Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers

Fei Wang; Li Pan; Vladislav A. Tuskaev; Svetlana Ch. Gagieva; Yue-Sheng Li

doi:10.1007/s10118-023-3044-x

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Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers

RESEARCH ARTICLE | Updated：2024-01-12

- Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers
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- Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers
- 高分子科学（英文版） 2024年42卷第2期页码：202-212
- Affiliations：
  
  a.Tianjin Key Lab of Composite & Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China
  b.Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1, Moscow 119991, Russian Federation
  c.A N Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova st., 28, Moscow 119991, Russian Federation
- Author bio：
  
  lilypan@tju.edu.cn (L.P.)
  ysli@tju.edu.cn (Y.S.L.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52130307).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3044-x.
- DOI：10.1007/s10118-023-3044-x
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Wang, F.; Pan, L.; Tuskaev, V. A.; Gagieva, S. C.; Li, Y. S. Phosphine/benzocyclone-based neutral nickel catalysts for ethylene polymerization and copolymerization with polar monomers. Chinese J. Polym. Sci. 2024, 42, 202–212

Fei Wang, Li Pan, Vladislav A. Tuskaev, et al. Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers[J]. Chinese Journal of Polymer Science, 2024,42(2):202-212.
Wang, F.; Pan, L.; Tuskaev, V. A.; Gagieva, S. C.; Li, Y. S. Phosphine/benzocyclone-based neutral nickel catalysts for ethylene polymerization and copolymerization with polar monomers. Chinese J. Polym. Sci. 2024, 42, 202–212 DOI： 10.1007/s10118-023-3044-x.

Fei Wang, Li Pan, Vladislav A. Tuskaev, et al. Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers[J]. Chinese Journal of Polymer Science, 2024,42(2):202-212. DOI： 10.1007/s10118-023-3044-x.

摘要

A series of strategically designed neutral nickel catalysts with phosphine/benzocyclone-based ligand skeleton displayed high activity and thermal stability in ethylene polymerization to afford linear polyethylene. These bulky nickel catalysts also exhibited excellent tolerance towards acrylate functional groups and high incorporating capability, producing random copolymers with high molecular weights.

Abstract

The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts (,Ni1,: Ar = Ph; ,Ni2,: Ar = 2-(C,6,H,5,)C,6,H,4,; ,Ni3,: Ar = 2-[2',6'-(MeO),2,-C,6,H,3,]C,6,H,4,) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes ,Ni2, and ,Ni3, contributed to high catalytic activities (up to 7.24×10,6, and 9.04×10,6, g·mol,Ni,‒1,·h,‒1, respectively), and produced high-molecular-weight polyethylene (,M,w, up to 545.7 kDa). Complex ,Ni3, exhibited high activities for ethylene polymerization at the level of 10,6, g·mol,Ni,‒1,·h,‒1, across a wide range from 30 °C to 120 °C, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights (,M,w, up to 80.5 kDa) and high polar monomer incorporation (up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.

关键词

Keywords

Neutral nickel catalystEthylene polymerizationCopolymerizationPolar acrylate monomers

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