Synthesis of Functional Metallocene Polyethylene through Masking Free Copolymerization of Polar Monomer with Ethylene

Metallocene polyethylene (mPE) is a high-performance polyolefin that is renowned for its exceptional material properties. Although polar functionalization of mPE can improve surface characteristics and expand its applications, conventional synthesis methods face challenges due to the poisoning effect of polar monomers on metallocene catalysts. In this study, we present a direct metallocene-catalyzed copolymerization of ethylene with oxygen- and nitrogen-containing polar monomers bypassing the need for masking reagents. Integrated experimental and computational analyses reveal that heteroatom interactions with the metallocene center do not deactivate the catalyst; rather, they fine-tune copolymerization behavior, influencing monomer insertion rates, catalytic activity, and molecular weight. Using titanocene [Ti(Cp)2Cl2], we synthesized ethylene/anisyl propylene (AP) copolymers with adjustable polar monomer incorporation (0–32 mol %). Meanwhile, a zirconocene catalyst [Zr(CpMe5)2Me2] produced high-molecular-weight functional plastics (e.g., 4.5 mol % AP, Mn = 370 kDa). The resulting polar mPE copolymers exhibited tailored surface and mechanical properties, highlighting their potential as advanced polyolefin-based adhesives and engineered plastic materials.