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题名: 功能化表面活性剂催化的无溶剂酯化反应研究
作者: 李刚
答辩日期: 2008-06-10
导师: 吾满江•艾力
专业: 有机化学
授予单位: 中国科学院研究生院
授予地点: 北京
学位: 博士
关键词: 酯化反应 ; 无溶剂 ; 功能化表面活性剂(FS)
摘要: 本论文系统研究了功能化表面活性剂(FS)催化各种不同结构的羧酸和醇的脱水酯化、聚酯化以及选择性酯化反应。在研究十二烷基苯磺酸有效催化油酸和辛醇的室温无溶剂酯化反应的基础上,通过复分解反应制备了阴离子为十二烷基苯磺酸根、十二烷基硫酸根以及十二烷基磺酸根和阳离子为Al3+、Sn4+、Cu2+、Zn2+和Co2+等Lewis酸离子的多种Lewis酸型功能化表面活性剂,并以油酸和辛醇为反应底物,在室温无溶剂条件下,考察筛选了这些催化剂对酯化反应的有效催化活性;通过与硫酸、对甲苯磺酸、硫酸铜、对甲苯磺酸铜以及十二烷基苯磺酸钠对酯化反应的催化比较,研究了FS催化酯化反应的脱水和除水机制,并进一步用透射电镜进行确证;用筛选过的活性较高的FS催化包括线性的,带有苯环、双键等功能基团的以及带支链位阻的不同结构的有机酸与醇的酯化,还用来催化二元以及多元底物的酯化,二元酸二元醇聚酯化反应以及选择性酯化反应,来考察FS催化不同类型酯化反应的催化效果和适用范围。研究表明FS既具有Brønsted或Lewis酸的催化作用,又具有表面活性剂的性能,因此这类催化剂具有双重特性,一是作为Brønsted酸或Lewis酸催化剂来催化有机反应,二是作为表面活性剂在体系中形成胶束或乳液,隔离水与产物酯,促进反应平衡向右进行,该催化酯化方法体现了绿色化学的优点:该酯化方法不需要任何溶剂,即使水也不需要;反应过程中不需要回流除去反应产生的水,从而节约能量,减少能源的消耗,降低成本;反应条件比较温和,甚至在室温下就能使酯化反应顺利进行;并且由于该类催化剂的亲油性质,能增加催化剂与反应物的接触,加速反应进行。因此,整体来说,功能化表面活性剂催化无溶剂酯化是一个相对绿色的酯化方法。
英文摘要:
Solvent-free esterifications, polyesterification and selective esterification of various carboxylic acids and alcohols catalyzed by functional surfactant are researched systemically in the paper. On the basis of esterification of oleic acid and 1-octanol effectived catalyzed by dodecylbenzene sulfonic acid (DBSA), we synthesize various Lewis acid functional surfactant (LAFS) from AlCl3 CuCl2, SnCl4, ZnCl2, MgCl2, CoCl2 and soldium dodecylbenzene sulfonate, soldium dodecyl sulfate, soldium dodecyl sulfonate by decomposition reaction。And used oleic acid and 1-ocanol as typical reaction substrates, their activation of catalyzing esterification are investigated on the condition of free solvent and at room temperature. By comparison of esterification catalyzed by sulfuric acid, toluence sulfuric acid, bluestone, copper toluence sulfate, sodium dodecylbenzene sulfonate, we research FS catalyzed esterification mechanism of removing water, and the micelle mechanism is confirmed furtherly by TEM. For investigating applicability and application scope of these FS catalysts to esterification, we use the screened effective catalysts to catalyze esterification of linear and nonlinear carboxylic acids and alcohols, substrates with functional group, polysesterification of dicarboxylic acid and diol, selective esterification. This study indicates that the catalysts FS with both catalysis function and surfactant function play dual roles during the esterification. First, as Brosted and Lewis acids, they effectively catalyze the esterification reaction. Secondly, as surfactants, they can form reverse micelles in system to separate water produced from the product ester and promotes the reaction equilibrium towards the product. The esterification method has following green chemistry advantages: Firstly, there is no need for any solvent, even water. Secondly, the method no need to remove water produced to promote the equilibrium process to shift towards the product side, saving energy. Thirdly, the condition of reaction is mild, even esterification can carry out smoothly at room temperature. And fourthly, hydrophobicity of FS enhances contact of catalyst and reactants, and quiken velocity of reaction. In conclusion, esterifications catalyzed by functional surfactant are a relative green chemistry method.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3524
Appears in Collections:新疆维吾尔自治区精细化工工程技术研究中心_学位论文

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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
李刚. 功能化表面活性剂催化的无溶剂酯化反应研究[D]. 北京. 中国科学院研究生院. 2008.
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