水杨醛亚胺共价修饰碳纳米管负载镍催化剂的合成及催化乙烯齐聚性能  

Anchoring via Covalent Binding of Salicylaldimine-Nickel Complexes in MWCNTs and Its Catalytic Performance in Ethylene Oligomerization

作　　者：李杨[1] 郭丽君 李锋[1] 高宇新 宋达 黄金[1] 王俊[1] 李翠勤[1] Yang Li;Lijun Guo;Feng Li;Yuxin Gao;Da Song;Jin Huang;Jun Wang;Cuiqin Li(Provincial Key Laboratory of Petroleum and Natural Gas Chemical Engineering,College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing Chemical Research Center of Petrochina,Daqing163714,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 [2]中国石油大庆化工研究中心,黑龙江大庆163714

出　　处：《高分子材料科学与工程》2021年第8期33-41,共9页Polymer Materials Science & Engineering

基　　金：黑龙江省自然科学基金资助项目(E2018012)。

摘　　要：以1,4-丁二胺为起始剂,4-羟基水杨醛和四水合乙酸镍为原料,经亲核加成和配位反应合成具有配位能力的水杨醛亚胺配体和含有活性羟基的水杨醛亚胺镍催化剂。通过缩合反应将水杨醛亚胺镍催化剂共价接枝到碳纳米管上,合成有机配体共价修饰碳纳米管催化剂。傅里叶变换红外光谱、核磁共振氢谱、X射线衍射等表征结果证实了合成的水杨醛亚胺配体及催化剂结构与理论结构相符。经助催化剂MAO活化后,2种催化剂均表现出良好的催化乙烯齐聚性能。条件优化实验确定了2种催化剂的较佳聚合条件,Ni用量5μmol、Al/Ni为500、反应压力0.7 MPa、反应时间30 min,均相催化剂和负载催化剂最佳反应温度分别为25℃和35℃。此条件下,均相催化剂催化乙烯齐聚活性为1.99×10^(5) g/(mol·Ni·h),齐聚产物C8和C10+选择性分别为30.38%和29.65%。负载催化剂催化乙烯齐聚活性为5.25×10^(5) g/(mol·Ni·h),齐聚产物C8和C10+选择性分别为38.14%和15.28%。与均相催化剂相比,负载催化剂具有更好的催化活性和重复利用性。A kind of salicylaldimine ligand with coordination ability and nickel catalyst with active hydroxyl groups were synthesized through nucleophilic addition reaction and coordination reaction using 1,4-butanediamine, salicylaldehyde and nickel chloride hexahydrate as material. The carbon nanotube-supported salicylaldimine nickel catalyst was synthesized by anchoring covalently to carbon nanotubes with nickel salicylaldimine catalyst. FT-IR,1H-NMR,XRD and TG have witnessed the structure of the salicylaldimine ligand and nickel salicylaldimine catalyst. Two salicylaldimine nickel catalysts all exhibit good catalytic performance for ethylene oligomerization after the activation of MAO. The optimization conditions were determined by condition optimization experiments, Ni of 5 μmol, Al/Ni of 500, reaction pressure of 0.7 MPa, reaction time of 30 min, reaction temperature of 25 ℃(homogeneous catalyst) and 35 ℃(heterogeneous catalyst), respectively. For the homogeneous catalyst, the catalytic activity is 1.99×10^(5) g/(mol·Ni·h) and the selectivities toward C8 and C10+ olefins are 30.38% and 29.65%, respectively. For the heterogeneous catalyst, the catalytic activity is 5.25×10^(5) g/(mol·Ni·h) and the selectivities toward C8 and C10+ olefins are 38.14% and 15.28%, respectively. Compared with the homogeneous catalyst, the heterogeneous catalyst has a better catalytic activity and reusability.

关 键 词：水杨醛亚胺 镍催化剂 碳纳米管 共价修饰 乙烯齐聚 

分 类 号：TQ316.3[化学工程—高聚物工业]