Ethylene oligomerization by salen-type zirconium complexes to low-carbon linear α-olefins
Ethylene oligomerization by salen-type zirconium complexes to low-carbon linear α-olefins
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DOI：
10.1016/s0021-9517(03)00306-3
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发表时间：
2003-12
影响因子：
7.3
通讯作者：
Mei Wang;Hongjun Zhu;Kun Jin;D. Dai;Licheng Sun
中科院分区：
文献类型：
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作者：
Mei Wang;Hongjun Zhu;Kun Jin;D. Dai;Licheng Sun
以四齿Schiff碱的钠盐和ZrCl 4为配体，合成了一系列Salen型锆配合物。在150°C、1.0- 1.8MPa的压力下，它们与Et 2AlCl配合使用时，对乙烯齐聚反应表现出中等至高的催化活性。主要产物为C4-C10烯烃，对直链α-烯烃有较好的选择性。Zr（salen）Cl 2·THF/Et 2AlCl催化剂体系在1.8 MPa、Al/Zr摩尔比为300的条件下，转化率（TOF）为4.93× 104 h-1，C4-C10烯烃选择性为89%，直链α-烯烃占95%。研究了配体对乙烯齐聚反应的空间位阻和共轭效应，以及助催化剂、Al/Zr摩尔比、反应温度、乙烯压力和催化剂寿命等因素对乙烯齐聚反应的影响。
A series of zirconium salen-type complexes were prepared by using ZrCl4and sodium salts of the tetradentate Schiff base ligands. In combination with Et2AlCl, they displayed moderate to high catalytic activities in ethylene oligomerization under a pressure of 1.0–1.8 MPa at 150°C in toluene. The main products are C4–C10olefins with good selectivity to linear α-olefins. The turnover frequency (TOF) of catalyst system Zr(salen)Cl2·THF/Et2AlCl, under a pressure of 1.8 MPa and in an Al/Zr molar ratio of 300, was 4.93×104h−1with a satisfactory selectivity to C4–C10olefins (89%), and linear α-olefins accounted for 95%. The steric and conjugate effects of the ligands on ethylene oligomerization, as well as the effects of cocatalysts, the Al/Zr molar ratios, the reaction temperature, the ethylene pressure, and the lifetime of the catalysts were studied.