Aqueous Coordination‐Insertion Copolymerization for Producing High Molecular Weight Polar Polyolefins

Hydrocarbons, when used as the medium for transition metal catalyzed organic reactions and olefin (co‐)polymerization, are ubiquitous. Environmentally friendly water is highly attractive and long‐sought, but is greatly challenging as coordination‐insertion copolymerization reaction medium of olefin and polar monomers. Unfavorable interactions from both water and polar monomer usually lead to either catalyst deactivation or the formation of low‐molecular‐weight polymers. Herein, we develop well‐behaved neutral phosphinophenolato nickel catalysts, which enable aqueous copolymerization of ethylene and diverse polar monomers to produce significantly high‐molecular‐weight linear polar polyolefins (219–549 kDa, 0.13–1.29 mol %) in a single‐component fashion under mild conditions for the first time. These copolymerization reactions occur better in water than in hydrocarbons such as toluene. The dual characteristics of high molecular weight and the incorporation of a small amount of functional group result in improved surface properties while retain the desirable intrinsic properties of high‐density polyethylene (HDPE). Water, a poison in traditional olefin polymerization processes using Ziegler–Natta catalysts, enables coordination‐insertion copolymerization of ethylene and diverse polar monomers to produce significantly high‐molecular‐weight linear polar polyolefins (219–549 kDa) using single‐component and neutral nickel catalysts under mild conditions.