三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能

doi:10.6023/cjoc201801004

有机化学 ›› 2018, Vol. 38 ›› Issue (6): 1544-1548.DOI: 10.6023/cjoc201801004 上一篇下一篇

研究简报

三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能

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化工研究院燕山分院北京 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:2018-01-04 修回日期:2018-02-09 发布日期:2018-03-08
通讯作者: 冯增国,E-mail:sainfeng@bit.edu.cn 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项目（No.214002）资助项目.

Synthesis of Tritertbutylphosphinimine Phenoxy Titanium Complexes and Their Catalytic Performance to 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:2018-01-04 Revised:2018-02-09 Published:2018-03-08
Contact: 10.6023/cjoc201801004 E-mail:sainfeng@bit.edu.cn
Supported by:
Project supported by the Technology Development Project of China Petroleum & Chemical Corporation (Sinopec) (No. 214002).

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摘要/Abstract

四种不同基团取代的苯酚锂盐分别与三叔丁基膦亚胺三氯化钛进行反应，制得相应三叔丁基膦亚胺苯氧钛配合物（t-Bu₃） PNTi（OAr） Cl₂[OAr＝O-C₆H₅（4a），O-2，6-Me₂C₆H₃（4b），O-2，6-i-Pr₂C₆H₃（4c）和O-2，6-t-Bu₂C₆H₃（4d）]，产物均借助¹H NMR，¹³C NMR，³¹P NMR及元素分析进行了结构表征，并利用X射线单晶衍射确定了配合物三叔丁基膦亚胺三氯化钛（3），4b和4d的分子结构.在助催化剂甲基铝氧烷（MAO）作用下，4a～4d对乙烯聚合均表现出高催化活性，并随配合物空间位阻增加而升高.4c热稳定性好，通过控制聚合反应条件，由此可以得到不同分子量及分子量分布的聚乙烯产物.

关键词: 三叔丁基膦亚胺, 取代苯氧基, 钛配合物, 乙烯聚合

Tritertbutylphosphinimine phenoxy titanium complexes (t-Bu₃)PNTi(OAr)Cl₂ [Ar=C₆H₅(4a), 2,6-Me₂C₆H₃ (4b), 2,6-i-Pr₂C₆H₃ (4c) and 2,6-t-Bu₂C₆H₃ (4d)] were synthesized via the reaction of corresponding substituted phenol lithium salts with tritertbutylphosphinimine trichloride titanium (3). The compounds were characterized by means of ¹H NMR, ¹³C NMR, ³¹P NMR spectroscopic and elemental analyses, and the molecular structures of 3, 4b and 4d were further confirmed by single-crystal X-ray diffraction analysis. When activated with methylaluminoxane (MAO), 4a~4d displayed not only high catalytic activities, but also increasing performances on ethylene polymerization with increasing the sterical hindrance of substituents. Furthermore, 4c depicted a good thermal stability, with which the polyethylene products of different molecular weights and molecular weight distributions can be obtained by tuning the polymerization conditions.

Key words: tritertbutylphosphinimine, substituted phenoxy, titanium complex, ethylene polymerization

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王铁石, 陈建军, 叶霖, 张爱英, 冯增国. 三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能[J]. 有机化学, 2018, 38(6): 1544-1548.

Wang Tieshi, Chen Jianjun, Ye Lin, Zhang Aiying, Feng Zengguo. Synthesis of Tritertbutylphosphinimine Phenoxy Titanium Complexes and Their Catalytic Performance to Ethylene Polymerization[J]. Chin. J. Org. Chem., 2018, 38(6): 1544-1548.

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三叔丁基膦亚胺苯氧钛配合物及其乙烯聚合性能

Synthesis of Tritertbutylphosphinimine Phenoxy Titanium Complexes and Their Catalytic Performance to Ethylene Polymerization

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