【作者】 袁先友；

【导师】 阳年发； 刘跃进；

【作者基本信息】 湘潭大学 ， 化学工程， 2005， 博士

【摘要】 微波技术是二十世纪八十年代兴起的一项有机合成新技术，与常规加热方法相比，具有反应体系受热均匀，增加分子间的碰撞几率，缩短反应时间，提高反应收率等特点。杂多酸环境友好，并具有低温高活性、热稳定性好以及独特的“假液相”行为、多功能（酸、氧化、光电催化）等优点，从而在催化研究领域中受到研究者们的广泛重视。利用微波技术促进杂多酸催化合成精细有机化学品，文献报道较少（只是最近几年才有少量文献报道）。本文对微波促进杂多酸催化合成精细有机化学品进行了研究。 1．微波促进杂多酸催化剂催化缩羰基化反应研究 （1）研究了在微波辐射条件下活性炭负载杂多酸催化合成季戊四醇单缩醛（酮）、双缩醛（酮）以及不同醛（酮）的季戊四醇二缩醛（酮）反应，合成了34种季戊四醇缩醛（酮），其中有2种季戊四醇单缩醛、5种季戊四醇双缩醛和10种不同醛（酮）的季戊四醇二缩醛（酮）属首次报道的新化合物，并进行了IR、¹HNRM和元素分析表征。结果表明：活性炭负载杂多酸对季戊四醇缩醛（酮）的合成具有催化活性高、催化剂用量少、产率高、催化剂可重复使用、不腐蚀设备等优点，同时利用微波技术可极大地加快反应速率，与常规加热法相比，微波法普遍要快（?）0～600倍以上，且不用或少用溶剂，具有广泛的工业应用前景。 （2）研究了含1，3-二噁烷环的双磺酸盐的可裂解表面活性剂的微波合成及临界胶束浓度（CMC）测定和酸性条件下的水解作用、微波促进杂多酸催化合成乙酰乙酸乙酯缩酮的反应。以活性炭负载磷钨酸作催化剂，利用微波辐射技术合成乙酰乙酸乙酯乙二醇缩酮，比常规加热法要快20倍以上，催化剂用量减少，且不用溶剂。 2．微波辐射杂多酸催化剂催化酯化反应研究 研究了微波辐射超稳Y沸石负载硅钨酸催化合成肉桂酸β-苯乙酯和苯乙酸β-苯乙酯，微波辐射活性炭负载磷钨酸催化合成苯乙酸β-苯乙酯以及微波辐射SiO₂负载磷钨酸催化合成丙酸苄酯。结果表明：以HSW／USY和HPW／C为催化剂，将微波技术应用于肉桂酸与β-苯乙醇和苯乙酸与β-苯乙醇的酯化反应，反应时间短，酸醇比小，酯化率高，操作简便，不用溶剂，有利于环境保护，催化剂可重复使用。同样，微波辐射对SiO₂负载磷钨酸催化剂催化合成丙酸苄酯具有显著的促进作用，与传统加热方法相比，反应速率提高45倍，酯化收率提高7.1％，带水剂用量减少50.0％，催化剂可重复使用。 3．微波促进杂多酸及SnCl₄催化α-蒎烯异构化反应研究 研究了微波促进杂多酸及SnCl₄催化α-蒎烯异构化反应，研究表明：微波辐射对活性炭负载磷钨酸和SnCl₄催化α-蒎烯异构化反应具有很大的促进作用。催化剂负载量增大、催化剂用量增加、微波辐射功率增大和辐射时间延长都能增加反应速率和提高转化率，同更多还原

【Abstract】 Microwave technique has been a novel method of organic synthesis since 1980s. Compared with the conventional heating way, the microwave technique has been proved to be more useful, for example, more average heated in reaction system, more collision factor of probability in intermolecular, shorter reaction time, higher yield. Since heteropoly acid possesses numerous merits, such as an environmental amity, and an excellent activity in low temperature, a good hot stability, a unique pseudofluid phase behavior, a multifunction catalysis for acid, oxidize, and photoelectricity heteropoly acid has extensively been attracted attention in the field of catalysis by catalytic researchers. Up to now, it has been limited to report the use of microwave technique to accelerate the heteropoly acid catalytic synthesis of fine organic chemicals. In this thesis, the use of microwave technique to accelerate the heteropoly acid catalytic synthesis of fine organic chemicals has in detail been studied as follow:1. Study of microwave irradiation promoting the heteropoly acid catalytic function for condensation reaction of carbonyl compoubds(1) Based on the microwave irradiation, mono-acetal (ketal) of pentaerythritol and diacetal (diketal) of pentaerythritol, and different kinds of diacetal (diketal) of pentaerythritol were synthesized by active carbon loading heteropoly acids. 34 kinds of such products were obtained and characterized by IR, ~1HNRM and element analysis. Among these products, such compounds were for the first time reported as two kinds of mono-acetal of pentaerythritol, five kinds of diacetal of pentaerythritol, and ten kinds of different kinds of diacetal (diketal) of pentaerythritol. The results demonstrate that the active carbon loading heteropoly acids possess good catalytic reactions, small dosage, high yield, repeated use, and incorrosive equipments in these synthetic processes. Meanwhile microwave techniques importantly have expediting reaction rates where these rates based on these microwave techniques have 30 to 600 times as many as those rates by the conventional heating ways and it is unnecessary to use solvent (if need, only a little of solvent is needed) in these catalytic reactions. So the microwave techniques are provided with potential applications in large-scale industry produces.(2) The microwave synthesis of disulfonate salt-type surfactants with a 1,3-dioxane ring and the determinations of critical micelle concentration (CMC), and hydrolyzation reactions in acidic conditions, and the promoting heteropoly acid catalytic syntheses of acetoacetic ester ketal by microwave techniques were researched. During the microwave techniques, based on these更多还原