摘要
为解决C_(22)-三元羧酸合成过程中均相催化剂残留、原料价格较高等问题,以油酸为原料,在路易斯酸催化下与马来酸酐进行Alder-ene加成反应,水解后得到C_(22)-三元羧酸。对C_(22)-三元羧酸的合成条件进行优化并对产物进行了鉴定;制备C_(22)-三元酸钠表面活性剂并研究其表面性能。结果表明:C_(22)-三元羧酸合成的最佳条件为以FePO4为催化剂、催化剂用量3%(以油酸物质的量计)、马来酸酐与油酸物质的量比3∶1、反应温度180℃、反应时间10 h,在此条件下C_(22)-三元羧酸产率达到78%,油酸转化率为77.4%;通过质谱及核磁共振表征证明得到了较纯的C_(22)-三元羧酸;催化剂经过5次回收利用并未出现明显的活性降低;以C_(22)-三元羧酸为原料制备的C_(22)-三元酸钠表面活性剂的临界胶束浓度为3.61×10^(-3)mol/L,在临界胶束浓度下的表面张力为28.39 mN/m。综上,油酸在FePO4催化下直接马来酸化制备C_(22)-三元羧酸,工艺绿色,原料成本较低,并可作为表面活性剂制备的良好原料。
To solve the problems of homogeneous catalyst residue and high raw material price in the synthesis of C_(22)-tricarboxylic acid, using oleic acid as the raw material, Lewis acid as catalyst, the Alder-ene addition reaction of oleic acid and maleic anhydride was realized, and C_(22)-tricarboxylic acid was obtained after hydrolysis. The synthesis conditions of C_(22)-tricarboxylic acid were optimized and the product was identified, and its product was neutralized to prepare C_(22)-tribasic acid sodium surfactant and its surface properties were studied. The results showed that the optimal conditions for C_(22)-tricarboxylic acid synthesis were obtained as follows: with Lewis acid FePO4as catalyst, dosage of catalyst 3%(calculated by the mole of oleic acid), molar ratio of maleic anhydride to oleic acid 3∶1, reaction temperature 180 ℃, and reaction time 10 h. Under the optimal conditions, the yield of C_(22)-tricarboxylic acid could reach 78% and oleic acid conversion rate was 77.4%. It was proved that C_(22)-tricarboxylic acid was obtained through mass spectrometry and nuclear magnetic resonance characterization. There was no obvious decrease in activity of catalyst after 5 times of recycling. The critical micelle concentration of C_(22)-tribasic acid sodium surfactant prepared by C_(22)-tricarboxylic acid was 3.61×10^(-3)mol/L, and the surface tension(γ) reached 28.39 mN/m. In conclusion, the preparation process of C_(22)-tricarboxylic acid by the Alder-ene addition reaction of oleic acid and maleic anhydride with FePO4as catalyst is green and the cost of materials is low, and the C_(22)-tricarboxylic acid prepared can used as good material for surfactant preparation.
作者
陈治家
赵杰
张铭远
邓林江
钮腾飞
CHEN Zhijia;ZHAO Jie;ZHANG Mingyuan;DENG Linjiang;NIU Tengfei(School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,Jiangsu,China)
出处
《中国油脂》
CAS
CSCD
北大核心
2023年第1期60-65,共6页
China Oils and Fats
基金
国家自然科学基金(21808085)。
