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Enhancing Suppression of Chain Transfer via Catalyst Structural Evolution in Ethylene (Co)Polymerization
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  • Beihang Ding,
  • Lihang Jiang,
  • Xiaohui Kang,
  • Shengyu Dai
Beihang Ding
Anhui University
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Lihang Jiang
Dalian Medical University
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Xiaohui Kang
Dalian Medical University
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Shengyu Dai
Anhui University

Corresponding Author:daiyu@ustc.edu.cn

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Usually, the aniline-based late-transition-metal catalysts often require bulky steric substituents on both sides of the ortho-aryl position to achieve efficient suppression of chain transfer in ethylene polymerization. In this contribution, we demonstrated that α-diimine catalysts based on naphthylamine with only one bulky ortho-aryl substituent also demonstrated excellent capabilities to suppress the chain transfer. Firstly, a class of α-diimine nickel and palladium complexes with only one o-aryl-dibenzhydryl or o-aryl-dibenzosuberyl substituent were synthesized and characterized. Secondly, the as-prepared naphthylamine-based nickel catalysts demonstrated outstanding activities and yielded lightly branched (16-40/1000C) polyethylenes with very high molecular weights (445.8-854.3 kg/mol) in ethylene polymerization. In comparison, the corresponding palladium catalysts showed moderate activities, generating moderately branched polyethylenes with moderate molecular weights (21.6-82.0 kg/mol). Moreover, the palladium catalysts could also copolymerize ethylene and methyl acrylate (MA), albeit in low activity (level of 103 g·mol-1·h-1),providing E-MA copolymers with low to moderate molecular weight (1.4-16.3 kg/mol) and a moderate level of incorporation ratio (2.4-7.4 mol%) and branching density. As compared with aniline-based nickel and palladium catalysts, the naphthylamine-based catalysts displayed a superior ability to suppress the chain transfer reactions and could give access to (co)polymers with orders of magnitude higher molecular weight in ethylene (co)polymerization.
29 Dec 2022Reviewer(s) Assigned
30 Jan 2023Review(s) Completed, Editorial Evaluation Pending
08 Feb 2023Editorial Decision: Revise Minor
19 Feb 20231st Revision Received
21 Feb 2023Submission Checks Completed
21 Feb 2023Assigned to Editor
21 Feb 2023Review(s) Completed, Editorial Evaluation Pending
24 Feb 2023Editorial Decision: Accept