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研究了十个希土元素(La、Ce、Pr、Nd、Sm、Gd、Dy,Ho、Er、Yb)的乙酰基丙酮配合物与三苯基膦、倍半氯乙基铝组成的均相体系对丙烯齐聚反应的催化性能,齐聚反应以二聚为主,二聚选择性一般在90％左右,二聚物的线性率均在32％左右。这三元体系的催化活性受PPh_3或Et_3Al_2Cl_3用量的影响很大,在最佳P/RE或Al_2/RE时,活性出现峰值。还考察了不同反应温度和不同反应时间下齐聚反应的结果。比较不同希土的乙酰基丙酮配合物,催化活性随希土元素的原子序数呈周期性的变化;前后两个周期的活性最高点分别出现在Pr和Dy处,最低点在Sm和Ho处。当反应条件为60℃,1.5h,Pr/RE=30,Dy/RE=25,P/RE=3.7时,Pr和Dy的二聚活性分别为1004和1261mol丙烯/(molRE·h)。
The phase composition of acetylacetonate complexes with triphenylphosphine and sesquichloroethyl aluminum in ten rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb) The catalytic performance of the system on the oligomerization of propylene, oligomerization reaction dimerization, dimerization selectivity is generally about 90%, the linearity of the dimer are about 32%. The catalytic activity of this ternary system is greatly affected by the dosage of PPh_3 or Et_3Al_2Cl_3. At the optimum P / RE or Al_2 / RE, the activity peaks. The results of oligomerization at different reaction temperatures and different reaction times were also investigated. Compared with the different acetylacetone complexes, the catalytic activity changes cyclically with the atomic number of the rare earth elements. The highest activity peaks in the two cycles appear at Pr and Dy and the lowest point at Sm and Ho, respectively. When the reaction conditions were 60 ℃, 1.5h, Pr / RE = 30, Dy / RE = 25 and P / RE = 3.7, the dimerization activities of Pr and Dy were 1004 and 1261 mol propylene / molRE · h, respectively.