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Highly branched and high‐molecular‐weight polyethylenes produced by 1‐[2,6‐bis(bis(4‐fluorophenyl)methyl)‐4‐MeOC6H2N]‐2‐aryliminoacenaphthylnickel(II) halides

Wu, Ruikai, Wang, Yifan, Guo, Liwei, Guo, Cun‐Yue, Liang, Tongling, Sun, Wen‐Hua
Journal of polymer science 2019 v.57 no.2 pp. 130-145
Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, ethylene, halides, molecular weight, nickel, nuclear magnetic resonance spectroscopy, polyethylenes, polymerization, temperature, tensile strength, thermoplastics
A series of unsymmetrical 1‐[2,6‐bis(bis(4‐fluorophenyl)methyl)‐4‐MeOC₆H₂N]‐2‐aryliminoacenaphthene‐nickel(II) halides has been synthesized and fully characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (¹H NMR), ¹³C NMR, and ¹⁹F NMR spectroscopy as well as elemental analysis. The structures of Ni1 and Ni6 have been confirmed by the single‐crystal X‐ray diffraction. On activation with cocatalysts either ethylaluminum sesquichloride or methylaluminoxane, all the title nickel complexes display high activities toward ethylene polymerization up to 16.14 × 10⁶ g polyethylene (PE) mol⁻¹(Ni) h⁻¹ at 30 °C, affording PEs with both high branches (up to 103 branches/1000 carbons) and molecular weight (1.12 × 10⁶ g mol⁻¹) as well as narrow molecular weight distribution. High branching content of PE can be confirmed by high temperature ¹³C NMR spectroscopy and differential scanning calorimetry. In addition, the PE exhibited remarkable property of thermoplastic elastomers (TPEs) with high tensile strength (σb = 21.7 MPa) and elongation at break (εb = 937%) as well as elastic recovery (up to 85%), indicating a better alternative to commercial TPEs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 130–145