Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization

doi:10.6023/cjoc201803035

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

Notes

杂环膦亚胺钛配合物的合成及催化乙烯聚合

王铁石^a, 陈建军^b, 叶霖^a,c, 张爱英^a,c, 冯增国^a,c

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 E-mail:sainfeng@bit.edu.cn
基金资助:
中国石油化工股份有限公司技术开发（No.214002）资助项目.

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

Received:2018-03-23 Revised:2018-04-25 Published:2018-05-03
Contact: 10.6023/cjoc201803035 E-mail:sainfeng@bit.edu.cn
Supported by:
Project supported by the Technology Development Project of China Petroleum & Chemical Corporation (Sinopec) (No. 214002).

1. Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization.PDF(5041KB)

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 M_w polyethylene at lower polymerization temperature.

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

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Wang Tieshi, Chen Jianjun, Ye Lin, Zhang Aiying, Feng Zengguo. Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization[J]. Chin. J. Org. Chem., 2018, 38(8): 2151-2160.

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杂环膦亚胺钛配合物的合成及催化乙烯聚合

Synthesis of Titanium Heteroarylphosphinimine Complexes and Application for Ethylene Polymerization

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