桥联环戊二烯金刚烷氨基二甲基钛配合物的合成及其催化丙烯聚合

doi:10.11944/j.issn.1000-0518.2015.09.140452

摘要/Abstract

摘要：

合成了新型限制几何构型四甲基环戊二烯金刚烷氨基二甲基钛配合物(1-Adamantyl)NSiMe₂(C₅Me₄)]TiMe₂(c)。通过¹H NMR、元素分析以及单晶衍射分析等技术手段确定了该配合物的结构。与其叔丁基氨配合物tBuNSiMe₂(C₅Me₄)]TiMe₂(a)对比,在修饰甲基铝氧烷(MMAO)/2,6-二叔丁基-4-甲基苯酚(BHT)活化下进行丙烯聚合,探讨了氨基配体结构及聚合条件对聚合性能的影响。在保持准活性聚合的条件下,金刚烷胺基配合物c的催化活性为562 kg_(PP)/(mol_(Ti)·h),为叔丁胺基配合物a的2倍以上,说明金刚烷胺的引入有助于提高体系的链增长速率。

关键词: 限制几何构型, 均相催化剂, 丙烯聚合

Abstract:

(1-Adamantyl)NSiMe₂(C₅Me₄)]TiMe₂(c) was synthesized and characterized by elemental analysis, ¹H NMR, and single-crystal X-ray analysis. Propylene polymerization was conducted with complex c using modified methyaluminoxane(MMAO)/butylated hydroxytoluene(BHT) as a cocatalyst to compare the polymerization activity of complex c with that of tert-butylamido complex(tBuNSiMe₂(C₅Me₄)]TiMe₂)(a). The c-heptane system shows an activity of 562 kg_(PP)/(mol_(Ti)·h) which is two times higher than that of a-heptane system indicating that the activity is improved by the introduction of 1-adamantyl substituent to the amido ligand.

Key words: constrained geometry catalyst, single-site catalyst, propylene polymerization

许波,孙延杰,杜飞瀑,蔡正国. 桥联环戊二烯金刚烷氨基二甲基钛配合物的合成及其催化丙烯聚合[J]. 应用化学, 2015, 32(9): 1028-1032.

XU Bo,SUN Yanjie,DU Feipu,CAI Zhengguo. Synthesis of ansa-(Cyclopentadienyl)(adamantylamido) titanium Complex for Propylene Polymerization[J]. Chinese Journal of Applied Chemistry, 2015, 32(9): 1028-1032.

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