摘要
本论文利用乙二醇和葡萄糖为原料合成乙二醇葡萄糖苷,研究乙二醇葡萄糖苷的分离纯化技术;再以乙二醇葡萄糖苷为中间体,研究非水相酶法合成乙二醇葡萄糖苷己酸酯的合成工艺,并对产物进行分离纯化,结构鉴定和性能分析。主要研究内容如下:
在酸催化剂存在下,以乙二醇和葡萄糖为原料制备得到乙二醇葡萄糖苷。在乙二醇葡萄糖苷的合成过程中,乙二醇是过量的,因此需要将合成产物中的乙二醇除去,必须对产物进行分离提纯。本文利用分子蒸馏法脱除产品中的乙二醇,并与萃取法、减压蒸馏法进行比较。结果表明分子蒸馏法脱醇效果较好。当进料速率80～100mL/h,刮膜器转速200r/min,预热温度80℃,冷凝面温度25℃,蒸馏温度150℃,体系真空度为200Pa时,能使残醇率降低到1%以下,解决了乙二醇葡萄糖苷产品中残醇量较高的问题,进一步扩大了乙二醇葡萄糖苷的应用范围。
以乙二醇葡萄糖苷和己酸为原料,Novozyme435脂肪酶为催化剂,用生物法合成乙二醇葡萄糖苷己酸酯。并研究反应溶剂、底物浓度、酶浓度、反应温度、反应时间等对己酸转化率的影响。得到最佳工艺条件为:以正己烷为溶剂体系,乙二醇葡萄糖苷0.3mol/L,正己酸1.8mol/L,酶浓度80mg/mL,反应温度70℃,反应时间24h,正己酸的转化率可达23.74%。
通过萃取法和硅胶柱色谱相结合的方式,实现酯化产物的分离,并确定了酯化产物的分离路线。以氯仿:甲醇(体积比为8:1)洗脱水相物质和氯仿相物质,通过薄层层析色谱、高效液相色谱和质谱鉴定,洗脱产物分别为乙二醇单葡萄糖苷己酸单酯和乙二醇单葡萄糖苷己酸二酯。
对乙二醇葡萄糖苷己酸酯混合物、乙二醇单葡萄糖苷己酸单酯和乙二醇单葡萄糖苷己酸二酯的乳化性和HLB值进行测定。结果表明三种物质乳化性能良好。
The preparation, separation of glycol glucosides, the biological synthesis of glycol glucoside caproate, and the analysis of the configuration and character of glycol glucoside caproate were studied in this paper. The main contents are as follow:
Glucose heated with ethylene glycol in the presence of an acid catalyst and forms a mixture of glycol glucoseds. In the process of synthesis glycol glucosides, the quantity of the glycol is superfluous, so it need to get rid of all the glycol from glycol glucosides. In the study, the mothod of molecular distillation was used to remove the excess glycol in the products, and had a comparison with the methods of solvent extraction and vacuum distillation. Experimental results showed that the method of molecular distillation was most effective when the conditions were as follows: feed flow rate 80～100mL/h,feed temperature 80℃, wiper rolling speed 200r/min, condensation temperature 25℃, evaporation temperature150℃and evaporation pressure 200Pa. Under this conditions, the residual glycol content can reduce to 1% and even less. So it enlarges the applications of the glycol glucoside.
Glycol glucoside caproate were synthesized by glycol glucosides and caproic acid as reaction materials, Novozyme435 lipase as catalyst. The effect of solvent, concentration of glycol glucosedes and caproic acid, the quantity of lipase, reaction temperature, reaction time on the conversion of caproic acid were studied. The optium conditions were as follows: in the solvent of hexane, glycol glucosides 0.3 mol/L ,caproic acid 1.8 mol/L, enzyme concentration 80mg/mL, reaction tempreture 70℃, reaction time 24h, and the conversion of caproic acid 23.74% was obtained.
The separation of esterification products were finished by the methods of solvent extraction and silica gel chromatography. The glycol glucoside caproic acid monoester was eluted by chloroform:methanol(v:v is 8:1) in the water phase and the glycol glucoside caproic acid diester was eluted by chloroform:methanol(v:v is 8:1) in the chloroform phase. The configurations of the products were identified by TLC, HPLC and MS.
The character of the glycol glucoside caproate, the glycol glucoside caproic acid monoester and the glycol glucoside caproic acid diester were studied. The results showed that they have good emulsification by test the emulsification and the HLB value.
引文
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