含桥联多膦配体的双核Cr(Ⅲ)乙烯齐聚催化剂  

Ethylene oligomerization catalyzed by binuclear Cr catalyst based on a bridged phosphine ligand

作　　者：郑明芳[1] 吴红飞 马旭峰 张军[2] Zheng Mingfang;Wu Hongfei;Ma Xufeng;Zhang Jun(Sinopec Yanshan Branch of Beijing Research Institute of Chemical Industry,Beijing 102500,China;School of Chemistry&Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]中国石化北京北化院燕山分院,北京102500 [2]华东理工大学化学与分子工程学院,上海200237

出　　处：《石油化工》2018年第9期924-928,共5页Petrochemical Technology

摘　　要：合成了1,3-二(1,2-二(二苯基膦基)乙烯基)苯(配体Ⅱ)。将该配体与铬源在改性甲基铝氧烷(MMAO-3A)的活化下,原位组成配体Ⅱ/Cr(Ⅲ)/MMAO-3A催化体系,用于乙烯齐聚。利用1H NMR,^(13)C NMR,^(31)P NMR,HRMS(EI)等方法对配体进行了表征,并考察了反应条件对催化体系聚合性能的影响。实验结果表明,以Cr(acac)_3为铬源的聚合活性和选择性高于以CrCl_3(THF)_3为铬源。适宜的聚合条件为:Cr(acac)_3用量3.0μmol、配体Ⅱ用量1.5μmol、温度40℃、甲基环己烷用量30 mL、n(Al)∶n(Cr)=600、乙烯压力3.5 MPa。在该条件下,催化活性可达314 kg/(g·h),1-己烯和1-辛烯的总选择性达到了77.6%。A bridged multiphosphine ligandⅡcontaining two backbone-unsaturated diphosphine moieties was synthesized and was fully characterized by the means of 1H NMR,13C NMR,31P NMR,HRMS(EI).The ligandⅡ/Cr(Ⅲ)/MMAO-3A catalyst system was prepared through the in-situ complexation reaction,followed by activation with modified methylal uminoxane(MMAO-3A).The performance of the catalytic system for ethylene oligomerization was investigated.When Cr(acac)3 was used as the chromium source,the catalytic system achieved better catalytic activity and selectivity.When running the ethylene oligomerization reaction at 40℃,3.5 MPa,n(Al)∶n(Cr)600,the catalytic activity reached 314 kg/(g·h),resulting in the highest total selectivity of 1-hexene and 1-octene 77.6%.

关 键 词：乙烯齐聚 双核铬催化剂 多膦配体 改性甲基铝氧烷 

分 类 号：TQ426.8[化学工程]