二苯亚甲基桥联吡啶亚胺双中心Ni催化剂的制备及催化乙烯齐聚  

Preparation and catalysis of ethyleneoligomerization by diphenyl-methylene-bridging pyridine-imide two-center Ni catalyst

作　　者：王俊[1] 付兴宇 陈丽铎 张娜[1] WANG Jun;FU Xingyu;CHEN Liduo;ZHANG Na(College of Chemistry and Chemical Engineering,Northeast Petroleum University,Provincial Key Laboratory of Petroleum and Natural Gas Chemical Industry,Daqing 163318,China)

机构地区：[1]东北石油大学化学化工学院石油与天然气化工省重点实验室,黑龙江大庆163318

出　　处：《化工科技》2024年第4期38-43,共6页Science & Technology in Chemical Industry

基　　金：黑龙江省重点研发计划项目(JD22A026);黑龙江省博士后科研启动基金项目(16220029)。

摘　　要：以4,4′-二氨基二苯甲烷、吡啶-2-甲醛和六水合氯化镍为原料制备用于乙烯齐聚的双中心Ni催化剂,利用红外光谱(FTIR)、紫外光谱(UV-vis)、核磁共振氢谱(1H NMR)及电喷雾电离质谱(ESI-MS)等对配体和催化剂结构进行分析,并通过乙烯齐聚实验对催化剂催化性能进行评价。结果表明,聚合反应条件对二苯亚甲基桥联双中心Ni催化剂催化乙烯齐聚性能具有较大影响,以环己烷为溶剂、改性甲基铝氧烷(MMAO)为助催化剂,t=25℃、n(Al)∶n(Ni)=1000、p(乙烯)=0.5 MPa、n(主催化剂)=3μmol、t=45 min,二苯亚甲基桥联双中心Ni催化剂催化活性最高为7.61×10^(4) g/(mol Ni·h),丁烯选择性为72.58%。此外,对二苯亚甲基桥联吡啶亚胺双中心Ni催化剂催化乙烯齐聚机理进行了推断。A two-center Ni catalyst for ethylene oligomerization was prepared using 4,4'-diaminodiphenylmethane,pyridine-2-formaldehyde and nickel chloride hexahydrate as raw materials.The structures of the ligands and catalysts were analyzed by infrared spectroscopy(FTIR),ultraviolet spectroscopy(UV-vis),hydrogen nuclear magnetic resonance spectroscopy(1H NMR)and electrospray ionization mass spectrometry(ESI-MS),and the catalytic performance was evaluated by ethylene oligomerization experiment.The results showed that polymerization conditions and catalyst structure have great influence on the performance of ethylene oligomerization catalyzed by two-center Ni catalyst.Using cyclohexane as solvent and modified methylaluminoxane(MMAO)as cocatalyst,the catalytic activity of the methyl-substituted diphenyl methylene bribed bicentral Ni catalyst was the highest when the reaction temperature was 25℃,n(Al)∶n(Ni)=1000,the ethylene pressure was 0.5 MPa,the amount of the main catalyst was 3μmol and the reaction time was 45 min.The maximum value was 7.61×10^(4) g/(mol Ni·h)and the selectivity of butene was 72.58%.In addition,the mechanism of ethylene oligomerization catalyzed by diphenylmethylene-brided pyridinimide two-center Ni catalyst was deduced.

关 键 词：双中心 乙烯齐聚 镍系催化剂 催化活性 催化机理 

分 类 号：TQ325.12[化学工程—合成树脂塑料工业]