离子液体介入的烯类、乳酸酯类可再生资源的催化转化

发布时间：2017-12-27 11:44

本文关键词：离子液体介入的烯类、乳酸酯类可再生资源的催化转化　出处：《湖南师范大学》2016年硕士论文　论文类型：学位论文

【摘要】：随着石化资源的日益匮乏,如何将可再生资源转变成可用的化工产品已经成为了近十年来的研究热点之一。离子液体作为新型绿色介质、催化剂或助剂,在有机合成等领域已得到了广泛研究。茴香脑是我国盛产的茴香油可再生资源的重要组分。α-蒎烯是重要的可再生资源松节油的主要成分之一。乳酸乙酯可由葡萄糖或淀粉等发酵、酯化得到。因此,利用来源丰富的烯类、乳酸酯类可再生资源合成具有高附加价值的精细化工产品具有重要的意义。本论文研究了离子液体介入的茴香脑、α-蒎烯以及乳酸乙酯的催化转化,取得了良好的研究效果。主要内容如下:(1)通过水热法及沉淀法合成了纳微尺度铜金属有机框架材料催化剂并进行了FT-IR、TG及TEM表征。系统考察了催化剂、助剂、溶剂种类及用量等因素对茴香脑氧化制备茴香醛的影响。结果表明,以H3BTC(均苯三甲酸)为配体时制备的催化剂Cu-BTC-1性能较佳,两亲性咪唑类离子液体[C12mim]Cl有利于提高催化剂Cu-BTC-1的反应性能及稳定性。以Cu-BTC-1为催化剂、30%H2O2为氧化剂、丙酮为介质、5.0 mol%[C12mim]Cl为助剂,在最优条件下茴香脑的转化率为74.8%-91.5%,茴香醛的选择性达到93.5%-94.6%。纳微尺度Cu-BTC-1催化剂体现了良好的重复使用性能。(2)以乙酰丙酮氧钒为催化剂,30%H2O2为氧化剂,离子液体为助剂,研究了α-蒎烯直接合成水合蒎醇的反应。考察了离子液体、溶剂、温度、反应时间等因素对催化性能的影响。结果表明,[C4min]Cl/VO(acac)2/H2O2形成的反应体系具有氧化还原-Lewis酸双重催化功能,易使α-蒎烯经氧化、异构、水合等步骤得到水合蒎醇。在n(H2O2):n(α-蒎烯):n(VO(acac)2):n(离子液体)=2.5:1:0.01:0.03、丙酮为溶剂、30 oC反应6 h条件下,α-蒎烯转化率为91.2%,主要产物水合蒎醇与马鞭草烯酮的选择性分别为52.0%和13.6%。(3)通过置换法一步合成了系列可用于乳酸乙酯乙酰化反应的功能化氨基酸离子液体催化剂,并对催化剂进行了FT-IR以及1HNMR表征。采用单因素优化法得到适宜的反应条件为:以丙氨酸离子液体为催化剂,催化剂用量为乳酸乙酯的5.0 mol%,n(乳酸乙酯):n(乙酸酐)=1:1.2,回流反应6 h,目标产物乳酸乙酯乙酸酯收率为99.4%。
[Abstract]:With the increasing shortage of petrochemical resources, how to convert renewable resources into usable chemical products has become one of the hotspots of research in the past ten years. As a new type of green medium, catalyst or auxiliaries, ionic liquids have been widely studied in the field of organic synthesis. Aniseed is an important component of the renewable resources of fennel oil in China. Pinene is one of the main components of the important renewable resources of turpentine. Ethyl lactate can be fermented and esterified by glucose or starch. Therefore, it is of great significance to synthesize fine chemical products with high added value by using renewable resources of rich sources of alkenes and lactic acid esters. This paper studied the ionic liquids in anethole, alpha pinene and catalytic conversion of ethyl lactate, achieved good research results. The main contents are as follows: (1) the nano scale copper metal organic frame material catalyst was synthesized by hydrothermal method and precipitation method, and the characterization of FT-IR, TG and TEM was carried out. The effects of catalysts, auxiliaries, kinds and dosage of solvents on anisaldehyde production by anisaldehyde were investigated. The results showed that the Cu-BTC-1 prepared by H3BTC (benzene three carboxylic acid) as ligand had better performance, and the two affinity imidazolium ionic liquid [C12mim]Cl was beneficial to improve the performance and stability of Cu-BTC-1 catalyst. With Cu-BTC-1 as catalyst, 30%H2O2 as oxidant, acetone as medium and 5 mol%[C12mim]Cl as assistant, under optimal conditions, the conversion rate of aniseed is 74.8%-91.5%, and the selectivity of anisaldehyde reaches 93.5%-94.6%. The nano scale Cu-BTC-1 catalyst shows good reuse performance. (2) with vanadyl acetylacetonate as catalyst and 30%H2O2 as oxidant, ionic liquids as additives on the direct synthesis of alpha pinene sobrerol reaction. The effects of ionic liquid, solvent, temperature, reaction time and other factors on the catalytic performance were investigated. The results show that the [C4min]Cl/VO (ACAC) 2/H2O2 reaction system formed with -Lewis double acid redox catalytic function, the alpha pinene sobrerol obtained by oxidation and isomerization, hydration and other steps. In n (H2O2): n (alpha pinene): n (VO (ACAC) n (2): =2.5:1:0.01:0.03 ionic liquid), acetone as solvent, 30 oC 6 h reaction conditions, pinene conversion rate of 91.2%, the main products of selective sobrerol and Verbenone respectively. 52% and 13.6%. (3) a series of functional amino acid ionic liquid catalysts for acetylation of ethyl lactate were synthesized by one-step substitution. The catalysts were characterized by FT-IR and 1HNMR. The optimum reaction conditions were obtained by single factor optimization: alanine ionic liquid was used as catalyst, the amount of catalyst was 5 mol% of ethyl lactate, n (ethyl lactate): n (acetic anhydride) =1:1.2, reflux reaction was 6 h, and the yield of target product ethyl lactate was 99.4%.
【学位授予单位】：湖南师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36

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