异长叶烯酮磺酸的合成及其催化性能

摘要

Isolongifolenone sulfonic acid (IFSA) was synthesized by sulfonation of isolongifolenone using concentrated sulfuric acid as the sulfonation reagent and isolongifolenone as the starting material, and the catalysis effect of IFSA was investigated by catalyzing the esterification reaction of dipropylene glycol methyl ether (DPM) and acetic acid (HAc). Effects of the charging sequence,dosage of sulfuric acid, reaction temperature, and the amount of acetic anhydride on the sulfonation reaction were examined,and the suitable sulfonation conditions were determined as follows: the reactants mole ratio of isolongifolenone and H2SO41:1.4; acetic anhydride was used as the solvent, and the mass ratio of isolongifolenone/acetic anhydride was 1:2.0;sulfonation temperature 40℃,reaction time 40 min. The yield of IFSA reached 82.36% in the aforesaid conditions. The catalysis effect of IFSA was compared with other catalysts by catalyzing esterification reaction of dipropylene glycol methyl ether (DPM) and acetic acid(HAc),and test results showed that IFSA was the best than others. Effects of DMP/HOAC molar ratio,dose of IFSA,esterification temperature and time on the esterification reaction were examined, and the suitable esterification conditions were as follows:the molar ratio of DPM and HAc 1:1.5, the mass ratio of isolongifolenone sulfonic acid and DPM 0.045:1, cyclohexane as the water-carrying reagent, esterification temperature 90 ℃, esterification time 6 h. The yield of dipropylene glycol methyl ether acetate (DPMA) reached 96.69% at the aforesaid esterification conditions. In addition, the yield of DPMA was still maintained at more than 90.07 % when IFSA was reused for 3 times. Qualitative analysis, quantitative analysis, and structure characterization of the products were carried out by GC, GC-MS, HPLC, FT-IR, 1H NMR, 13C NMR, X-ray single crystal diffraction methods.%以异长叶烯酮为原料,以浓硫酸为磺化剂,合成异长叶烯酮磺酸(IFSA),并以二丙二醇甲醚(DPM)和乙酸(HAc)的酯化反应为模板,探索了IFSA对酯化反应的催化性能.采用GC、GC-MS、FT-IR、HPLC、1H NMR、13C NMR、X射线单晶衍射等分析手段对合成产物进行了定性和定量分析,对产物的结构也进行了表征.异长叶烯酮磺化反应过程中,研究了加料顺序、浓硫酸用量、反应温度、乙酸酐用量等对磺化反应的影响,异长叶烯酮适宜的磺化条件为:n(异长叶烯酮):n(浓硫酸)为1:1.4,以乙酸酐为溶剂,m(异长叶烯酮):m(乙酸酐)为1:2.0,反应温度40℃.在此条件下反应40min异长叶烯酮磺酸得率为82.36%.以DPM与HAc酯化反应为模板,实验结果表明IFSA的催化效果优于其他催化剂;研究了IFSA用量、反应温度、反应时间、环己烷用量等对酯化反应的影响,确定了适宜的酯化工艺条件:以0.1mol的二丙二醇甲醚为基准,当n(DPM):n(HAc)为1:1.5,m(IFSA):m(DPM)为0.045:1,环己烷用量24mL,反应温度90℃,反应时间6h.在此反应条件下,二丙二醇甲醚乙酸酯(DPMA)得率为96.69%,催化剂IFSA重复利用3次时,DPMA得率还能达到90.07%.