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葡萄糖苷基Gemini表面活性剂的合成与性能研究

Study on Synthesis And Properties of Glycosidase Base Gemini Surfactants

作者: 专业:化学 导师:芦艳 年度:2015 学位:硕士  院校: 东北石油大学

Keywords

Green surfactant, Gemini reagent, Glucoside, response surface, physical chemical properties

        Gemini表面活性剂是近十几年来迅速发展起来的一种新型表面活性剂。与传统的表面活性剂相比具有明显的优势:较低的表面张力和CMC值、较强的去污能力和润湿性、较低的Krafft点、奇特的黏度特性等性能优势。实验首次采用淀粉、乙二醇、酸酐、脂肪酸为原料来合成不同系列的脂肪酸乙二醇葡萄糖苷马来酸(苯酐)双酯,反应分为以下几步:第一步:以磷酸作为催化剂,使淀粉中的葡萄糖单元与乙二醇发生缩醛反应生成乙二醇葡萄糖苷,通过单因素和响应面法,考察了搅拌速率、醇糖比、催化剂的量、反应温度和反应时间对产率的影响和各个因素之间的交互作用,确定了最佳反应条件:搅拌速率为800r·min-1,醇糖比为4:1,催化剂的量为淀粉质量的1.5%,温度为130℃,时间为2h。在最佳反应备件下,产物收率可达98.14%。第二步:以二甲氨基吡啶(DMAP)为催化剂,以酸酐为酰化剂,酸酐与乙二醇葡萄糖苷发生酰化反应生成乙二醇葡萄糖苷双酯中间体,采用响应面法考察了催化剂量的量、温度、时间和物料比对产率的影响和各个因素之间的交互作用,确定了最佳反应条件:催化剂用量为淀粉质量的1%、温度为90℃、时间为6h、物料比(n酸酐:n乙二醇葡萄糖苷)为3,得到的收率可达79.627%。第三步:以对甲苯磺酸为催化剂,n脂肪酸:n乙二醇葡萄糖苷马来酸(苯酐)双酯为2.5:1,生成最终产物脂肪酸葡萄糖基Gemini表面活性剂。通过红外光谱、核磁共振谱(13C-NMR)分别对以上三步所合成产物的结构进行了表征,确定产物最终结构。通过测定脂肪酸葡萄糖苷基Gemini表面活性剂的表面张力、临界胶束浓度CMC、溶解性、泡沫性及乳化性,研究不同碳链长度、不同温度和不同连接基团对表面活性剂物化性能的影响。结果表明,合成的新型表面活性剂具有很好的表面活性,而且随着碳链的增加,表面张力可由36.18mN/m降低到29.57mN/m;当温度由25℃升至60℃时,14-slys-14表面活性剂的表面张力由32.53mN/m降低到29.67mN/m,16-slys-16表面活性剂的表面张力由29.57m N/m降低到27.64mN/m。这说明该Gemini表面活性剂具有较强的耐温性能。同时发现脂肪酸葡萄糖苷基Gemini表面活性剂具有优良的溶解性,并且随着碳链的增长,乳化性能和泡沫性也呈现规律的变化,是一种较理想的绿色表面活性剂,具有很好的应用前景。
    Gemini surfactant is a new class of surfactant that has been developed rapidly in the last decade. It has significant performance advantages compared with classic surfactant, such as higher surfactant, lower cmc value, strong detergency and wettability, lower Krafft point,strange viscosity characteristics.For the first time, experiments using starch, glycol, acid anhydride and saturated fatty acid as raw material to synthesize different series of fatty acid glycol glucoside maleic acid(phthalic anhydride) double ester. Reaction can be divided into the following steps:Step 1 : Taking phosphoric acid as catalyst to prepare glycol glucoside by the reaction of glucose unit of starch and glycol acetal. By single factor and response surface method, some influence facts have been investigated, such as alcohol sugar ratio, stirring speed, the quantity of catalyst, reaction temperature, reaction time on the yield, and the interaction between different factors. The optimum reaction conditions were determined: stirring speed is800r·min-1, alcohol sugar ratio is 4:1, the amount of catalyst is 1.5%, the temperature is 130℃,the reaction time is 2h. Under this condition, the aim product yield can reach 98.14%. Step 2:Taking dimethyl amine pyridine(DMAP) as catalyst, acid as acylating agent to prepare glycol glucoside double ester intermediates, when acylation reaction of the acid and ethylene glycol glucoside occurs. Response surface method is used to examine the amount of the catalyst dosage, reaction temperature, reaction time and material ratio on the yield and the interaction between the factors. The optimum reaction conditions were determined: the amount of catalyst is 1mol, reaction temperature is 90℃, reaction time is 6h, material ratio of anhydride and glycol glucoside is 3, the product yield can reach 79.627%. Step 3: Taking p-toluene sulfonic acid as catalyst to prepare the end product fatty acid glycol glucoside maleic acid(phthalic anhydride) double ester, when the mole ratio of fatty acids and glycol glucoside maleic acid(phthalic anhydride) double ester is 2.5:1. By infrared spectroscopy, nuclear magnetic resonance spectroscopy(13C-NMR), the structure of synthetic products were characterized respectively, and determined the final product.Through the determination of surface tension, critical micelle concentration, CMC,solubility, foam and emulsification of fatty acid glucoside base Gemini surfactant, the effect of different carbon chain length, different temperature and different linkers on the surfactant properties can be research. The results show that the new type of surfactant has a good surface activity, and with the increase of carbon chain, surface tension can be reduced by 36.18 mN/m to 29.57 mN/m; When the temperature rising from 25 ℃ to 60 ℃, the surface tension of14-slys-14 surfactant decrease from 32.53 m N/m to 29.67 mN/m, the surface tension of16-slys-16 surfactant decrease from 29.57 mN/m to 27.64 mN/m. It is shown that the Gemini surfactant has a strong heat resistance performance. It is also found that fatty acid glucoside base Gemini surfactant has an excellent solubility, and with the increase of carbon chain,emulsifying properties and foam also presents the regularity of change. The new type Geminisurfactant is a kind of ideal green surfactant, which has the very good application prospect.
        

葡萄糖苷基Gemini表面活性剂的合成与性能研究

摘要4-5
Abstract5-6
创新点摘要7-10
第一章 文献综述10-36
    1.1 研究背景10
    1.2 Gemini表面活性剂的发展历程10-11
    1.3 Gemini表面活性剂的分类11-15
        1.3.1 阳离子Gemini表面活性剂11-12
        1.3.2 阴离子Gemini表面活性剂12-14
        1.3.3 非离子Gemini表面活性剂14
        1.3.4 两性Gemini表面活性剂14-15
    1.4 Gemini表面活性剂的合成方法15-18
        1.4.1 极性头基加入法15-16
        1.4.2 连接基加入法16-17
        1.4.3 疏水链加入法17-18
    1.5 Gemini表面活性剂的合成进展18-32
        1.5.1 阳离子型Gemini表面活性剂的合成进展18-20
        1.5.2 阴离子型Gemini表面活性剂的合成进展20-25
        1.5.3 非离子离子型Gemini表面活性剂的合成进展25-28
        1.5.4 两性型Gemini表面活性剂的合成进展28-29
        1.5.5 不对称型Gemini表面活性剂的合成进展29-31
        1.5.6 对称型Gemini表面活性剂的合成进展31-32
    1.6 Gemini表面活性剂的应用32-34
    1.7 选题意义和研究内容34-36
        1.7.1 选题意义34
        1.7.2 主要研究内容34-36
第二章 实验部分36-40
    2.1 实验药品及仪器36-37
    2.2 葡萄糖基Gemini非离子表面活性剂实验合成路线37-38
    2.3 实验方法和步骤38-40
        2.3.1 淀粉的精制38
        2.3.2 乙二醇葡萄糖苷的合成38
        2.3.3 乙二醇葡萄糖苷马来酸双酯的合成38
        2.3.4 酸值的测定38-39
        2.3.5 脂肪酸葡萄糖酯乙二醇苷马来酸酐双酯的合成39-40
第三章 实验结果讨论40-50
    3.1 缩醛化反应工艺条件的优化40-45
        3.1.1 缩醛化反应机理40
        3.1.2 溶解扩散过程对缩醛化反应产物组成的影响40-41
        3.1.3 醇糖对缩醛化反应产物组成的影响41-42
        3.1.4 其他条件对缩醛化反应的影响42-45
    3.2 乙二醇葡萄糖苷马来酸双酯合成条件的优化45-49
        3.2.1 酰化反应中催化剂的选择与反应机理45
        3.2.2 酰化反应最优条件的确定45-49
    3.3 本章小结49-50
第四章 产品结构表征50-59
    4.1 红外谱图分析50-53
        4.1.1 傅立叶红外测试50
        4.1.2 乙二醇糖马来酸(苯酐)双苷酯的结构表征50-52
        4.1.3 脂肪酸乙二醇葡萄糖苷马来酸双酯的IR图52-53
        4.1.4 脂肪酸葡萄糖酯乙二醇苯酐双酯的IR图53
    4.2 产品的核磁表征53-58
        4.2.1 核磁碳谱分析53-54
        4.2.2 乙二醇葡萄糖苷马来酸(苯酐)双酯核磁碳图谱分析54-56
        4.2.3 脂肪酸葡萄糖酯乙二醇马来酸(苯酐)双酯核磁碳图谱分析56-58
    4.3 本章小结58-59
第五章 葡萄糖苷基Gemini表面活性剂性能测试59-69
    5.1 引言59
    5.2 实验部分59-61
        5.2.1 表面张力和CMC(临界胶束浓度)的测定59-60
        5.2.2 溶解性的测定60
        5.2.3 表面活性剂乳化能力实验60
        5.2.4 葡萄糖苷基Gemini表面活性剂泡沫性能的研究60-61
    5.3 实验结果与分析61-67
        5.3.1 Gemini表面活性剂对物化性能影响的研究61-65
        5.3.2 溶解性的测定65
        5.3.3 碳链长度对Gemini表面活性剂乳化性能的影响65-66
        5.3.4 碳链长度对葡萄糖苷基Gemini表面活性剂起泡性的影响66-67
    5.4 本章小结67-69
结论69-70
参考文献70-75
发表文章目录75-76
致谢76-77
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