Copolymerization of ethylene with cyclohexene (CHE) catalyzed by nonbridged half-titanocenes containing aryloxo ligand: notable effect of both cyclopentadienyl and anionic donor ligand for efficient CHE incorporation.
Copolymerization of ethylene with cyclohexene (CHE) catalyzed by nonbridged half-titanocenes containing aryloxo ligand: notable effect of both cyclopentadienyl and anionic donor ligand for efficient CHE incorporation.
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DOI：
10.1021/ja050274s
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发表时间：
2005-03
影响因子：
15
通讯作者：
Wei Wang-;M. Fujiki;K. Nomura
中科院分区：
文献类型：
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作者：
Wei Wang-;M. Fujiki;K. Nomura
在甲基铝氧烷 (MAO) 助催化剂存在下，通过含有 Cp'TiCl2(O-2,6-iPr2C6H3) 类型芳氧基配体的非桥联半二茂钛，将环己烯 (CHE) 引入乙烯/CHE 共聚的聚合物链中。研究发现环戊二烯基片段中的取代基对于 CHE 的掺入非常重要； tert-BuCp (3) 和 1,2,4-Me3Cp 类似物 (4) 均显示出有效的 CHE 掺入，而茚基 (1) 和 Cp* 类似物 (2) 在相同条件下观察到的 CHE 掺入量可忽略不计。 Cp-酮亚胺类似物、CpTiCl2(N=CtBu2) (5)、类二茂锆 Cp2ZrCl2 (6) 和类连接半二茂钛 [Me2Si(C5Me4)(NtBu)]TiCl2 (7) 在相同条件下没有表现出任何 CHE 掺入；因此强调了使用此类催化剂前体进行本发明共聚的独特特性。
Cyclohexene (CHE) has been incorporated into the polymer chain in ethylene/CHE copolymerization by nonbridged half-titanocenes containing aryloxo ligands of the type, Cp'TiCl2(O-2,6-iPr2C6H3), in the presence of methylaluminoxane (MAO) cocatalyst. The effect of the substituent in the cyclopentadienyl fragment was found to be very important for CHE incorporation; both the tert-BuCp (3) and 1,2,4-Me3Cp analogues (4) showed efficient CHE incorporation, whereas a negligible amount of CHE incorporation was observed by both the indenyl (1) and the Cp* analogue (2) under the same conditions. Cp-ketimide analogue, CpTiCl2(N=CtBu2) (5), zirconocene-like Cp2ZrCl2 (6), and linked half-titanocene-like [Me2Si(C5Me4)(NtBu)]TiCl2 (7) did not show any CHE incorporation under the same conditions; unique characteristics for using this type of catalyst precursor for the present copolymerization have thus been emphasized.