双膦胺配体氮原子上取代基的空间和电子效应对于乙烯四聚催化体系的影响  

Steric and Electronic Effect of Substituents Attached to Nitrogen Atoms of Bis(phosphine)amine Ligand on Catalyst System for Ethylene Tetramerazation

作　　者：宁英男[1] 牛博[1] 姜涛[1] 丁万友[1] 殷喜丰[1] 

机构地区：[1]大庆石油学院化学化工学院,黑龙江大庆163318

出　　处：《化工生产与技术》2009年第6期19-22,共4页Chemical Production and Technology

摘　　要：在乙酰丙酮铬、甲基铝氧烷(MAO)、配体三元催化体系中,以乙烯为原料在高压下齐聚生成1-辛烯,主要考察N原子上取代基不同的PNP配体对催化剂活性及1-辛烯选择性的影响。结果表明,苯环取代基为3,5-二甲基的配体效果较为理想,其活性达到4990kg/(mol·h),对1-辛烯选择性为72.31%。PNP配体中苯环取代基上间、对位给电子基团有助于提高催化活性和1-辛烯选择性,而空间位阻较大的基团和吸电子基团则不利于催化反应。1-Octylene was synthesized via tetramerization of ethylene at the presence of a catalyst system consisted of chromium acaet as primary catalyst, methylaluminoxane (MAO) as cocatalyst, bis(phosphine)amine (PNP) as ligand under high pressure. The effects of different PNP ligands on catalyst activity and selectivity to 1-octene were investigated. The results showed that ligands with 3,5- dimethylmatches attached on benzene ring are more effective. Activity of catalyst with PNP ligand above is up to 4 990 kg/(mol·h) and selectivity of 1-octene can reach 72.31%. Electron-donating groups on m-position and o-position attached on benzene ring of PNP ligand can improve catalyst activity and selectivity to 1-octene. Substituents with large steric hindrance and electron withdrawing groups are detrimental to the catalytic reaction.

关 键 词：乙烯四聚 1-辛烯 催化剂 活性 PNP配体 

分 类 号：O643.32[理学—物理化学]