环丁烷四甲酸二酐的制备研究

Study on preparation of cyclobutanetetracarboxylic dianhydride

以反丁烯二酸二甲酯为原料,去离子水为溶剂,在紫外光照射下,合成环丁烷四羧酸四甲酯,水解后得到环丁烷四羧酸,再经过脱水,得到环丁烷四甲酸二酐。环加成反应、水解反应及脱水反应的最佳反应条件为:反丁烯二酸二甲酯与去离子水的质量比为1∶5,反应时间20 h,反应温度10℃时,环丁烷四羧酸四甲酯的收率可达96.5%;环丁烷四羧酸四甲酯与盐酸溶液的质量比为1∶3,反应时间20 h,反应温度80℃时,环丁烷四羧酸的收率可达80%;环丁烷四羧酸和醋酸酐的质量比为1∶6,反应时间25 h,反应温度140℃时,产品环丁烷四甲酸二酐的收率可达84.0%。

Under the condition of UV, tetramethyl cyclobutane tetracarboxylate is synthesized by using dimethyl fumarate as the raw material and water as the solvent. Cyclobutanetetracarboxylic acid is obtained after hydrolysis of tetramethyl cyclobutane tetracarboxylate, and then the cyclobutanetetracarboxylic dian- hydride is obtained after dehydration. The optimal reaction condition for the cycloaddition reaction, hydrol- ysis reaction and dehydration reaction were as follows ： the yield of tetramethyl cyclobutane tetracarboxylate is up to 96.5% under the condition as the proportion of dimethyl fumarate to water 1：5 ,the reaction time 20 h and the reaction temperature 10 ℃ ;the yield of cyclobutanetetracarboxylic acid is up to 80% under the condition as the proportion of tetramethyl cyclobutane tetracarboxylate to hydrochloric acid 1 ： 3, the re- action time 20 h and the reaction temperature 80 ℃ ; the yield of cyclobutanetetracarboxylic dianhydride is up to 84.0% under the condition as the proportion of cyclobutanetetracarboxylic acid to acetic anhydride 1： 6,the reaction time 25 h and the reaction temperature 140 ℃.