Unprecedented living olefin polymerization derived from an attractive interaction between a ligand and a growing polymer chain.

Ti complexes incorporating fluorine-containing phenoxy-imine chelate ligands (fluorinated Ti-FI catalysts) have been demonstrated to induce an unprecedented living polymerization effect with both ethylene and propylene, through an attractive interaction between the fluorine atom in the ligand and a beta-hydrogen atom on the growing polymer chain. With the aid of this attractive interaction, highly controlled living ethylene polymerization, highly-syndiospecific living propylene polymerization, the synthesis of unique block copolymers from ethylene and propylene, and the catalytic production of monodisperse polyethylene and Zn-terminated polyethylene have been realized. The attractive interaction provides a conceptually new strategy for the achievement of controlled living olefin polymerization.