Amberlyst 70磺酸树脂催化合成丙二酸二乙酯
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摘要
以Amberlyst 70磺酸树脂为催化剂催化丙二酸与乙醇的酯化反应,合成重要的精细化工中间体丙二酸二乙酯。考察反应时间、反应温度、醇酸物质的量比、催化剂用量等对酯化反应的影响,优化反应条件。结果表明,在醇酸物质的量比为3∶1、催化剂用量为丙二酸质量的10%、反应时间2 h和反应温度120℃的条件下,丙二酸二乙酯产率和选择性98.9%。表明Amberlyst 70磺酸树脂对丙二酸与乙醇的酯化反应有较高的催化活性。
Important fine chemical intermediate diethyl malonate was synthesized by Amberlyst 70 sulfonic acid resin catalyzed esterification of malonic acid and ethanol. Effects of various reaction parameters such as mole ratio of ethanol to malonic acid,amount of catalyst,reaction time,reaction temperture were discussed and the optimum reaction conditions were found out. Experimental results showed that when mole ratio of ethanol to malonic acid was 3∶ 1,amount of catalyst was 10% of malonic acid weight,reaction time was 2 h and reaction temperature was 120 °C,yield and selectivity of diethyl malonate reached 98. 9%. It was proved that the catalyst had high activity to esterification and could be used repeatedly.
Important fine chemical intermediate diethyl malonate was synthesized by Amberlyst 70 sulfonic acid resin catalyzed esterification of malonic acid and ethanol. Effects of various reaction parameters such as mole ratio of ethanol to malonic acid,amount of catalyst,reaction time,reaction temperture were discussed and the optimum reaction conditions were found out. Experimental results showed that when mole ratio of ethanol to malonic acid was 3∶ 1,amount of catalyst was 10% of malonic acid weight,reaction time was 2 h and reaction temperature was 120 °C,yield and selectivity of diethyl malonate reached 98. 9%. It was proved that the catalyst had high activity to esterification and could be used repeatedly.
引文
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[11]刘贤响,毛丽秋,徐琼等.磺酸树脂Amberlyst 70催化环己酮肟液相重排制己内酰胺[J].精细石油化工,2011,28(4):1-3.Liu Xianxiang,Mao Liqiu,Xu Xiong,et al.Liquid phase rearrangement of cyclohexanone oxime toε-caprolactam catalyzed by amberlyst 70 sulfoacid resin[J].Speciality Petrochemicals,2011,28(4):1-3.
[2]丁同梅,吴文滨,田恒水.丙二酸二乙酯在Cu/Si O2催化剂上的加氢过程[J].石油化工,2016,45(6):664-670.Ding Tongmei,Wu Wenbin,Tian Hengshui.The hydrogenation process of diethyl malonate over Cu/Si O2catalyst[J].Petrochemical Technology,2016,45(6):664-670.
[3]龚菁,王云翔,钱蕙,等.微波辐射相转移催化丙二酸二乙酯的烷基化反应研究[J].苏州科技学院学报,2006,23(1):58-61.Gong Jing,Wang Yunxiang,Qian Hui,et al.A study on alkylation of diethyl malonate catalyzed by microwave irradiation and phase transfer catalyst[J].Journal of University of Science and Technology of Suzhou(Natural Science Edition),2006,23(1):58-61.
[4]宋璐娜,于静文.苯胺类化合物与丙二酸二乙酯的酰胺化反应[J].太原师范学院学报(自然科学版),2017,16(2):83-86.
[5]张东卫,杨国忠,王虹.丙二酸二乙酯的生产工艺改进[J].山东化工,2015,44(1):105-106.Zhang Dongwei,Yang Guozhong,Wang Hong.Malonic diethyl production process improvement[J].Shandong Chemical Industry,2015,44(1),105-106.
[6]李慧,胡远卓,徐琼.磷酸活化-微波炭化法制备炭基磺酸及其催化性能研究[J].湖南师范大学自然科学学报,2017,40(6):61-65.Li Hui,Hu Yuanzhuo,Xu Xiong.Study on preparation of carbon-based sulfonic acid by phosphoric acid-microwave activated carbonization and its catalytic performance[J].Journal of Natural Science of Hunan Normal University,2017,40(6):61-65.
[7]印香俊,薛叙明.硅胶负载硫酸钛催化合成丙二酸二乙酯[J].精细石油化工进展,2005,6(3):42-43.Yin Xiangjun,Xue Xuming.Synthesis of diethyl malonate catalyzed by titanic sulfate supported on silica gel[J].Advances in Fine Petrochemical,2005,6(3):42-43.
[8]林世静,孙阳昭,陈中元.微波辐射硫酸铁催化合成丙二酸二乙酯的研究[J].香料香精化妆品,2009,(1):27-29.Lin Shijing,Sun Yangzhao,Chen Zhongyuan.Synthesis of diethyl malonate catalyzed by ferric sulfate under microwave irradiation[J].Flavour Fragrance Cosmetics,2009,(1):27-29.
[9]王升文,李继忠.活性炭负载磷钨酸催化合成丙二酸二乙酯的研究[J].工业催化,2007,15(7):44-46.Wang Shenwen,Li Jizhong.Syntheis of diethyl malonate over phosphotungstic acid supported on activated carbon[J].Industrial Catalysis,2027,15(7):44-46.
[10]邓斌,王存嫦,徐安武.甲烷磺酸铜催化合成丙二酸二乙酯[J].精细石油化工,2008,25(6):11-14.Deng Bin,Wang Cunchang,Xu Anwu.Catalytic synthesis of diethyl malonate with cupper methanesulfonate[J].Speciality Petrochemicals,2008,25(6):11-14.
[11]刘贤响,毛丽秋,徐琼等.磺酸树脂Amberlyst 70催化环己酮肟液相重排制己内酰胺[J].精细石油化工,2011,28(4):1-3.Liu Xianxiang,Mao Liqiu,Xu Xiong,et al.Liquid phase rearrangement of cyclohexanone oxime toε-caprolactam catalyzed by amberlyst 70 sulfoacid resin[J].Speciality Petrochemicals,2011,28(4):1-3.