呋喃类平台化合物的衍生化反应研究

发布时间：2018-04-16 14:21

本文选题：糠醛 + HMF　；参考：《天津工业大学》2017年硕士论文

【摘要】：生物质作为唯一可再生的有机碳资源,具有来源丰富,价格低廉,绿色环保以及可再生等优点,是替代石油生产燃料和化学品的理想选择。其中,糠醛和5-轻甲基糠醛(HMF)是两种重要的生物质基平台分子,可以通过不同的基元反应制备具有高附加值的平台分子下游化学品,例如:糠偶姻、糠偶酰、5,5'-二羟甲基糠偶姻(DHMF),5,5'-二羟甲基糠偶酰(BHMF)等。但是目前这些转化还存在反应条件苛刻、产物选择性差、催化体系过于复杂以及催化剂难以回收重复利用等问题。因此,发展更多高效温和催化体系来解决上述问题,为这些基元反应提供新的方法和思路显的尤为重要。本文主要分为以下几个部分:第一章主要介绍了生物质和平台分子的概念以及目前生物质转化制备燃料的发展状况;接着详细介绍了平台分子糠醛和HMF的制备以及各自转化成为化学品或者燃料分子的最具代表性的研究进展;最后,简单介绍了本文所应用的催化体系及研究进展。第二章介绍了平台分子糠醛和HMF通过自身碳-碳偶联反应制备C10和C12糠偶姻的方法。反应使用蒙脱土负载的噻唑类离子液体和碱结合形成的卡宾为催化剂,实现了糠醛和HMF的自身增碳偶联,获得了最高99%的C10糠偶姻产率以及98%的C12糠偶姻产率。考察了不同溶剂对反应的影响,发现在无溶剂条件下该反应依然可以得到很高的收率。同时,研究了不同噻唑类离子液体对反应产率的影响,发现噻唑环上带有给电子基团的离子液体比带有吸电子基团的具有更高的催化活性。最后研究了负载催化剂的重复利用性能,发现该催化体系重复利用四次以后产率并没有明显的减少。第三章介绍了C10和C12糠偶姻选择性氧化制备α-呋喃基二酮的方法。合成了具有典型Keggin型结构的八钼酸季铵盐和十钨酸季铵盐催化剂,在较为温和的条件下,获得了100%的糠偶酰收率和94%的BHMF收率。提出了八钼酸季铵盐催化该反应可能的反应机理,发现与八钼酸季铵盐催化剂相比,十钨酸季铵盐催化剂在C10和C12糠偶姻选择性氧化反应中的催化活性较低。与传统方法相比,该方法具有操作简单、环境友好、催化剂可以回收利用等特点。第四章对全文进行了总结。综上所述,本文主要以平台分子糠醛和HMF为研究对象,发展了蒙脱土负载的卡宾催化体系以及具有典型Keggin型结构的八钼酸季铵盐和十钨酸季铵盐催化体系,实现了平台分子到不同化学品的绿色转化过程,研究了不同催化剂对反应活性和选择性的影响规律,拓展了生物质基平台分子的转化和应用。
[Abstract]:Biomass, as the only renewable organic carbon resource, has the advantages of rich sources, low price, green environment and renewable. It is an ideal alternative to oil to produce fuels and chemicals.Among them, furfural and 5-light methylfurfural (HMF) are two important biomass-based platform molecules, which can be used to prepare high value-added downstream chemicals, such as furfural, furfural and 5-methylfurfural, such as furfural and 5-methylfurfural.BHMFs, DHMFN, DHMFN, DHMFN, DHMFN, DHMF5, DHMF5, BHMFs, and BHMFs, and so on.However, at present, there are still some problems such as harsh reaction conditions, poor selectivity of products, complex catalytic system and the difficulty of catalyst recovery and reuse.Therefore, it is very important to develop more efficient and moderate catalytic systems to solve the above problems and provide new methods and ideas for these elementary reactions.This paper is divided into the following parts: the first chapter mainly introduces the concept of biomass and platform molecules and the current development of biomass conversion to fuel;Then, the preparation of furfural and HMF and the most representative research progress of their conversion to chemical or fuel molecules are introduced in detail. Finally, the catalytic system and research progress in this paper are briefly introduced.In chapter 2, the method of preparing C _ 10 and C _ 12 furfural with HMF by self-carbon-carbon coupling reaction was introduced.Using montmorillonite supported thiazole ionic liquid and carbene formed by alkali as catalyst, the coupling of furfural and HMF was realized. The highest yield of C10 furfurin and 98% C12 furfural was obtained.The effects of different solvents on the reaction were investigated. It was found that the yield of the reaction was still high under the condition of no solvent.At the same time, the effect of different thiazole ionic liquids on the yield of the reaction was studied. It was found that the ionic liquids with electron donating groups on the thiazole ring had higher catalytic activity than those with electron absorbing groups.Finally, the reutilization performance of the supported catalyst was studied, and it was found that the yield of the catalyst was not significantly reduced after the reuse of the catalyst system for four times.In chapter 3, the method of selective oxidation of C _ 10 and C _ 12 furanyl diketones was introduced.Quaternary ammonium octamolybdate and quaternary ammonium decatungstate catalysts with typical Keggin structure were synthesized. Under mild conditions, 100% furfuryl yield and 94% BHMF yield were obtained.The possible reaction mechanism of quaternary ammonium octamolybdate was proposed. It was found that the catalytic activity of quaternary ammonium decatungstate catalyst was lower than that of quaternary ammonium octamolybdate catalyst in the selective oxidation of C 10 and C 12 furfurin.Compared with the traditional method, this method has the advantages of simple operation, friendly environment and recyclable catalyst.Chapter four summarizes the full text.To sum up, in this paper, the montmorillonite supported carbene catalytic system and the quaternary ammonium octamolybdate and decatungstate quaternary ammonium salt with typical Keggin structure were developed with the platform molecule furfural and HMF as the research objects.The green conversion process from platform molecules to different chemicals was realized. The effects of different catalysts on the activity and selectivity of the reaction were studied. The conversion and application of biomass based platform molecules were expanded.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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