Citation: Ling-pan Lu, Kai-ti Wang, Yi Liu, Jia-jun Wu. Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization[J]. Acta Polymerica Sinica, ;2020, 51(2): 174-182. doi: 10.11777/j.issn1000-3304.2019.19128 shu

Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

Ling-pan Lu ¹ ,
Kai-ti Wang ^2,, ,
Yi Liu ² ,
Jia-jun Wu ²

1.
School of Pharmacy and Chemical Engineering, Zhengzhou University of Industrial Technology, Zhengzhou 451199
2.
School of Materials Science and Engineering, Chongqing University of Technology, Chongqing 400054

Corresponding author: Kai-ti Wang, ktwang@cqut.edu.cn
Received Date: 3 July 2019
Revised Date: 25 July 2019

Vanadium catalysts always show outstanding catalytic properties towards ethylene (co)polymeriztaion, while the high-valent vanadium species would be deactivated because of the generation of inactive or less active low-valent species at elevated temperature and/or in prolonged time. As proved, introducing of bulky groups into the ligands is benefit to improving the catalytic properties of vanadium complexes. Herein, in order to well control the oxidation state of vanadium species, a series of tridentate β-ketoimine type vanadium(III) complexes bearing cyclic skeleton {[(R)X(C₆H₄)N＝CH(C₆H₅)C₁₀H₇O]VCl₂(THF): 2a , R = CH₃, X = S; 2b , R = CF₃, X = S; 2c , R = Ph, X = S; 2d , R = ^tBu, X = S; 2e , R = Ph₂, X = P; 2f , R = Ph, X = O}, were synthesized and characterized. Because of the constrained effects of the cyclic skeleton and the stabilizing effects of the bi-chelating ring, these synthesized catalysts showed high activities and improved stabilities in ethylene (co)polymerization. In the presences of Et₂AlCl and ethyl trichloroacetate, catalysts 2a − 2f showed 8.16 − 19.9 kg_polymer/(mmol_V·h), 7.68 − 26.9 kg_polymer/(mmol_V·h) and 4.80 − 42.2 kg_polymer/(mmol_V·h) of catalytic activities towards ethylene polymerization, ethylene/norbornene (NBE) copolymerization and ethylene/exo-1,4,4a,9,9a,10-hexahy-dro-9,10(1′,2′)-benzeno-1,4-methanoanthracene (HBM) copolymerization, respectively. All of the resultant polymers exhibited a unimodal distribution, indicating that these vanadium catalysts showed single-site catalytic behaviour, even at elevated temperatures (50 − 70 °C). Catalysts 2b , 2d , 2e and 2f showed “positive” comonomer effects in both ethylene/NBE copolymerization and ethylene/HBM copolymerization. Besides, 2a and 2c also exhibited “positive” comonomer effects in ethylene/HBM copolymerization. Cyclic olefin copolymers possessing high molecular weights (NBE: 43.1 − 66.4 kg/mol; HBM: 90.2 − 138 kg/mol) and high comonomer incorporations (NBE: 30.9 mol% − 42.1 mol%; HBM: 14.7 mol% − 25.0 mol%) were obtained facilely via direct copolymerization. The glass transition temperature is dominantly affected by the cyclic olefin incorporations and the steric hindrance of the cyclic olefin. Compared with the ethylene/NBE copolymers, the obtained ethylene/HBM copolymers showed much higher glass transition temperatures (NBE: 84 − 105 °C versus HBM: 173 − 188 °C).
- Vanadium complexs,
- Olefin polymerization,
- Polyethylene,
- Cyclic olefin copolymers
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