PCSiN/Ni(Ⅱ)配合物/一氯二乙基铝催化乙烯二聚  

Ethylene dimerization catalyzed by PCSiN/Ni(Ⅱ)complex/diethylaluminum chloride

作　　者：邵若星 张钰 李俊辰 姜涛 SHAO Ruoxing;ZHANG Yu;LI Junchen;JIANG Tao(College of Chemical Engineering and Materials Science,Tianjin University of Science&Technology,Tianjin 300457,China)

机构地区：[1]天津科技大学化工与材料学院,天津300457

出　　处：《石油化工》2025年第3期325-332,共8页Petrochemical Technology

基　　金：国家自然科学基金项目(22071178);中国石油科技计划项目(2020B2512)。

摘　　要：合成了系列PCSiN型配体,将它们与溴化镍(Ⅱ)络合得到相应的镍配合物,利用GC,NMR,FTIR,UV-Vis等方法对配合物结构进行了表征。考察了配合物催化乙烯二聚时,反应条件对反应活性和选择性的影响,并通过密度泛函理论验证了实验结果。实验结果表明,硅原子连接两个甲基和一个四氢吡咯基官能团的配合物Ni3的包埋体积分数最小,因而表现出较高的活性。配合物Ni3催化乙烯二聚的适宜工艺条件为:反应温度30℃、一氯二乙基铝为助催化剂、n(Al)∶n(Ni)=1000∶1、催化剂用量0.6μmol、反应时间15 min。在该条件下,Ni3的催化活性可达24.31×10^(6) g/(mol·h),丁烯选择性为85.50%,其中1-丁烯选择性为65.56%。乙烯二聚机理可能为金属环化机理。A series of PCSiN-type ligands were synthesized and complexed with nickel(Ⅱ)bromide to obtain the corresponding nickel complexes.The structure of the complexes was characterized with GC,NMR,FTIR,and UV-Vis.The effects of reaction conditions on the reactivity and selectivity of ethylene dimerization catalyzed by the complexes were investigated.The experimental results were verified by density functional theory.The results show that the complex Ni3,where a silicon atom is bonded to two methyl groups and one tetrahydropyrrole functional group,has the smallest embedding volume fraction and therefore exhibits higher activity.The optimal reaction conditions for ethylene dimerization catalyzed by the complex Ni3 are as follows:reaction temperature of 30℃,diethylaluminum chloride as co-catalyst,n(Al)∶n(Ni)=1000∶1,catalyst amount of 0.6μmol,and reaction time of 15 min.Under these conditions,the catalytic activity of Ni3 reaches 24.31×10^(6) g/(mol·h),with a butene selectivity of 85.50%,of which the selectivity of 1-butene is 65.56%.The mechanism of ethylene dimerization may be a metal-catalyzed cyclization mechanism.

关 键 词：乙烯二聚 PCSiN型配体 1-丁烯 镍系催化剂 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]