Enhancing Suppression of Chain Transfer via Catalyst Structural Evolution in Ethylene (Co)Polymerization

Author:

Ding Beihang1,Jiang Lihang2,Kang Xiaohui2,Dai Shengyu13

Affiliation:

1. Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education Anhui University Hefei Anhui 230601 China

2. College of Pharmacy Dalian Medical University Dalian Liaoning 116044 China

3. School of Chemical and Environmental Engineering Anhui Polytechnic University Wuhu Anhui 241000 China

Abstract

Comprehensive SummaryUsually, 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 (up to 13.02 × 106 g·mol–1·h–1) 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 (level of 104—105 g·mol–1·h–1), generating moderately branched (47—78/1000C) 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 activities (level of 103 g·mol–1·h–1), providing E‐MA copolymers with low to moderate molecular weights (1.4—16.3 kg/mol) and a moderate level of incorporation ratio (2.4—7.4 mol%) and branching density (53—84/1000C). 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.

Funder

Natural Science Foundation of Anhui Province

Publisher

Wiley

Subject

General Chemistry

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