双膦镍络合物/EADC催化乙烯齐聚与Friedel-Crafts烷基化的串联反应  

Ethylene Oligomerization and Friedel-Crafts Alkylation Tandem Action Catalyzed by Diphosphine Nickel Complex/EADC

作　　者：孟雪姣 张乐[1] 陈延辉[1] 姜涛[1] MENG Xuejiao ZHANG Le CHEN Yanhui JIANG Tao(College of Chemical Engineering and Material Science , Tianjin University of Science ＆ Technology , Tianjin 300457, Chin)

机构地区：[1]天津科技大学化工与材料学院,天津300457

出　　处：《石油学报（石油加工）》2017年第3期431-438,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：天津市应用基础与前沿技术研究计划重点资助项目(16JCZDJC31600);天津市应用基础与前沿技术研究计划一般项目(14JCYBJC20800)基金资助

摘　　要：合成并表征了二苯基膦甲基-二苯基膦基-二甲基硅烷络合物(C1);考察了反应温度、nAl/nNi及溶剂的种类等对C1/EtAlCl2催化乙烯齐聚行为的影响。结果表明,以二氯乙基铝(EADC)为助催化剂、甲基环己烷为溶剂时,C1/EADC催化乙烯齐聚的活性可达4.32×10~6 g/(molNi·h),产物为C4和C6馏分,其中C_4馏分中1-丁烯的选择性大于94%;以甲苯为溶剂时,C_1/EADC催化乙烯齐聚得到的短链烯烃与甲苯发生原位Friedel-Crafts烷基化反应,产物为多取代烷基甲苯;EADC在该催化体系中起到了双功能的作用,一是齐聚反应的助催化剂,二是烷基化反应的催化剂。In this work, bis （diphenyl phosphine） methyl dimethyl silane （L1） and its nickel （II） halide complexes L1/NiBr2 （C1）, were synthesized and characterized. The influence of reaction temperature, nAI/nNi and various solvents on ethylene oligomerization were studied. Among these catalytic systems, Cl/methyl cyclohexane/EtAlCl2 （EADC） was proved to be highly active with the activity up to 4. 32 ×10^6g/（molNi ·h） , while the product consisted of mainly α-olefins （C4 , C6 ） without polymers. The selectivity of 1-butylene in C4 fractions was more than 94%. It was also found that oligomerization of ethylene gave C4 and C6 alkenes, followed by subsequent situ Friedel- Crafts alkylation of the toluene solvent to alkylated toluene products using C1 catalyst, in which the obtained α-olefins were then converted into the corresponding Friedel-Crafts alkylated-toluene products. EADC in the catalytic systems played an important role to serve double functions, one is the cocatalyst of oligomerization, and the other is the catalyst for alkylation reaction.

关 键 词：镍络合物 EADC 乙烯齐聚 Friedel-Crafts烷基化 烷基苯 

分 类 号：O632.12[理学—高分子化学]