双核离子液体的合成及其对酯化反应的催化活性

doi:10.6023/cjoc201207002

有机化学 ›› 2012, Vol. 32 ›› Issue (12): 2382-2389.DOI: 10.6023/cjoc201207002 上一篇下一篇

研究简报

双核离子液体的合成及其对酯化反应的催化活性

赵地顺^a, 刘猛帅^a, 葛京京^a, 张娟^a, 任培兵^a,b

a 河北科技大学化学与制药工程学院石家庄 050018;
b 石家庄焦化集团有限责任公司石家庄 050031

收稿日期:2012-07-02 修回日期:2012-08-03 发布日期:2012-08-10
通讯作者: 赵地顺 E-mail:zhao_dsh@hebust.edu.cn
基金资助:
国家自然科学基金(Nos. 20576026, 21106032)、河北科技大学2012年度大学生科技创新基金资助项目.

Synthesis of Binuclear Ionic Liquids and Their Catalytic Activity for Esterification

Zhao Dishun^a, Liu Mengshuai^a, Ge Jingjing^a, Zhang Juan^a, Ren Peibing^a,b

a College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018;
b Shijiazhuang Coking and Chemical Group Co., Ltd., Shijiazhuang 050031

Received:2012-07-02 Revised:2012-08-03 Published:2012-08-10
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 20576026, 21106032) and the Scientific and Technological Innovation of Hebei University of Science and Technology (2012).

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摘要/Abstract

合成了双-(3-甲基-1-咪唑)亚丁基双对甲苯磺酸盐(Im-PTSA)、双-(3-甲基-1-咪唑)亚丁基双硫酸氢盐(Im-HSO₄)、双-(1-吡啶)亚丁基双对甲苯磺酸盐(Py-PTSA)、双-(1-吡啶)亚丁基双硫酸氢盐(Py-HSO₄)等4种功能化双核离子液体. 分别采用红外光谱(FT-IR)、核磁共振氢谱(¹H NMR)对合成的离子液体进行结构分析; 采用热重(TG)测试了离子液体的热稳定性; 此外, 考察了离子液体的酸性和溶解性. 以丁二酸和乙醇的酯化反应考察了4种离子液体的催化活性, 结果表明: 当n(C₄H₆O₄):n(C₂H₅OH)=1:3, 催化剂Im-PTSA量占总质量的1.90%, 反应温度70 ℃, 反应时间2.5 h, 酯收率可达93.6%, 选择性达100%, 且离子液体经真空干燥重复使用8次, 催化活性没有明显降低. 以奥氏体316 L不锈钢为试样, 考察了双核功能化离子液体的腐蚀性, 与浓硫酸进行对比, 其对钢试样的腐蚀率不到浓硫酸的1/10. 以双-(3-甲基-1-咪唑)亚丁基双对甲苯磺酸盐(Im-PTSA)为催化剂, 考察了一元有机酸和二元有机酸与系列醇的酯化反应, 均获得较高的酯收率和选择性, 反应结束后产品与催化剂自动分层, 简化了分离, 有望成为一种具有发展潜力的酯化催化剂.

关键词: 双核离子液体, 酯化反应, 催化剂, 丁二酸二乙酯, 腐蚀性

A series of functional binuclear ionic liquids based on bis-(3-methyl-1-imidazole)butylidene double P-toluene sulfonic acid salt (Im-PTSA), bis-(3-methyl-1-imidazole)butylidene double bisulfate (Im-HSO₄), bis-(1-pyridine)butylidene double p-toluene sulfonic acid salt (Py-PTSA), bis-(1-pyridine)butylidene double bisulfate (Py-HSO₄) were synthesized by a two-step proceeding and their structures were characterized by FT-IR and ¹H NMR spectra. Their thermal stabilities were characterized by TG. In addition, the acidity and solubility of functional binuclear ionic liquids were also studied. The catalytic activity of the binuclear ionic liquids for the esterification of succinic acid with ethanol was measured. The results show that under the optimized conditions of n(succinic acid):n(ethanol)=1:3, catalyst used dosage 1.90% (wt), 70 ℃ and 2.5 h, the yield of diethyl succinate reached 93.6% and the selectivity was near up to 100%. Im-PTSA was reused at least 8 times without significant decrease in activity after drying under vacuum. Austenitic stainless steel 316L was used for conducting the corrosion test under the above esterificaion condition, the corrosion rates of the steel plates dipped in the systems with these ionic liquids were less than one tenth of that with sulfuric acid. Fischer esterification of monocarboxylic acids and dicarboxylic acids with different alcohols was observed on using Im-PTSA as catalyst which gave high product yield and selectivity. Use of such a reaction catalyst should be appreciated for its convenient separation.

Key words: binuclear ionic liquid, esterification, catalyst, diethyl succinate, corrosion

引用此文

赵地顺, 刘猛帅, 葛京京, 张娟, 任培兵. 双核离子液体的合成及其对酯化反应的催化活性[J]. 有机化学, 2012, 32(12): 2382-2389.

Zhao Dishun, Liu Mengshuai, Ge Jingjing, Zhang Juan, Ren Peibing. Synthesis of Binuclear Ionic Liquids and Their Catalytic Activity for Esterification[J]. Chin. J. Org. Chem., 2012, 32(12): 2382-2389.

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双核离子液体的合成及其对酯化反应的催化活性

Synthesis of Binuclear Ionic Liquids and Their Catalytic Activity for Esterification

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