| 含希土乙酰基丙酮配合物的均相催化体系催化丙烯齐聚反应的研究 Ⅰ.不同希土催化性能的比较和反应条件的影响 |
| OLIGOMERIZATION OF PROPYLENE CATALYZED BY HOMOGENEOUS SYSTEM CONTAINING RARE EARTH COMPLEXES WITH ACETYLACETONE Ⅰ. CATALYTIC ABILITY OF DIFFERENT RARE EARTH ELEMENTS AND INFLUENCE OF REACTION CONDITIONS |
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| 摘要: 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PPh3或Et3Al2Cl3用量的影响很大,在最佳P/RE或Al2/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). |
| 关键词: 希土配合物 倍半氯乙基铝 三苯基铝 均相催化 齐聚 丙烯 |
| 基金项目: 中国科学院科学基金资助的课题 |
| Abstract: The catalytic behavior of the homogeneous systems of ten rare earth(La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Yb)acetylacetonates with ethylaluminum sesquichloride and triphenylphosphine toward the oligo-merization of propylene has been studied. The selectivity of dimers is around 90% and the linearity of the dimers is around 32% in all cases. The catalyst activity of these three-component systems is greatly affected by the relative amounts of PPh3 or Et3Alsub>2Cl3 to the rare earth complex. At the optimum P/RE or Al2/RE the catalyst activity exhibits a peak value. The optimum Al2/RE increases with increasing reaction temperature, but the activity and selectivity of dimerization drop drastically when the temperature is raised to 100℃.The catalyst activity and conversion of propylene to dimers vary with the duration of reaction time. The conversion usually reaches its maximum after 1.5h. The results of oligo-merization of propylene using nine rare earth acetylacetonates were compared. It is found that the dimerization activity changes periodically with the atomic number of the rare earth elements. The highest activity in the former and the later periods appears at Pr and Dy respectively, and at Sm and Ho the activity is minimum. At 60℃, 1.5h, Pr/RE=30, Dy/ RE=25 and P/RE=3.7, the dimerization activity of Pr and Dy is 1044 and 1261 mol C3H6/(mol RE·h)respectively. |
| Keywords: rare earth complex ethylaluminum sesquichloride triphenylphosphine homogeneous catalysis oligomerization propylene |
| 投稿时间：1986-06-19 |
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| 吕俊民,张纪梅.含希土乙酰基丙酮配合物的均相催化体系催化丙烯齐聚反应的研究 Ⅰ.不同希土催化性能的比较和反应条件的影响[J].无机化学学报,1987,3(3):50-57. |
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