邻苯二甲酸酐与烯丙醇酯化反应动力学

摘要

为给邻苯二甲酸二烯丙酯的中试放大乃至工业生产提供必要的动力学数据支持,在前期工艺探讨与优化工作基础之上,文中较为系统地研究了无催化剂和以对甲苯磺酸为催化剂条件下,邻苯二甲酸酐与烯丙醇合成邻苯二甲酸二烯丙酯的反应动力学.经模型简化,分别得出了第2步关键反应在这2种反应条件下的反应级数、反应速率常数、表观活化能和指前因子.结果表明:无论是在无催化剂条件还是以对甲苯磺酸为催化剂条件下,第2步酯化反应速率对单酯酸和烯丙醇的反应级数是相同的,分别为2和1.此外,对甲苯磺酸催化效果明显,可使反应表观活化能和指前因子分别由无催化剂条件下的65.13 kJ/mol和8.47×105 L2/(mol2·min)降至35.24 kJ/mol和4.46×102 L2/(mol2 · min),同时反应速率常数由0.001 9 L2/(mol2·min)升高到0.009 4 L2/(mol2·min) (393 K温度基准),提升了近4倍.%Abstract;To provide necessary kinetics data for the pilot amplification and even industrial production of diallyl phthalate, the reaction kinetics of the esterification of phthalic anhydride and allyl alcohol without catalyst and with p-toluenesulfonic acid as catalyst was systematically studied on the basis of previous technology discussion and optimization. By using simplified model, reaction order, reaction rate constant, apparent activation energy and apparent pre-exponential factor for the second key step of the reaction in both conditions were obtained. The results show that the reaction orders to monoallyl phthalate and allyl alcohol in both reaction conditions are respectively 2 and 1. In addition, the effect of p-toluenesulfonic acid is remarkable. The apparent activation energy and apparent pre-exponential factor is reduced from 65. 13 kJ/mol and 8.47 × 105 L2/(molz · min) to 35. 24 kJ/mol and 4.46 × 102 L2/(mol2 · min). Its reaction rate constant at 393 K increases nearly four times from 0. 001 9 L2/(mol2 · min) to0.009 4 L2/(mol2 · min).