Polymerization of higher α-olefins with a bis(phenoxyimine)Ti complex/i-Bu3Al/Ph3CB(C6F5)4 : Formation of stereo- and regioirregular high molecular weight polymers with high efficiency
Polymerization of higher α-olefins with a bis(phenoxyimine)Ti complex/i-Bu3Al/Ph3CB(C6F5)4 : Formation of stereo- and regioirregular high molecular weight polymers with high efficiency
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DOI：
10.1021/ma060284t
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发表时间：
2006-05
期刊：
影响因子：
5.5
通讯作者：
Junji Saito;Yasuhiko Suzuki;H. Makio;Hidetsugu Tanaka;M. Onda;T. Fujita
中科院分区：
文献类型：
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作者：
Junji Saito;Yasuhiko Suzuki;H. Makio;Hidetsugu Tanaka;M. Onda;T. Fujita
本文讨论了双（苯氧亚胺）钛配合物与i-Bu_3Al/Ph_3CB（C_6F_5）_4（其活性物种为苯氧胺钛配合物）组合用于高级α-烯烃（即α-烯烃）聚合的独特催化行为。1-己烯、1-辛烯、1-癸烯和4-甲基-1-戊烯）。该催化剂体系作为单活性中心催化剂工作，并对本研究中使用的高级α-烯烃表现出高活性。活性与普通茂金属催化剂外消旋-[C2 H4-（1-茚基）2] ZrCl 2所见的活性相当或超过。聚合速率与单体浓度呈零级关系。令人惊讶的是，该体系对更高级的α-烯烃表现出更高的活性，所述更高级的α-烯烃在烯烃部分附近引入更多的空间位阻取代基（活性顺序：4-甲基-1-戊烯> 1-癸烯> 1-辛烯> 1-己烯）。所得聚合物具有非常高的分子量（Mw 846 000−1 450 000），代表了一些最高的聚（更高...
The unique catalytic behavior of a bis(phenoxyimine)Ti complex combined with i-Bu3Al/Ph3CB(C6F5)4 (whose active species is a phenoxyamine Ti complex) is discussed here for use in the polymerization of higher α-olefins (i.e., 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene). The catalyst system works as a single-site catalyst and exhibits high activities toward the higher α-olefins that were used in this study. The activities are comparable to or exceed those seen with a common metallocene catalyst, rac-[C2H4-(1-indenyl)2]ZrCl2. The polymerization rate has a zeroth-order dependence on the concentration of the monomer. To our surprise, the system exhibited higher activities toward higher α-olefins that incorporate more sterically encumbered substituents in close proximity to the olefinic moieties (activity order: 4-methyl-1-pentene > 1-decene > 1-octene > 1-hexene). The resultant polymers have very high molecular weights (Mw 846 000−1 450 000), representing some of the highest reported for poly(higher...