Synthesis of Ultralow-Density Polyethylene Elastomers Using Triarylnaphthyl Iminopyridyl Ni(II) Catalysts.

Recently, the chain-walking ethylene polymerization strategy has garnered widespread attention as an efficient and straightforward method for preparing polyolefin elastomers. In this study, a series of 2,4,8-triarylnaphthyl iminopyridyl nickel catalysts were synthesized and used in ethylene polymerization. These catalysts demonstrated moderate catalytic activity (10⁵ g mol^-1 h^-1), producing high-molecular-weight (up to 145.5 kg/mol) polyethylene materials with high branching degrees (75-95/1000C) and correspondingly low melting points. Detailed analysis using ¹³C NMR spectroscopy revealed that the polyethylenes primarily featured methyl and long-chain branches. Mechanical testing of the polyethylene samples obtained from catalysts Ni1-Ni3 exhibited moderate stress at break (4.64-6.97 MPa) coupled with a very high strain at break (1650-3752%), indicating their very good ductility. Furthermore, these polyethylenes showcased great elastic recovery abilities, with strain recovery values ranging from 72% to 85%. In contrast, the polyethylene produced by Ni4 displayed notably inferior tensile strength (0.16 MPa) and tensile recovery (43%). To the best of our knowledge, this study represents the inaugural utilization of a nickel iminopyridyl catalyst in the preparation of a polyethylene thermoplastic elastomer.