., Debuigne, A. Polym. Chem., 2018, 9(3), 273-278. [4] Detrembleur, C. ; Demarteau, J.; Debuigne, A.; Kermagoret, A. Patent WO2019/12409 A1. [5] Scholten, P., Demarteau, J., Gennen, S., De Winter, J., Grignard, B., Debuigne, A., Meier, M. A. R., Detrembleur, C. Macromolecules 2018, 51(9), 3379-3393.