Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged <italic style="font-style: italic">ansa</italic>-(3-<italic style="font-style: italic">R</italic>-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes

Bo Li; Haiyan Ma; Jiling Huang

doi:10.1007/s10118-023-3034-z

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Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes

RESEARCH ARTICLE | Updated：2023-12-26

- Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes
- Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes
- 高分子科学（英文版） 2024年42卷第1期页码：42-51
- Affiliations：
  
  Shanghai Key Laboratory of Functional Materials Chemistry and Laboratory of Organometallic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  haiyanma@ecust.edu.cn (H.M.)
  jlhuang@ecust.edu.cn (J.H.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 21274041).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3034-z.
- DOI：10.1007/s10118-023-3034-z
  中图分类号：
- 收稿：2023-06-08，
  
  修回：2023-7-23，
  
  录用：2023-7-24，
  
  网络首发：2023-09-15，
  
  纸质出版：2024-01-01
- Accepted：
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Li, B.; Ma, H.; Huang, J. Access to high-molecular-weight polyethylenes through high temperature ethylene polymerization catalysed by ethylene-bridged ansa-(3-R-cyclopentadienyl)(fluorenyl) zirconocene complexes. Chinese J. Polym. Sci. 2024, 42, 42–51

Bo Li, Haiyan Ma, Jiling Huang. Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes[J]. Chinese Journal of Polymer Science, 2024, 42(1): 42-51. DOI: 10.1007/s10118-023-3034-z.
Li, B.; Ma, H.; Huang, J. Access to high-molecular-weight polyethylenes through high temperature ethylene polymerization catalysed by ethylene-bridged ansa-(3-R-cyclopentadienyl)(fluorenyl) zirconocene complexes. Chinese J. Polym. Sci. 2024, 42, 42–51 DOI： 10.1007/s10118-023-3034-z.

Bo Li, Haiyan Ma, Jiling Huang. Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes[J]. Chinese Journal of Polymer Science, 2024, 42(1): 42-51. DOI: 10.1007/s10118-023-3034-z. DOI：

摘要

Novel ethylene-bridged

ansa

-(3-R-cyclopentadienyl)(fluorenyl) zirconocene and hafnocene complexes have been synthesized and characterized. Among them zirconocene complexes showed high catalytic activities toward the polymerization of ethylene at high temperatures. By adopting low Al/Zr ratios such as 125

polyethylenes with ultra-high molecular weights up to 2.86×10

g/mol were obtained.

Abstract

A series of

-symmetric ethylene-bridged

ansa

-(3-

-cyclopentadienyl)(fluorenyl) metallocene complexes (Zr:

−

; Hf:

) have been synthesized

characterized and investigated as catalyst precursors for the high temperature ethylene polymerization. Using methylaluminoxane (MAO) as the cocatalyst

zirconium complexes

−

bearing a bulky substituent on the 3-position of the cyclopendienyl ring showed high catalytic activities up to 1.48×10

·mol

−1

·h

−1

toward the polymerization of ethylene and afforded polyethylenes with high molecular weights (1.49×10

−6.31×10

g/mol)

meanwhile exhibting great thermal stability at high temperatures up to 120 °C together with a long catalytic life time up to 2 h. By adopting low Al/Zr ratios

such as 125

polyethylenes with ultra high molecular weights up to 2.86×10

g/mol were obtained. It is worthy of noting that zirconium complexes

−

bearing a substituent with an aryl pendant showed temperature-dependent activities

which increased rapidly with the increase of polymerization temperature

thus weak interaction of the pendent aryl group with the cationic active center is proposed to account for the very low activities displayed at low temperatures. In contrast to zirconocene complexes

−

hafnocene complex

only displayed very low catalytic activities toward the polymerization of ethylene and afforded polyethylenes with molecular weights ten times smaller than those obtained by zirconocene complexes

−

. Zirconocene complexes

−

were also able to catalyse the polymerization of propylene at high temperatures

but only afforded waxes with low molecular weights.

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references

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Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes

DOI：10.1007/s10118-023-3034-z

摘要

Abstract

关键词

Keywords

references