吡啶亚胺基酞菁镍系催化剂催化乙烯齐聚性能及其动力学研究  

Study on the Catalytic Performance and Its Kinetics of Ethylene Oligomerization Catalyzed by Pyridinimine Phthalocyanine Nickel Catalyst

作　　者：张娜[1] 王晓月 陈豫平 李翠勤[1] 陈丽铎 王俊[1] ZHANG Na;WANG Xiao-yue;CHEN Yu-ping;LI Cui-qin;CHEN Li-duo;WANG Jun(Provincial Key Laboratory of Polyolefin New Materials,College of Chemistry and Chemical Engineering Northeast Petroleum University,Daqing 163318,China;Zhejiang Petrochemical Co.,Ltd.,Zhoushan 316000,China)

机构地区：[1]东北石油大学化学化工学院黑龙江省聚烯烃新材料重点实验室,大庆163318 [2]浙江石油化工有限公司,舟山316000

出　　处：《高分子通报》2024年第5期685-693,共9页Polymer Bulletin

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

摘　　要：以四氨基镍酞菁、吡啶-2-甲醛和NiCl2·6H2O为原料,先后经过席夫碱反应和络合反应得到一种新型吡啶亚胺基酞菁配体及其镍系催化剂。合成产物的结构通过红外光谱(FTIR)、紫外(UV-Vis)、核磁共振氢谱(1H-NMR)、电感耦合等离子体质谱(ICP-MS)、同步热分析(TG-DSC)及电喷雾电离质谱(ESI-MS)等方法进行表征。对其催化乙烯齐聚性能进行考察,并研究了该反应的动力学。催化乙烯齐聚实验结果表明,当溶剂为环己烷、助催化剂为甲基铝氧烷(MAO)、催化剂用量为5μmol/L、齐聚压力为1.0 MPa、齐聚温度为35℃、Al/Ni摩尔比为500时,吡啶亚胺基酞菁镍系催化剂的活性可达8.82×10^(5)g/(mol Ni·h),丁烯和己烯的含量分别为58.22%和39.85%。对吡啶亚胺基酞菁镍系催化剂催化乙烯齐聚反应动力学方程进行拟合计算,结果表明该反应对催化剂摩尔浓度的反应级数为1.24,对齐聚压力的反应级数为0.95,当活性中心的浓度为5μmol/L、齐聚压力为1.0 MPa、齐聚温度为5~35℃时,该反应的表观活化能为71.42 kJ/mol。A kind of novel pyridinimine phthalocyanine nickel catalyst was prepared with tetraamine nickel phthalocyanine,pyridine-2-carboxaldehyde and NiCl26H,O as the raw materials through the Schiff base reaction and the complex reaction.The structures were characterized by Fourier transform infrared(FTIR),ultraviolet-visible(UV-Vis),nuclear magnetic resonance(^(1)H-NMR),inductively coupled plasma mass(ICP-MS),thermogravimetric differential scanning calorimeter(TG-DSC)and electrospray ionization mass(ESI-MS).The catalytic performance and the kinetic of ethylene oligomerization were investigated.The results showed that the catalytic activity could reach up to 8.82×10^(5)g/(mol Ni-h)-l,and the selectivity of butene and hexene were 58.22%and 39.85%,respectively,when the cyclohexane was used as solvent,the MAO was used as co-catalyst,the catalyst molar concentration was 5μmol/L,the oligomerization pressure was 1.0 MPa,the oligomerization temperature was 35℃and Al/Ni molar ratio was 500.After the fitting calculation of the kinetics equation for ethylene oligomerization catalyzed by pyridinimine phthalocyanine nickel catalyst,it could be obtained that the order of the reaction to the catalyst molar concentration was 1.24,and that to oligomerization pressure was 0.95.The apparent activation energy of the reaction was 71.42 kJ/mol when the catalyst concentration was 5μmol/L,the oligomerization pressure was 1.0 MPa,and the oligomerization temperature was 5-35℃.

关 键 词：酞菁 吡啶亚胺配体 催化剂 乙烯齐聚 动力学 

分 类 号：O643.36[理学—物理化学]