Trifluoromethoxy- and Fluorobenzhydryl-Tuned Nickel Catalysts for Polyethylene Elastomers

A series of para-trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-C₆H₄)₂CH}₂-4-F₃COC₆H₂N]-2-(ArN)C₂C₁₀H₆ (Ar = 2,6-Me₂C₆H₃L1, 2,6-Et₂C₆H₃L2, 2,6-iPr₂C₆H₃L3, 2,4,6-Me₃C₆H₂L4, 2,6-Et₂-4-MeC₆H₂L5), were synthesized and used to generate their corresponding nickel(II) bromide complexes (Ni1-Ni5). Elemental analysis, ¹⁹F NMR, and FT-IR spectroscopy were employed to characterize these five nickel complexes. Single-crystal X-ray diffraction of Ni2 and Ni4 confirmed distorted tetrahedral geometries. Upon activation with either EtAlCl₂ (ethylaluminum dichloride) or EASC (ethyl aluminum sesquichloride), these complexes showed exceptional high activities (up to 22.0 × 10⁶ g PE mol^-1 (Ni) h^-1) and remarkable thermal stability (4.82 × 10⁶ g PE mol^-1(Ni) h^-1 at 80 °C) towards ethylene polymerization. The resulting polyethylenes are highly branched, with the type and extent of branches tunable by temperature, solvent, and co-catalyst choice. Moreover, these polymers demonstrated excellent tensile strength (σ_b up to 20.7 MPa) and elastic recovery (up to 58%), characteristic of thermoplastic elastomers (TPEs). These results highlight the dual role of trifluoromethoxy and fluorobenzhydryl groups in enhancing catalytic performance and polymer properties.