Heteroatom-assisted olefin polymerization by rare-earth metal catalysts.

Heteroatom-functionalized polyolefins are of fundamental interest and practical importance. This has spurred investigations of the copolymerization of polar and nonpolar olefins. We report the first syndiospecific polymerization of a series of heteroatom-containing α-olefins and their copolymerization with ethylene catalyzed by half-sandwich rare-earth complexes. We have found that the interaction between a heteroatom in a functional α-olefin monomer and a rare-earth metal catalyst can significantly raise the olefin polymerization activity and thereby promote its copolymerization with ethylene. By using this heteroatom-assisted olefin polymerization (HOP) strategy, we have successfully synthesized a series of heteroatom (O, S, Se, N, and P)-functionalized polyolefins with high molecular weights and controllable functional monomer contents. The mechanistic aspect of the HOP process has been elucidated by computational studies. We expect that our findings will guide the design of new catalyst systems for the synthesis of various desired functional polyolefins.