Citation: Wang Tieshi, Chen Jianjun, Ye Lin, Zhang Aiying, Feng Zengguo. Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization[J]. Chinese Journal of Organic Chemistry, ;2018, 38(8): 2151-2160. doi: 10.6023/cjoc201803035 shu

Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization

Wang Tieshi ^a ,
Chen Jianjun ^b ,
Ye Lin ^a,c ,
Zhang Aiying ^a,c ,
Feng Zengguo ^a,c,,

a.
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081
b.
Sinopec Yanshan Branch, Beijing Research Institute of Chemical Industry, Beijing 102500
c.
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, Beijing 100081

Corresponding author: Feng Zengguo, sainfeng@bit.edu.cn
Received Date: 23 March 2018
Revised Date: 25 April 2018
Available Online: 3 August 2018
Fund Project: Project supported by the Technology Development Project of China Petroleum & Chemical Corporation (Sinopec) (No. 214002)the Technology Development Project of China Petroleum & Chemical Corporation (Sinopec) 214002

Figures(5)

Mono-and bisdiphenyl substituted heteroarylphosphines R-PPh₂[R=2-pyridyl (3a), 2-thienyl (3b) and 2-furyl (3c)] and Ph₂P-R'-PPh₂[R'=2, 6-pyridyl (6a), 2, 5-thienyl (6b) and 2, 5-furyl (6c)] were synthesized. After Staudinger reaction with Me₃SiN₃, those heteroarylphosphines were converted into the heteroarylphosphinimine ligands, R-PPh₂(NSiMe₃) and (Me₃SiN)Ph₂P-R"-PPh₂(NSiMe₃). The subsequently dehalosilylation reaction with CpTiCl₃ afforded the corresponding Ti heteroarylphosphinimine halfmetallocenes as olefin polymerization catalysts. The structures of all the complexes were determined by means of ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopic methods and further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane (MAO) at a ratio of Al/Ti=600 and under 0.5 MPa of ethylene, these bimetallic Ti phosphinimine complexes displayed a higher catalytic activity compared to the monometallic analogues, but resulted in polymers with bimodal molecular weight distributions. Unexpectedly, 6b produced ultrahigh M_w polyethylene at lower polymerization temperature.
- bimetallic titanium catalyst,
- heteroaryl,
- phosphinimine,
- ethylene polymerization
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