含N-Si键相转移催化剂的合成、性能及应用研究

【作者】 张其坤；

【导师】 贝逸翎；

【作者基本信息】 山东大学 ， 高分子化学与物理， 2006， 硕士

【摘要】 本课题把相转移催化技术应用到碳官能基有机硅化合物的合成中，在研究过程中，发现传统的季铵盐类相转移催化剂在催化有机硅单体与盐类反应的两相体系时催化效率不高，催化效果也不理想。考虑到结构和组成上的相似相溶原理，含有有机硅基的催化基团应更有利于在体系中迁移交换等因素，在传统的季铵盐类相转移催化剂的基础上，通过引入N-Si键合成了含硅烷基的新型相转移催化剂，以期在比较温和的条件下，以较高的产率、简便经济的手段一步合成出酰氧烃基硅烷化合物。 本研究合成了一系列含有有机硅基团的相转移催化剂。其中包括通过N-Si键形成的季铵盐类，也包括通过N-Si配键形成的配合物类。对于后者由于对其能否存在以及以何种结构形式存在，研究者们存在很大争议，本文在研究了其制备方法、催化性能的同时，应用红外光谱、核磁及元素分析等手段对其结构进行了表征，并对其热稳定性及导电性进行了检测。 在一氯取代的六甲基二硅氧烷、一氯取代的八甲基环四硅氧烷与醋酸钾酯化的两相反应中验证了新型相转移催化剂的催化性能。首先，应用文献提供的方法对两种硅氧烷进行了氯化，然后，把一氯代物与醋酸钾在水相中进行酯化反应，验证了新型催化剂的催化性能，并把其催化效果与传统的同类型的季铵盐类催化剂进行比较，结果令人满意。 一氯取代的六甲基二硅氧烷与醋酸钾的酯化反应实验结果表明：在相同反应条件下，同种类型的含硅烷基的相转移催化剂比相应的不含硅烷基的季铵盐催化剂酯化产率提高10％左右。一氯取代的八甲基环四硅氧烷与醋酸钾的酯化反应实验结果表明：在相同反应条件下，含硅烷基的季铵盐催化剂比相应的不含硅烷基的季铵盐更多还原

【Abstract】 This paper describes the synthesis of carbon functional groups organic silicon compound with phase transfer catalysis. We have found the traditional phase transfer catalyst’s efficiency is not satisfying in this system. According to the theory that compound with similar configuration and composing can dissolve each other and the catalyst with organic silicon group should benefit for catalyst’s transferring and exchanging in this system. Basing on traditional catalyst of quaternary ammonium salt, we synthesize the novel phase transfer catalyst containing N-Si bonds, which can synthesize acyloxyalkyl silicon compound with more productivity in a mild condition.We have synthesized a series of phase transfer catalysts containing organic silicon compound, which including the quaternary ammonium salt with N-Si bonds and also including the complex compounds with N-Si match bonds. There is a great disputed between investigators for the latter’s configuration and existing state. We have investigated its preparation method and catalyze performance, and also have launched great energy into describing its configuration.with IR、 NMR and EA,The catalytic capability of the catalyst was validated in the esterification reaction of chlorine substituted Hexamethyl disiloxane, chlorine substituted octamethyl cyclotetra siloxane with potassium acetate. To begin with, we have chloridized the two compounds with the method that literature provided. One is chloridized with chlorine, and the other is chloridized with sulfuryl chloride. Two methods all can reach the aim, we get a mixture that include one chlorine substituted production and multi chlorine substituted production. we separated them though rectified the mixture in vcuum conditions. The更多还原