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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