Highly active chromium-based selective ethylene tri-/tetramerization catalysts supported by N, N-diphospholylamines
Highly active chromium-based selective ethylene tri-/tetramerization catalysts supported by N, N-diphospholylamines
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N,N-二磷胺负载的高活性铬基选择性乙烯三聚/四聚催化剂
DOI：
10.1016/j.ica.2017.05.042
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发表时间：
2017
影响因子：
2.8
通讯作者：
Zhang Jun
中科院分区：
文献类型：
--
作者：
Ji Xiaoyu;Song Liubing;Zhang Chengye;Jiao Jiajun;Zhang Jun
我们已经开发了新型的Cr（III）催化剂支持的不对称N，N-二磷胺配体轴承phenoxaphosphine基团。在用MMAO-3A活化后，由PNP配体负载的Cr（III）催化剂对乙烯三聚/四聚具有高活性，具有相当大的选择性。发现配体取代和低聚条件对于实现高活性和可控选择性是必不可少的。不对称双磷酰胺配体的催化体系比对称配体的催化体系具有更高的催化活性。具有N-环己基的不对称二磷酰胺配体在35巴、80 ° C下实现了282.2 kg/（g Cr/h）的最高活性，对有价值的1-己烯（28.7%）和1-辛烯（54.5%）的高总选择性为83.2%。
We have developed novel Cr(III) catalysts supported by asymmeticN,N-diphospholylamine ligands bearing a phenoxaphosphine group. Upon activation with MMAO-3A, the Cr(III) catalysts supported by the PNP ligands are highly active for ethylene tri-/tetramerization with considerable selectivity. The ligand substitution and oligomerization conditions are found to be essential to achieve high activity and controllable selectivity. The catalytic system with asymmetric diphospholylamine ligands exhibited higher activity than that supported by symmetric ligands. Asymmetric diphospholylamine ligand with aN-cyclohexyl group achieved the highest activity of 282.2 kg/(g Cr/h) with a high total selectivity of 83.2% toward valuable 1-hexene (28.7%) and 1-octent (54.5%) at 35 bar under 80 °C.