Organo‐Cobalt Complexes in Reversible‐Deactivation Radical Polymerization

Abstract Cobalt complexes have played an essential role in different chemical reactions. One of them that has attracted substantial attention in polymer science is cobalt mediated radical polymerization (CMRP), which is famous for its remarkable efficiency in controlling the radical polymerization of vinyl acetate (VAc) and other less active monomers (LAMs). Two pathways, reversible termination (RT) and degenerative transfer (DT), were recognized to control the polymerization in CMRP and could be further used to rationalize the mechanism of other RDRP methods. These control mechanisms were then found to be correlated to the redox potential of cobalt complexes and thus could be judged more quantitatively. The control of polymer composition and tacticity could also be achieved by using CMRP. The hybridization of CMRP and atom transfer radical polymerization (ATRP) could directly synthesize the vinyl acetate/methyl methacrylate and vinyl acetate/styrene block copolymers in one pot. The copolymer of acrylates and 1‐octene could be obtained by visible‐light‐induced CMRP. With the addition of bulky Lewis acid, CMRP of N,N ‐dimethylacrylamide (DMA) showed high isotacticities with the contents of meso dyads ( m ) and meso triads ( mm ) up to 94 % and 87 %, respectively, and generated the crystalline PDMA with T m as high as 276 °C. This personal account reviewed the development of CMRP with the mechanistic understanding, the control of composition and stereoselectivity of the polymeric products, and its perspective.