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Chinese Journal of Organic Chemistry >

2018 , Vol. 38 >Issue 8: 2151 - 2160

DOI: https://doi.org/10.6023/cjoc201803035

Notes

Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization

  • Wang Tieshi ,
  • Chen Jianjun ,
  • Ye Lin ,
  • Zhang Aiying ,
  • Feng Zengguo
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  • 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 date: 2018-03-23

  Revised date: 2018-04-25

  Online published: 2018-05-03

Supported by

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

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Abstract

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

Cite this article

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

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