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Synthesis and application of fluorinated α-diimine nickel catalyst for ethylene polymerization: deactivation mechanism

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Abstract

A fluorinated LTM catalyst of [bis(N,N′-2-fluorophenylimino)acenaphthene] nickel(ΙΙ) dibromide was prepared and applied for ethylene polymerization. We established a reasonable hypothesis, highlighting the role of fluorine in ligand structure. In addition, density functional theory (DFT) studies have been applied to strengthen our propositions. DFT calculations of the β-agostic cationic species at room temperature and 75 °C suggest that the β-agostic structure for the latter was destabilized by 19 eV which rendered it less prone to β-H transfer reactions than the species at room temperature. In addition, a mechanism for the catalyst deactivation for fluorinated α-diimine nickel based catalysts has been proposed.

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Acknowledgements

The authors wish to thank Ferdowsi University of Mashhad for financial support and staff of DSC Lab of Engineering Department of Chemical Engineering Faculty of Ferdowsi University of Mashhad for their kind help.

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Authors and Affiliations

  1. Department of Catalyst, Iran Polymer and Petrochemical Institute, Tehran, Iran

    S. Ahmadjo

  2. Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran

    S. Damavandi, G. H. Zohuri, A. Farhadipour, N. Samadieh & Z. Etemadinia

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  1. S. Ahmadjo
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  2. S. Damavandi
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Correspondence to S. Ahmadjo or G. H. Zohuri.

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Ahmadjo, S., Damavandi, S., Zohuri, G.H. et al. Synthesis and application of fluorinated α-diimine nickel catalyst for ethylene polymerization: deactivation mechanism. Polym. Bull. 74, 3819–3832 (2017). https://doi.org/10.1007/s00289-017-1924-3

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  • DOI: https://doi.org/10.1007/s00289-017-1924-3

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