Citation: Kai-ti Wang, Yong-xia Wang, Bin Wang, Yan-guo Li, Yue-sheng Li. Introduction of Constrained Cyclic Skeleton into β-Enaminoketonato Vanadium Complexes:A Strategy for Stabilization of Active Centre of Vanadium Catalyst for Ethylene Polymerization[J]. Chinese Journal of Polymer Science, ;2017, 35(9): 1110-1121. doi: 10.1007/s10118-017-1956-z shu

Introduction of Constrained Cyclic Skeleton into β-Enaminoketonato Vanadium Complexes:A Strategy for Stabilization of Active Centre of Vanadium Catalyst for Ethylene Polymerization

a.
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
Tianjin Key Lab of Composite & Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Yue-sheng Li, ysli@tju.edu.cn
Received Date: 20 February 2017
Revised Date: 6 March 2017
Accepted Date: 7 March 2017

Fund Project: China National High-tech R&D Program 2015AA034002This work was financially supported by the National Natural Science Foundation of China 21234006

Several novel mono(β-enaminoketonato) vanadium complexes bearing constrained cyclic skeleton, including[(C₆H₅)C₆H₃C(O)=C(CH₂)nCH=N-Ar]VCl₂(THF)₂ (V3a:n=1, Ar=C₆H₅; V4a:n=2, Ar=C₆H₅; V4b:n=2, Ar=C₆F₅; V4c:n=2, Ar=(C₃H₇)₂C₆H₃; V5a:n=3, Ar=C₆H₅), were synthesized and their structure and properties were characterized. The structures of V4c and V5a in solid-state were further confirmed by X-ray crystallographic analysis. Density functional theory (DFT) results indicated that these complexes showed enhanced steric hindrance around the metal center as compared with the acyclic analogues. Upon activation with Et2AlCl and in the presence of ethyl trichloroacetate as a reactivator, all of the complexes exhibited high catalytic activities (10⁷ gPE/(molV·h)) toward ethylene polymerization, and the obtained polymers exhibited unimodal distributions (Mw/Mn=2.0-2.3) even produced at elevated temperatures (70-100℃) and prolonged reaction time. When MAO was employed as a cocatalyst, they only showed moderate catalytic activities (10⁵ gPE/(molV·h)), but the resulting polymers had higher molecular weights (168-241 kg/mol). These vanadium complexes with cyclic skeleton also showed high catalytic activities toward ethylene/norbornene copolymerization. The produced copolymers displayed approximate alternating structure at high in-feed concentration of norbornene. The catalytic capabilities of these complexes could be tuned conveniently by varying ligand structure. Furthermore, the cyclic voltammetry results also proved that these complexes exhibited better redox stabilities than the complexes bearing linear skeleton.
- Vanadium catalysts,
- Ethylene polymerization,
- Cyclic skeleton,
- Steric protection
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