1-癸烯齐聚反应动力学研究

Kinetics of 1-decene oligomerization

构建了基于AlCl3催化剂体系的1-癸烯齐聚反应的反应网络及动力学模型,利用过渡态搜索的方法计算各齐聚反应的速率常数,研究不同温度时的聚合产物分布,并通过实验结果验证模型预测效果。计算结果表明,1-癸烯齐聚反应过程中,二聚体与二聚体碳正离子间的四聚反应活化能最低,三聚体与二聚体碳正离子间的五聚反应活化能最高;升高反应温度,产物中低聚合度产物含量增加,且有利于合成更低黏度等级的聚α-烯烃基合成润滑油基础油产品;反应温度为60℃时,二聚体、三聚体、四聚体含量模拟计算值与实验结果的相对偏差分别为6.13%,1.09%,1.24%,五聚体含量的相对偏差最大,为12.32%;反应温度为80℃时,三聚体、四聚体、五聚体含量模拟计算值与实验结果的相对偏差分别为4.16%,2.77%,4.46%,二聚体含量的相对偏差最大,为8.26%。

The reaction network and kinetics model for 1-decene oligomerization employing AlCl_(3) catalyst are established. Reaction rate constants are calculated via the transition state search method. Product distributions at different temperatures were examined and the prediction results were verified by experimental findings. It is indicated that the tetramerization reaction between dimer and dimer carbonium ion has the lowest activation energy while the pentamerization reaction between trimer and dimer carbonium ion exhibits the highest activation energy. With an increase of reaction temperature,the contents of oligomers with low degree of oligomerization in product increase. High reaction temperatures facilitate the synthesis of lower-viscosity poly-α-olefin synthetic lubricant base oil products. In comparison with the experimental results at reaction temperature of 60 ℃,the prediction results have the relative deviations of contents of dimer,trimer,and tetramer are 6.13%,1.09%,and 1.24% respectively,and the predicated pentamer content shows the largest deviation of 12.32%. As for the reaction temperature of 80 ℃,the corresponding predication deviations for trimer,tetramer,and pentamer are 4.16%,2.77%,and 4.46% respectively,while the content of dimer gives the largest deviation of 8.26%.