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Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations

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Abstract

Branched polyolefins with controllable topology structures were generated from the chain-walking (co)polymerizations of ethylene, 1-pentene (1P) and 2-pentene (2P) using Brookhart-type a-diimine Ni(II)-based catalysts possessing different para-substituted groups, {[(4-R-2-Et-6-Me-C6H2N = C)2Nap]NiBr2, Nap: 1,8-naphthdiyl; R = CHMePh, Ni1; R = Ph, Ni2; R = H, Ni3}. The X-ray diffraction analysis demonstrated that the crystalline structure of Ni1’ is in centrosymmetric dimer structure mode with the bimetallic Ni center connected by two bromide bridges. The para-sec-phenethyl moiety in the catalyst Ni1 obviously improved its catalytic performance and thermal stability in the ethylene polymerization. The Ni1/Et2AlCl system showed great catalytic activities (up to 7.73×106 g·mol−1·h−1) and achieved polyethylene (PE) with alkyl chains, including Me, Et, n-Pr, n-Bu, sec-Bu branches and longer chains (Lg). Compared with the 1-pentene polymerization, this catalyst system successfully mediated the polymerization of 2P to give highly branched polymers with approximately 195 branches/1000C possessing Me, Et, and n-Pr branches and a long methylene sequence due to the monomer isomerization. The Et branches derived from 2,3-insertion is slightly less than the sum of Me and n-Pr branches derived from 3,2-insertion, indicating that the 3,2-insertion mode is a slightly favorable pathway in the polymerization of 2P.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21801002), the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province (No. 2021LCX022), the Key R&D Projects in Anhui Province (No. 2022i01020012), and the Natural Science Foundation of Hefei (No. 2022039).

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  1. Institutes of Physical Science and Information Technology, School of Computer Science and Technology, Anhui University, Hefei, 230601, China

    Hong-Ju Liu, Wan-Lu Tian, **ao-Yue Wang, Tong Lei, Pei Li, Guo-Yong Xu, Chao Li, Shao-Jie Zhang & Fu-Zhou Wang

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Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations

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Liu, HJ., Tian, WL., Wang, XY. et al. Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations. Chin J Polym Sci 41, 905–914 (2023). https://doi.org/10.1007/s10118-022-2875-1

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