文献类型：期刊文献

中文题名：含桥联多膦配体的双核Cr(Ⅲ)乙烯齐聚催化剂

英文题名：Ethylene oligomerization catalyzed by binuclear Cr catalyst based on a bridged phosphine ligand

作者：郑明芳[1];吴红飞[1];马旭峰[2];张军[2]

机构：[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

年份：2018

卷号：47

期号：9

起止页码：924

中文期刊名：石油化工

外文期刊名：Petrochemical Technology

收录：CSTPCD;;Scopus;北大核心:【北大核心2017】；CSCD:【CSCD2017_2018】；

语种：中文

中文关键词：乙烯齐聚;双核铬催化剂;多膦配体;改性甲基铝氧烷

外文关键词：ethylene oligomerization;binuclear chromium catalyst;multiphosphine ligand;modifi ed methylaluminoxane

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%.