【摘要】 <正>直链低碳α-烯烃（指十碳以下的正构α-烯烃）是重要的基本化工原料,广泛用于合成润滑油、增塑剂、精细化工产品及共聚单体.以过渡金属络合物催化乙烯齐聚获得直链α-烯烃被认为是当前最先进的方法.镍络合物体系催化乙烯齐聚得到α-烯烃的SHOP法是Ⅷ族金属络合物催化反应的代表.它是以得到高碳α-烯烃为目的.以ⅣB族金属络合物为基础的体系主要催化烯烃高聚,催化齐聚的研究工作尚少.近年来曾有锆酸酯和烷基铝催化乙烯齐聚的报导,其C₄-C₈烯烃的收率最高可达92%.本文将报导用简单易得的锆盐和烷基铝为基础组成的体系催化乙烯齐聚的结果,及对此类催化体系的失活问题进行探讨.更多还原

【Abstract】 In this paper is presented the preparation of linear α-olefins by catalytic homogeneous oligomerization of ethylene under lower pressure. A binary system composed of ZrCl4 and ( C2H6 ) 2A1C1 is an active catalyst at Al/Zr>10, with a maximum at Al/Zr = 30. The catalyst activity is reduced sharply by increasing the ageing temperature.ZrCl4- ( C2H5 ) 3Al2Cl3 system can also catalyse oligomerization of ethylene with a poor catalytic activity, but its catalytic behavior can be improved by adding small amount of n-C4H9ONa. IR spectrum shows that Zr-O bond exists in this ternary catalyst system.The catalyst activity is reduced on prolonged oligomerization for the ZrCl4- ( C2H6 ) 2A1C1 system. ESR spectrum of this binary system shows that the Zr3+ concertration increases ( i.e. the Zr4+ concentration decreases) at the beginning of the reaction. It thus appears that: (1 ) Zr4+ complexes are active catalysts for the oligomerization of ethylene. ( 2 ) The reduced activity of these catalytic systems may be correlated to the partial reduction of Zr4+ . ( 3 ) n-C4H9ONa can delay the reduction of Zr4+.更多还原