Unprecedented Living Olefin Polymerization Derived from an Attractive Interaction between a Ligand and a Growing Polymer Chain

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Abstract
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 β‐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.

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