Living Olefin Polymerization and Block Copolymer Formation with FI Catalysts

This contribution reports on the recent advances in living olefin polymerization catalysis and block copolymer formation made by fluorinated bis(phenoxy-imine)Ti complexes (fluorinated Ti-FI catalysts), which were discovered by Mitsui Chemicals. Fluorinated Ti-FI catalysts are capable of mediating thermally robust living ethylene and highly stereoselective living propylene polymerization. This highly controlled living nature has made it possible to synthesize a wide variety of monodisperse polymers, functionalized polymers and block copolymers from ethylene, propylene, higher α-olefins, cyclic olefins and styrene. The living FI polymers possess unique and often previously inaccessible microstructures, and some of the FI polymers were revealed to display unique morphologies and useful material properties. Therefore, the discovery and development of the fluorinated Ti-FI catalysts has not only made a significant impact on living olefin polymerization catalysis but has also given industry opportunities to make unique polyolefin-based materials for the benefit of the world at large.