Controllable Preparation of Branched Polyolefins with Various Microstructural Units <italic style="font-style: italic">via</italic> Chain-walking Ethylene and Pentene Polymerizations

Hong-Ju Liu; Wan-Lu Tian; Xiao-Yue Wang; Tong Lei; Pei Li; Guo-Yong Xu; Chao Li; Shao-Jie Zhang; Fu-Zhou Wang

doi:10.1007/s10118-022-2875-1

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

RESEARCH ARTICLE | Updated：2023-05-26

- Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations
- Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations
- 高分子科学（英文版） 2023年41卷第6期页码：905-914
- Affiliations：
  
  Institutes of Physical Science and Information Technology, School of Computer Science and Technology, Anhui University, Hefei 230601, China
- Author bio：
  
  lichao22049@ahu.edu.cn (C.L.)
  zhangshaojie@ahu.edu.cn (S.J.Z.)
  wangfuzhou@ahu.edu.cn (F.Z.W.)
- Funds：
  
  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).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-022-2875-1.
- DOI：10.1007/s10118-022-2875-1
  中图分类号：
- 收稿：2022-08-04，
  
  修回：2022-9-10，
  
  录用：2022-9-19，
  
  网络首发：2022-11-18，
  
  纸质出版：2023-06-01
- Accepted：
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Liu, H. J.; Tian, W. L.; Wang, X. Y.; Lei, T.; Li, P.; Xu, G. Y.; Li, C.; Zhang, S. J.; Wang, F. Z. Controllable preparation of branched polyolefins with various microstructural units via chain-walking ethylene and pentene polymerizations. Chinese J. Polym. Sci. 2023, 41, 905–914

Hong-Ju Liu, Wan-Lu Tian, Xiao-Yue Wang, et al. Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations[J]. Chinese Journal of Polymer Science, 2023, 41(6): 905-914. DOI: 10.1007/s10118-022-2875-1.
Liu, H. J.; Tian, W. L.; Wang, X. Y.; Lei, T.; Li, P.; Xu, G. Y.; Li, C.; Zhang, S. J.; Wang, F. Z. Controllable preparation of branched polyolefins with various microstructural units via chain-walking ethylene and pentene polymerizations. Chinese J. Polym. Sci. 2023, 41, 905–914 DOI： 10.1007/s10118-022-2875-1.

Hong-Ju Liu, Wan-Lu Tian, Xiao-Yue Wang, et al. Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations[J]. Chinese Journal of Polymer Science, 2023, 41(6): 905-914. DOI: 10.1007/s10118-022-2875-1. DOI：

摘要

The chain-walking (co)polymerization of ethylene

1-pentene and 2-pentene was carried out using

α-

diimine Ni(II) catalysts in combination with Et

AlCl

leading to the formation of branched polyolefins with various types of branches and microstructural units. This catalyst system can efficiently obtain highly branched amorphous polyethylene with alkyl chains including Me

sec-

Bu branches and longer chains. Compared with the 1-pentene polymerization

this catalyst system successfully conducted polymerization of 2-pentene to give highly branched polymers of approximately 195 branches/1000C possessing Me

and

Pr branches and a long methylene sequence.

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

α-

diimine Ni(II)-based catalysts possessing different

para-

substituted groups

{[(4-R-2-Et-6-Me-C

N＝C)

Nap]NiBr

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

/Et

AlCl system showed great catalytic activities (up to 7.73×10

g·mol

−1

·h

−1

) and achieved polyethylene (PE) with alkyl chains

including Me

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

and

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

Pr branches derived from 3

2-insertion

indicating that the 3

2-insertion mode is a slightly favorable pathway in the polymerization of 2P.

关键词

Keywords

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

DOI：10.1007/s10118-022-2875-1

摘要

Abstract

关键词

Keywords

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