吡啶/吡咯亚胺型钴、镍配合物合成及其催化甲基丙烯酸甲酯聚合研究  

Synthesis of Pyridine/Pyrrolimidine Cobalt/Nickel Complexes and Methyl Methacrylate Polymerization Catalyzed by Them

作　　者：朱晓艳 檀银银 郑成宇 张琦[1] 孙浩天 苏碧云[1] ZHU Xiao-yan;TAN Yin-yin;ZHENG Cheng-yu;ZHANG Qi;SUN Hao-tian;SU Bi-yun(Shaanxi University Engineering Research Center of Oil and Gas Field Chemistry,Xi'an Shiyou University,Xi'an 710065,China)

机构地区：[1]西安石油大学油气田化学陕西省高校工程研究中心,西安710065

出　　处：《高分子通报》2024年第4期491-499,共9页Polymer Bulletin

基　　金：西安石油大学青年科技创新团队(项目号YCS222213090)。

摘　　要：以冰醋酸/微波辐射催化2-乙酰基吡啶/吡咯与对苯二胺、卡巴肼发生Schiff碱缩合反应得到系列配体L1~L4,在甲醇/四氢呋喃中进一步与钴/镍氯化物反应获得配合物1~8。用元素分析、核磁氢谱、红外、紫外光谱和X-射线单晶衍射等手段对产物进行全面结构表征发现,配体L1~L3为二胺桥连的双亚胺吡啶/吡咯结构,L4为单亚胺吡咯结构,配合物1~6均为双核配合物,而7、8为单核配合物。配体合成实验中发现L1的产率最高,达到89.8%,说明苯胺与直链胺相比亲核性更强,更有利于产物的生成。通过系统研究配合物1~8对甲基丙烯酸甲酯(MMA)聚合催化行为与催化剂结构、聚合反应条件的关系发现,当聚合时间为6 h,温度为90℃,单体与催化剂比例n(M)/n(Ni)为3000:1,主催剂和引发剂比例n(Ni)/n(AIBN)为2:1时,由2-乙酰基吡啶与对苯二胺缩合形成的双亚胺配体Ni(Ⅱ)配合物的催化活性最高,可达到4.3281×10^(4)g·mol^(-1)·h^(-1)。A series of ligands L1–L4 were synthesized by Schiff base condensation reaction of 2-acetylpyridine/pyrrole with p-phenylenediamine and carbazide catalyzed by glacial acetic acid/microwave radiation.Complexes 1–8 were further synthesized by reaction with cobalt/nickel chloride in methanol/tetrahydrofuran.The comprehensive structural characterization of the product was carried out using elemental analysis,nuclear magnetic resonance spectroscopy,infrared spectroscopy,ultraviolet spectroscopy,and X-ray single-crystal diffraction.It was found that the ligands L1–L3 has a diamine bridged double imine pyridine/pyrrole structure,L4 has a single imine pyrrole structure,and complexes 1–6 are all binuclear complexes,while complexes 7 and 8 are mononuclear.In the ligand synthesis experiment,it was found that the yield of L1 was the highest,reaching 89.8%,indicating that aniline has stronger nucleophilicity compared to linear amines and is more conducive to the generation of products.Through a systematic study of the relationship between the catalytic behavior of complexes 1–8 for the polymerization of methyl methacrylate(MMA)and the catalyst structure and polymerization reaction conditions,it was found that when the polymerization time was 6 h,the temperature was 90℃,the ratio of monomer to catalyst n(M)/n(Ni)was 3000:1,and the ratio of main catalyst to initiator n(Ni)/n(AIBN)was 2:1,the catalytic activity of the double imine ligand Ni(II)complex formed by the condensation of 2-acetylpyridine and p-phenylenediamine was the highest,reaching 4.3281×10^(4)g·mol^(-1)·h^(-1).

关 键 词：吡咯/吡啶 双胺 钴/镍配合物 聚合催化 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学] TQ316.3[化学工程—高聚物工业]