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Synthesis of hyperbranched low molecular weight polyethylene oils by an iminopyridine nickel(II) catalyst

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Abstract

A 6-(2,6-dimethylphenyl)-2-(2,6-diisopropylphenyl)iminopyridine dibromo nickel(II) complex was synthesized, characterized by X-ray diffraction analysis and tested in ethylene polymerization using diethylaluminumchloride as the cocatalyst. Low molecular weight (Mn ∼ 103 g mol−1) polyethylene oils were obtained under a variety of reaction conditions. Detailed NMR analysis showed the formation of hyperbranched macromolecules (branching density >100 branches per 1000 carbons) with a high fraction of “branches on branch” and one unsaturation per chain, resulting in polymer features comparable to those of polymers produced by α-diimine Pd(II) catalysts. The DFT model of the catalytic species showed that the ortho-2,6-dimethylphenyl substituent of the pyridine group destabilizes the ethylene coordination to the metal centre but does not encumber both axial coordination site. So the polymerization performance of 1 can be addressed to the catalytic pocket generated by the coordinated ligand that favors both chain transfer and chain walking over propagation.

Graphical abstract: Synthesis of hyperbranched low molecular weight polyethylene oils by an iminopyridine nickel(ii) catalyst

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Publication details

The article was received on 20 Jul 2017, accepted on 02 Oct 2017 and first published on 03 Oct 2017


Article type: Paper
DOI: 10.1039/C7PY01215B
Citation: Polym. Chem., 2017, Advance Article
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    Synthesis of hyperbranched low molecular weight polyethylene oils by an iminopyridine nickel(II) catalyst

    I. D'Auria, S. Milione, T. Caruso, G. Balducci and C. Pellecchia, Polym. Chem., 2017, Advance Article , DOI: 10.1039/C7PY01215B

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