含氨高温液态水中四氟邻苯二甲酸脱羧反应动力学.PDF

含氨高温液态水中四氟邻苯二甲酸脱羧 反应动力学 莫 静，傅 杰，吕秀阳 （浙江大学化学工程与生物工程学系生物质化工教育部重点实验室，杭州 310027 ） 摘要：2,3,4,5- 四氟苯甲酸是一种重要的药物合成中间体，本文以含氨高温液态水为反应介质 开发了以四氟邻苯二甲酸为原料脱羧绿色制备 2,3,4,5- 四氟苯甲酸的方法，并系统地研究了该 脱羧反应动力学。在考察了不同氨水浓度对四氟邻苯二甲酸脱羧反应的影响后，系统地研究 了150~180℃温度范围内含氨高温液态水中四氟邻苯二甲酸的脱羧反应动力学。结果表明，四 氟邻苯二甲酸在高温液态水中能顺利脱羧转化成 2,3,4,5- 四氟苯甲酸，高温液态水中的氨水浓 度和反应温度对四氟邻苯二甲酸的脱羧反应速率有显著的影响，反应体系的初始pH 值和脱羧 反应速率常数之间有着重要的联系。采用一级反应动力学方程对不同温度下的动力学数据进 行拟合，并用阿伦尼乌斯方程关联得到了四氟邻苯二甲酸脱羧反应的表观活化能为190kJ/mol。 关键词：含氨高温液态水；脱羧；2,3,4,5- 四氟苯甲酸；反应动力学 Decarboxylation Kinetics of Tetrafluorophthalic Acid in NH - 3 Enriched High Temperature Liquid Water Jing Mo, Jie Fu, Xiuyang Lu* (Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027) Abstract: 2,3,4,5-Tetrafluorobenzoic acid is an important pharmaceutical intermediate. In this article, we developed a green technology of tetrafluorophthalic acid to 2,3,4,5-Tetrafluorobenzoic acid in NH3-enriched high temperature liquid water and the decarboxylation kinetics of tetrafluorophthalic acid was studied. On the basis of investigating the effect of different ammonia solution volume fraction on the decarboxylation of tetrafluorophthalic acid, the decarboxylation kinetics of tetrafluorophthalic acid was systematically studied in NH3-enriched high temperature liquid water in the temperature range from 150 ℃ to 180 ℃. The results showed that the technical feasibility of tetrafluorophthalic acid to 2,3,4,5-Tetrafluorobenzoic acid in high temperature liquid water and the ammonia solution volume fraction and reaction temperature play an important role in decarboxylation of tetrafluorophthalic acid, and the initial pH value of