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Elastomeric polyethylenes accessible via ethylene homo-polymerization using an unsymmetrical α-diimino-nickel catalyst

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posted on 10.08.2017, 14:45 by Xinxin Wang, Linlin Fan, Yanping Ma, Cun-Yue Guo, Gregory A. Solan, Yang Sun, Wen-Hua Sun
Five types of unsymmetrical bis(arylimino)acenaphthenes, 1-[2,4,6-(CHPh2)3C6H2N]-2-(ArN)C2C10H6 (Ar = 2,6-Me2Ph L1, 2,6-Et2Ph L2, 2,6-i-Pr2Ph L3, 2,4,6-Me3Ph L4 and 2,6-Et2-4-MePh L5), each containing a single N-2,4,6-tribenzhydrylphenyl group, have been prepared and fully characterized. The interaction of L1–L5 with (DME)NiBr2 (DME = 1,2-dimethoxyethane) afforded the corresponding 1 : 1 nickel(II) bromide chelates, LNiBr2 (Ni1–Ni5), in good yield. Distorted tetrahedral geometries are a feature of the X-ray structures of Ni1 and Ni3; broad paramagnetically shifted peaks are seen in the 1H NMR spectra for all the nickel complexes in solution. Upon activation with relatively low amounts of Et2AlCl or Me2AlCl (200–700 equivalents), Ni1–Ni5 exhibited exceptionally high activities for ethylene polymerization (up to 1.07 × 107 g of PE (mol of Ni)−1 h−1), displayed good thermal stability [2.97 × 106 g of PE (mol of Ni)−1 h−1 even at 90 °C] and produced hyperbranched polyethylenes. Dynamic mechanical analysis and stress–strain testing reveal that the polymeric materials possess good elastomeric recovery and high elongation at break, indicating a promising alternative material to thermoplastic elastomers (TPEs).

History

Citation

Polymer Chemistry, 2017, 8, 2785-2795.

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

Polymer Chemistry

Publisher

Royal Society of Chemistry

issn

1759-9954

eissn

1759-9962

Acceptance date

05/04/2017

Copyright date

2017

Available date

13/04/2018

Publisher version

http://pubs.rsc.org/en/Content/ArticleLanding/2017/PY/C7PY00434F#!divAbstract

Notes

The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above. Crosscheck: This document is CrossCheck deposited related_data: Supplementary Information related_data: Crystal Structure Data identifier: Gregory A. Solan (ORCID) identifier: Wen-Hua Sun (ORCID) identifier: Wen-Hua Sun (ResearcherID) copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal history: Received 14 March 2017; Accepted 5 April 2017; Accepted Manuscript published 5 April 2017; Advance Article published 13 April 2017

Language

en

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