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High molecular weight PE elastomers through 4,4-difluorobenzhydryl substitution in symmetrical alpha-diimino-nickel ethylene polymerization catalysts

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journal contribution
posted on 2022-10-04, 08:35 authored by Yuting Zheng, Shu Jiang, Ming Liu, Zhixin Yu, Yanping Ma, Gregory A Solan, Wenjuan Zhang, Tongling Liang, Wen-Hua Sun

The following family of N,N-diaryl-2,3-dimethyl-1,4-diazabutadienes, ArN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NAr (Ar = 2,6-Me2-4-{CH(4-FC6H4)2}C6H2 L1, 2-Me-6-Et-4-{CH(4-FC6H4)2}C6H2 L2, 2,4-{CH(4-FC6H4)2}2-6-MeC6H2 L3, 2,4-{CH(4-FC6H4)2}2-6-EtC6H2 L4, 2,4-{CH(4-FC6H4)2}2-6-iPrC6H2 L5), each incorporating para-substituted 4,4-difluorobenzhydryl groups but differing in the ortho-pairing, have been synthesized and used as precursors to their respective nickel(II) bromide complexes, Ni1–Ni5. Compound characterization has been achieved through a combination of FT-IR, multinuclear NMR spectroscopy (1H, 13C, 19F) and elemental analysis. In addition, L1, Ni1 and Ni5 have been structurally characterized with Ni1 and Ni5 revealing similarly distorted tetrahedral geometries about nickel but with distinct differences in the steric protection offered by the ortho-substituents. All nickel complexes, under suitable activation, showed high activity for ethylene polymerization with a predilection towards forming branched high molecular weight polyethylene with narrow dispersity. Notably the most sterically bulky Ni5, under activation with either EtAlCl2, Et2AlCl or EASC, was exceptionally active (0.9–1.0 × 107 g of PE per (mol of Ni) per h) at an operating temperature of 40 °C. Furthermore, the polyethylene generated displayed molecular weights close to one million g mol−1 (Mw range: 829–922 kg mol−1) with high branching densities (86–102/1000 carbons) and a selectivity for short chain branches (% Me = 94.3% (EtAlCl2), 87.2% (Et2AlCl), 87.7% (EASC)). Further analysis of the mechanical properties of the polymers produced at 40 °C and 50 °C using Ni5 highlighted the key role played by crystallinity (Xc) and molecular weight (Mw) on tensile strength (σb) and elongation at break (εb). In addition, stress–strain recovery tests reveal these high molecular weight polymers to exhibit characteristics of thermoplastic elastomers (TPEs).

Funding

National Natural Science Foundation of China (No. 21871275)

History

Author affiliation

Department of Chemistry, University of Leicester

Version

  • VoR (Version of Record)

Published in

RSC ADVANCES

Volume

12

Issue

37

Pagination

24037 - 24049

Publisher

Royal Society of Chemistry (RSC)

eissn

2046-2069

Copyright date

2022

Available date

2022-10-04

Language

English