摘要/Abstract

以5-氨基邻甲酚与二苯基氯化膦为原料，通过取代反应合成了一种含有PNP和P-O结构的膦配体并确定了其结构.通过与Cr（acac）₃原位生成以及与CrCl₃（THF）₃预制的方法制成配合物作为主催化剂，以甲基铝氧烷（MAO）为助催化剂，形成催化体系用于催化乙烯齐聚反应，考察了溶剂种类、反应温度、反应压力及Al/Cr摩尔比对该催化剂的活性和选择性的影响，并与原位生成的邻位和对位氨基酚类膦配体催化体系催化乙烯齐聚反应效果进行了对比.试验结果表明，以环己烷为溶剂，MAO为助催化剂，当反应温度为50℃、反应压力为2.5 MPa、Al/Cr摩尔比为700的条件下，该催化剂的活性最高达5.91×10⁶ g/（mol·Cr·h），液相产物中1-辛烯选择性高达72.94%，1-己烯和1-辛烯总的选择性为82.11%.
关键词: 5-氨基邻甲酚, 膦配体, 铬催化剂, 乙烯齐聚, 活性, 选择性
A phosphorus ligand containing PNP and P-O structure was synthesized by substitution reaction of 5-amino-o-cresol with chlorodiphenylphosphine and its structure was conformed. Its in situ prepared complex with Cr(acac)₃ and preformed complex with CrCl₃(THF)₃ were used as main catalysts in catalyzing ethylene oligomerization, accompanied with methylaluminoxane (MAO) as cocatalyst. The effects of solvent, temperature, pressure and Al/Cr molar ratio on the activity and selectivity of the catalyst were investigated and compared with the in situ formation of 2-aminophenol and 4-aminophenol phosphine ligands catalytic system of catalyzing ethylene oligomerization effect. The experimental results showed that the activity reached 5.91×10⁶ g/(mol·Cr·h), when the reaction was carried at 50℃ with reaction pressure of 2.5 MPa and the Al/Cr molar ratio of 700. The selectivity of 1-octene was 72.94% and the total selectivity of 1-hexene and 1-octene was 82.11%.
Key words: 5-amino-o-cresol, phosphorus ligand, chromium catalyst, ethylene oligomerization, activity, selectivity


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