University of Leicester
Browse
catalysts-12-01569-v2.pdf (10.76 MB)

Thermally Stable and Highly Efficient N,N,N-Cobalt Olefin Polymerization Catalysts Affixed with N-2,4-Bis(Dibenzosuberyl)-6-Fluorophenyl Groups

Download (10.76 MB)
journal contribution
posted on 2023-09-20, 09:32 authored by Muhammad Zada, Desalegn Demise Sage, Qiuyue Zhang, Yanping Ma, Gregory A Solan, Yang Sun, Wen-Hua Sun
The cobalt(II) chloride N,N,N-pincer complexes, [2-{(2,4-(C15H13)2-6-FC6H2)N=CMe}-6-(ArN=CMe)C5H3N]CoCl2 (Ar = 2,6-Me2C6H3) (Co1), 2,6-Et2C6H3 (Co2), 2,6-i-Pr2C6H3 (Co3), 2,4,6-Me3C6H2 (Co4), 2,6-Et2-4-MeC6H2 (Co5), and [2,6-{(2,4-(C15H13)2-6-FC6H2)N=CMe}2C5H3N]CoCl2 (Co6), each containing at least one N-2,4-bis(dibenzosuberyl)-6-fluorophenyl group, were synthesized in good yield from their corresponding unsymmetrical (L1–L5) and symmetrical bis(imino)pyridines (L6). The molecular structures of Co1 and Co2 spotlighted their distorted square pyramidal geometries (τ5 value range: 0.23–0.29) and variations in steric hindrance offered by the dissimilar N-aryl groups. On activation with either MAO or MMAO, Co1–Co6 all displayed high activities for ethylene polymerization, with levels falling in the order: Co1 > Co4 > Co5 > Co2 > Co3 > Co6. Indeed, the least sterically hindered 2,6-dimethyl Co1 in combination with MAO exhibited a very high activity of 1.15 × 107 g PE mol−1 (Co) h−1 at the operating temperature of 70 °C, which dropped by only 15% at 80 °C and 43% at 90 °C. Vinyl-terminated polyethylenes of high linearity and narrow dispersity were generated by all catalysts, with the most sterically hindered, Co3 and Co6, producing the highest molecular weight polymers [Mw range: 30.26–33.90 kg mol−1 (Co3) and 42.90–43.92 kg mol−1 (Co6)]. In comparison with structurally related cobalt catalysts, it was evident that the presence of the N-2,4-bis(dibenzosuberyl)-6-fluorophenyl groups had a limited effect on catalytic activity but a marked effect on thermal stability.

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

Catalysts

Volume

12

Issue

12

Pagination

1569

Publisher

MDPI AG

eissn

2073-4344

Copyright date

2022

Available date

2023-09-20

Language

en

Usage metrics

    University of Leicester Publications

    Categories

    Licence

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC