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Issue 22, 2018
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Synthesis of poly(α-olefins) containing rare short-chain branches by dinuclear Ni-based catalysts

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Abstract

1-Hexene homopolymer samples produced by a series of mononuclear (MCn, n = 1–3) and rigid/flexible bridged dinuclear (BCn, n = 1–7) Ni-based catalysts were characterized by 13C NMR, DSC, and GPC-IR analyses. Mononuclear catalysts through normal insertion produced poly(1-hexene) with a high amount of butyl branches, while dinuclear catalysts were able to polymerize 1-hexene with a high level of rare branches (ethyl and propyl) due to the partial chain walking mechanism. Theoretical calculation was employed in order to study the dinuclear catalysts, which confirmed the presence of two stereoisomers via the broadening of MWD, a different mechanism of polymerization and short chain branch (SCB) curves. The effects of the cocatalyst type (DEAC, EASC and MMAO) and concentration, time and temperature along with the polymerization of higher α-olefins (1-octene and 1-decene) on the behavior of dinuclear catalyst BC2 and polymer properties were investigated. As a result, in addition to catalyst structure, the monomer length and polymerization temperature were the two factors controlling the stability of the stereoisomers due to agostic interaction and kinetic energy, respectively.

Graphical abstract: Synthesis of poly(α-olefins) containing rare short-chain branches by dinuclear Ni-based catalysts

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Publication details

The article was received on 03 Sep 2018, accepted on 01 Oct 2018 and first published on 02 Oct 2018


Article type: Paper
DOI: 10.1039/C8NJ04481C
Citation: New J. Chem., 2018,42, 18288-18296
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    Synthesis of poly(α-olefins) containing rare short-chain branches by dinuclear Ni-based catalysts

    M. Khoshsefat, A. Dechal, S. Ahmadjo, S. M. M. Mortazavi, G. H. Zohuri and J. B. P. Soares, New J. Chem., 2018, 42, 18288
    DOI: 10.1039/C8NJ04481C

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