苯胺基亚胺镍催化剂的合成及催化环烯烃和-烯烃的均聚...04017.docVIP

苯胺基亚胺镍催化剂的合成及催化环烯烃和α-烯烃的均聚和共聚研究 陈 言 伍 青* (中山大学化学与化工学院，广州，510275） 摘要 本文介绍了苯胺基亚胺镍催化剂[{(C6H3Me2-2,6)N=CH-5-NO2-C6H3N(C6H3Me2-2,6)}NiBr]的合成，研究了其在助催化剂甲基铝氧烷（MAO）的作用下对降冰片烯、乙烯的均聚以及对降冰片烯和乙烯的共聚的催化性能。考察了不同反应温度和Al/Ni比对降冰片烯聚合反应的影响。结果表明，随着温度的升高，催化活性是先提高后下降的。随着Al/Ni比的增加，催化活性逐渐增加，但分子量逐渐降低。硝基的引入改善了电子效应，催化乙烯的聚合得到了高分子量的聚乙烯。考察了不同温度和Al/Ni比对反应的影响。考察了不同降冰片烯的加入量对降冰片烯和乙烯共聚反应的影响，并对其中一个聚合产物做了13C NMR研究。结果表明，催化体系催化降冰片烯和乙烯的共聚效果不理想，共聚物中降冰片烯含量高。 关键词： 苯胺基亚胺镍配合物，降冰片烯，乙烯，均聚，共聚 Abstract The anilido-imino nickel complex [{(C6H3Me2-2,6)N=CH-5-NO2-C6H3N (C6H3Me2-2,6)}NiBr] was first synthesized. This complex [{(C6H3Me2-2,6)N=CH-5-NO2-C6H3N (C6H3Me2-2,6)}NiBr] exhibited high polymerization activities toward norbornene and ethylene activated with methylaluminoxane(MAO). The copolymerization of norbornene and ethylene were also investigated in detail. Influence of the polymerization temperature and Al/Ni ratio on the polymerization of the norbornene was studied. The results indicated that the polymerization activity increased and then decreased with the temperature increase. With Al/Ni ratio increase, polymerization activity increased, but molecular weights of the obtained polynorbornene decrease. The polyethylene with high molecular weights was obtained because of the introduction of the electron-withdrawing nitro group. The influence of the polymerization temperature and Al/Ni ratio were investigated. The copolymerization of norbornene and ethylene catalyzed by complex [{(C6H3Me2-2,6)N=CH-5-NO2-C6H3N (C6H3Me2-2,6)}NiBr]/MAO was also studied. Influence of different norbornene quantity feed ratio was investigated. 13C NMR of copolymer shows that the content of norbornene in the copolymer is high. Key words: anilido-imino nickel complexes, norbornene, ethylene, polymerization and copolymerization 综合以前的文献报道以及我们实验小组的研究成果，水杨醛亚胺Ni配合物具有很好的共轭效应，并且容易修饰，缺点是邻位引入大位阻的取代基难度大。而β-二亚胺Ni配合物则显示出了更大的位阻效应和好的共轭效应，但配合物稳定性差。综合这两者的优点，我们实验室的高海洋师兄首次设计、合成出苯胺基亚胺镍的系列配合物。本论文则选取了苯胺基亚胺镍系列配合物中的一种进行研究，考察其催化性能。 根据文献报道，?-二亚胺镍催化体系