Bio‐Based Solution for Polyolefin Synthesis Enabled by Carbonate Solvent and Comonomer

ABSTRACT Polyolefins, the dominant class of synthetic polymers, remain entirely dependent on fossil fuels throughout their lifecycle. Developing green manufacturing solutions is the long‐sought aspiration to reduce the carbon footprint of polyolefins and alleviate dependence on petroleum resources. Herein, electron‐rich phosphinephenolato nickel(II) complexes render bio‐based dimethyl carbonate (DMC) the desirable medium for the practically efficient production of high‐density polyethylene (HDPE) with comparable activity to metallocene catalysts. Mechanistic investigation identified that DMC could facilitate pyridine dissociation yet avoid overly strong coordination to nickel, enabling smooth ethylene substitution and consequently polymerization. Incorporation of carbonate‐containing comonomer afforded polar polyethylene with robust activity, which could be further tailored through microstructural refinement to customized functionalities. This work illustrated the harmonious interaction of carbonate with a polymerization catalyst that contributes a bio‐based solution toward sustainable manufacturing and functionalization of polyolefins.