Design and Synthesis of Bis-<italic style="font-style: italic">β</italic>-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization

Ming Zhou; Meng-Yuan Xue; Ping-Zhou Huang; Ting-Cheng Li; Qing-Liang You; Guang-Yong Xie

doi:10.1007/s10118-025-3312-z

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Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization

RESEARCH ARTICLE | Updated：2025-07-14

- Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization
- Chinese Journal of Polymer Science Vol. 43, Issue 5, Pages: 756-768(2025)
- Affiliations：
  
  a.Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central Minzu University, Wuhan 430074, China
  b.Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Chemical and Environmental Engineering, Jianghan University, Wuhan 430056, China
- Author bio：
  
  xiegy@scuec.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3312-z
  CLC：
- Received：10 November 2024，
  
  Revised：2025-01-23，
  
  Accepted：26 January 2025，
  
  Online First：07 April 2025，
  
  Published：30 April 2025
- Accepted：
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Zhou, M.; Xue, M. Y.; Huang, P. Z.; Li, T. C.; You, Q. L.; Xie, G. Y. Design and synthesis of bis-β-ketoimine binuclear titanium complex isomers to probe bimetallic synergistic effect for ethylene polymerization. Chinese J. Polym. Sci. 2025, 43, 756–768

Ming Zhou, Meng-Yuan Xue, Ping-Zhou Huang, et al. Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(5): 756-768. DOI: 10.1007/s10118-025-3312-z.
Zhou, M.; Xue, M. Y.; Huang, P. Z.; Li, T. C.; You, Q. L.; Xie, G. Y. Design and synthesis of bis-β-ketoimine binuclear titanium complex isomers to probe bimetallic synergistic effect for ethylene polymerization. Chinese J. Polym. Sci. 2025, 43, 756–768 DOI： 10.1007/s10118-025-3312-z.

Ming Zhou, Meng-Yuan Xue, Ping-Zhou Huang, et al. Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(5): 756-768. DOI: 10.1007/s10118-025-3312-z. DOI：

摘要

Six bis-β-ketoimine binuclear titanium complexes were synthesized and showed good performance for ethylene (co)polymerization. The intermetallic distances of isomers

and

influenced significantly the catalytic performance. Complex

with the shortest bimetallic distance exhibited the best performance because of more appropriate bimetallic distance and stronger synergistic effect.

Abstract

Binuclear complexes have attr

acted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect; however

the mechanism and factors influencing this synergism remain unclear. In this work

six bis-

-ketoimine binuclear titanium complexes

–

containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum (

H-NMR)

nuclear magnetic resonance carbon spectrum (

C-NMR)

Fourier transform infrared spectrum (FTIR)

and elemental analysis. The intermetallic distances of isomeric complexes

and

determined through density functional theory (DFT) optimization were in the order

and were found to significantly influence the catalytic performance for ethylene (co)polymerization. These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce high-molecular-weight ethylene homo- and co-polymers. Among the three binuclear titanium complexes

–

with similar structures but different lengths of alkylthio sidearms

complex

which contained the shortest methylthio sidearm

exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene. Additionally

for ethylene/1-hexene or ethylene/1-octene copolymerization

it showed the highest comonomer incorporation compared with propylthio (

) and octylthio (

) derivatives because of the smaller steric hindrance of the methyl group in

and the more open coordination space for vinyl monomers. Furthermore

among the isomeric complexes

and

complex

with the shortest bimetallic distance also exhibited the h

ighest activity towards ethylene (co)polymerization

and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts

and

-phenyl-bridged analog

owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.

关键词

Keywords

references

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⁰

Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization

DOI：10.1007/s10118-025-3312-z

摘要

Abstract

关键词

Keywords

references