Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization

Biao Li; Yuan-Bo Liu; Ying-Li Ding; Li Pan; Yue-Sheng Li

doi:10.1007/s10118-025-3443-2

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Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization

RESEARCH ARTICLE | Updated：2025-12-03

- Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization
- Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization
- Chinese Journal of Polymer Science 2025年43卷第12期页码：2299-2309
- Affiliations：
  
  a.School of Materials Science and Engineering, State Key Laboratory of High-Performance Roll Materials and Composite Forming, Tianjin University, Tianjin 300350, China
  b.PetroChina Refining, Chemicals & New Materials Company, Beijing 100007, China
  c.Tianjin Key Laboratory of Composite and Functional Materials, Key Laboratory of Organic Integrated Circuits, Ministry of Education, Tianjin 300350, China
- Author bio：
  
  lilypan@tju.edu.cn
- 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/s10118-025-3443-2.
- DOI：10.1007/s10118-025-3443-2
  中图分类号：
- 收稿：2025-07-24，
  
  录用：2025-08-22，
  
  网络首发：2025-11-12，
  
  纸质出版：2025-12-15
- Accepted：
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Li, B.; Liu, Y. B.; Ding, Y. L.; Pan, L.; Li, Y. S. Super-high active, homogeneous vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands for diverse olefins (co)polymerization. Chinese J. Polym. Sci. 2025, 43, 2299–2309

Biao Li, Yuan-Bo Liu, Ying-Li Ding, et al. Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2299-2309.
Li, B.; Liu, Y. B.; Ding, Y. L.; Pan, L.; Li, Y. S. Super-high active, homogeneous vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands for diverse olefins (co)polymerization. Chinese J. Polym. Sci. 2025, 43, 2299–2309 DOI： 10.1007/s10118-025-3443-2.

Biao Li, Yuan-Bo Liu, Ying-Li Ding, et al. Super-high Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins (Co)polymerization[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2299-2309. DOI： 10.1007/s10118-025-3443-2.

摘要

Vanadium complexes bearing bidentate phenoxy-phosphine ligands demonstrated remarkable efficiency in ethylene homopolymerization and copolymerization with various olefins. Their catalytic performance was strongly influenced by the electronic and steric environment of ligands and comonomers. These results highlight the importance of rational ligand design and comonomer selection in optimizing catalyst performance.

Abstract

A series of imido-vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR

elemental analysis

and single-crystal X-ray diffraction. These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization

achieving high activities of 12.0×10

–49.0×10

polymer

·(mol

)

–1

·h

–1

and affording random copolymers with tunable 1-hexene incorporations. These catalysts also exhibited ultrahigh activity

to 112.2×10

polymer

·(mol

)

–1

·h

–1

in ethylene/norbornene (NB) copolymerization

yielding cyclic olefin copolymers with adjustable NB incorporations. Remarkably

these catalysts demonstrated exceptional tolerance toward polar functional groups

enabling efficient copolymerization of ethylene with both 10-undecen-1-ol (U-OH) and 5-norbornene-2-methanol (NB-OH)

incorporating about 2 mol% polar comonomers with high efficiency. Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers

the catalytic activities in E/U-OH copolymerization (25.7×10

polymer

·(mol

)

–1

·h

–1

) were much higher than those in E/NB-OH copolymerization (8.6×10

polymer

·(mol

)

–1

·h

–1

). DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects. For E/NB copolymerization

strong preference for cyclic olefins was attributed to favorable transition state stabilization. In polar comonomer systems

steric effects were predominant

with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH. Overall

this work provides fundamental insights into vanadium-catalyzed (co)polymerization and offers new strategies for tailored polyolefin design.

关键词

Keywords

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