Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (8): 2151-2160.DOI: 10.6023/cjoc201803035 Previous Articles     Next Articles

Special Issue: 元素有机化学合辑2018-2019



王铁石a, 陈建军b, 叶霖a,c, 张爱英a,c, 冯增国a,c   

  1. a 北京理工大学材料学院 北京 100081;
    b 中国石油化工股份有限公司北京北化院燕山分院 北京 102500;
    c 北京市结构可控先进功能材料与绿色应用重点实验室 北京 100081
  • 收稿日期:2018-03-23 修回日期:2018-04-25 发布日期:2018-05-03
  • 通讯作者: 冯增国
  • 基金资助:


Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization

Wang Tieshia, Chen Jianjunb, Ye Lina,c, Zhang Aiyinga,c, Feng Zengguoa,c   

  1. 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
  • Received:2018-03-23 Revised:2018-04-25 Published:2018-05-03
  • Contact: 10.6023/cjoc201803035
  • Supported by:

    Project supported by the Technology Development Project of China Petroleum & Chemical Corporation (Sinopec) (No. 214002).

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 Mw polyethylene at lower polymerization temperature.

Key words: bimetallic titanium catalyst, heteroaryl, phosphinimine, ethylene polymerization