Study on microwave-assisted catalytic synthesis of dimethyl fumarate in presence of ionic liquid catalyst and its application
HUANG Fei1, QU Feiqiang1, WEI Xianwen2*, REN Xiaoqiong1, LAN Yansu1
(1 College of Chemistry and Chemical Engineering, Huangshan University, Huangshan 245041, Anhui, China; 2 College of Chemistry and Materials Science, Anhui Normal University; The Key Laboratory of Functional Molecular Solids, Ministry of Education, Wuhu 241000, Anhui, China)
Abstract:
The dimethyl fumarate was synthesized using maleic anhydride and methanol with microwave-assisted in presence of ionic liquid \[HSO3-pmim\]+\[HSO4\]- as catalyst and sulfocarbamide as isomerization agent. The molar ratio of maleic anhydride to methanol, the amount of catalyst, microwave power and microwave time were explored by single factor experiment and orthogonal experiment. The results show that under optimal conditions for the synthesis of dimethyl fumarate, the molar ratio of maleic anhydride to methanol being 1∶6, the amount of catalyst being 2.5 g, the microwave power being 400 W, and microwave time being 7 min, the dimethyl fumarate yield was up to 95.3%. In microwave irradiation, the ionic liquid \[HSO3-pmim\]+\[HSO4\]-exhibited excellent stability and catalytic activity,and it can be reused seven times without considerable loss of activity and still makes the conversion rate reach to above 90%.
KeyWords:
dimethyl fumarate; ionic liquid \[HSO3-pmim\]+\[HSO4\]-; microwave-assisted; catalytic synthesis; preservative富马酸二甲酯(DMF)化学名为反丁烯二酸二甲酯,俗称延胡索酸二甲酯,是一种优良的新型防腐保鲜剂;其具有高效、广谱、低毒、实用等特点,对霉菌有特殊的抑制效果,且化学稳定性好,适用pH范围宽,作用时间长,综合防腐效果突出;其综合抗菌防腐性能优于目前常用的苯甲酸、脱氢醋酸、山梨酸、对羟基苯甲酸及其盐类和酯类等防腐剂\[1-2\]。富马酸二甲酯作为防霉剂具有很强的生物活性及薰蒸性,有接触杀菌和熏蒸杀菌的双重作用\[3\];同时,富马酸二甲酯进入人体后会很快转变成正常代谢产物富马酸,因此其应用安全性极高\[4-5\]。富马酸二甲酯广泛应用于食品、饮料、蔬菜、水果、粮食、饲料的防腐与保鲜,也可用于皮革、烟草、造纸、化妆品、纺织品、电子、制药等行业\[6-7\],并且正在不断开发新的应用领域,是一种很有发展前景的新型防腐剂。最新研究表明,富马酸二甲酯是一种激活抑制剂,可用于治疗多发性硬化症,能将患者复发的概率降低约50%,同时可将多发性硬化症的致残率降低38%。富马酸二甲酯还具有潜在的解毒作用,可显著减少大脑损伤\[8-10\]。