羧基功能化离子液体催化α-蒎烯水合反应体系的研究

发布时间：2018-05-16 00:35

本文选题：羧基功能化离子液体 + α-蒎烯　；参考：《青岛科技大学》2017年硕士论文

【摘要】：在天然生物质资源松脂松节油的高值化利用中,α-蒎烯水合制备松油醇的反应具有重要的工业价值与研究意义。为了摒弃传统矿物酸催化产生大量废酸废水、控制条件严苛、产物处理繁琐等弊端,本文基于“环境友好催化”的理念,兼顾反应的有效性与分离的简易性,结合α-蒎烯一步水合法合成α-松油醇的反应体系特性,将羧基官能团(-COOH)引入离子液体结构加以修饰以优化其在α-蒎烯水合反应中的催化性能,同时以杂多酸阴离子调变其酸性,设计合成了多种兼具离子液体与杂多酸盐结构特征的羧基功能化离子液体催化剂。并且将其应用于α-蒎烯一步水合法合成α-松油醇的反应中,开发出三个富有新意的绿色催化工艺路线。采用核磁共振谱(~1HNMR)、傅里叶红外变换光谱(FT-IR)等方法对羧基功能化离子液体催化剂的结构进行了表征,用热重分析法(TGA)测试了其稳定性,并用正丁胺(n-BuNH_2)电位滴定方法测试了所合离子液体催化剂的酸强度与酸量,分别测试了各种催化剂在水/α-蒎烯中的溶解性,考察了催化剂的阴/阳离子部分对其酸性和溶解性能等理化性质的影响,探讨了催化剂的构效关系规律。将设计合成的一系列烷基咪唑类羧基功能化离子液体催化剂应用于催化α-蒎烯的水合反应中,实验结果表明,羧基及卤素基团的引入提高了松油醇的选择性,具有较高酸强度的羧酸功能化杂多酸式盐类催化剂[N-C_(14),N’-(CO_2H)_2-C_2H_2-I m-Br]_2HPW_(12)O_(40)催化效果较好。在催化剂用量0.25 mmol,水用量0.30 mol,α-蒎烯用量0.06 mol,70°C反应8 h的条件下,α-蒎烯转化率达89.4%,α-松油醇的选择性为30.1%,水合产物的总选择性达38.7%。且反应结束后静置,催化剂不溶于水相和油相,经过简单的倾析分离即可实现催化剂的回收再利用,并且表现出一定的重复使用性能。将羧基官能团引入到以苯并咪唑为有机阳离子母体环的离子液体结构中以合成多种苯并咪唑类的羧基功能化离子液体,并通过调控母体环上的烷基链长和结构以调变其催化性能,并且应用于α-蒎烯的水合反应,研究结果表明,短烷基链长的[C_6H_4-CH(Et)N_2-C_2H_3-(CO_2H)_2]H_2PW_(12)O_(40)具有较好的催化效果,α-蒎烯转化率达95.2%,α-松油醇的选择性为24.8%,水合产物的总选择性达31.6%。此外,该催化剂具有良好的重复使用性,在循环利用5次后仍保持较高的催化活性。基于α-蒎烯水合反应中水油两相互不相溶的特性,本文还设计合成了同时具有表面活性和酸性的十八胺聚醚型羧基功能化离子液体催化剂。以卤代羧酸为羧基供体,磷钨酸/硫酸为阴离子酸式基团,合成了一系列不同聚合度n(离子液体结构中亚乙氧基单元的个数)的羧基功能化离子液体催化剂。发现该类催化剂表现出一定的表面活性作用,反应体系在反应温度(80°C)下呈微乳相,增加了底物分子间的有效碰撞几率,获得较高的转化率,但在反应结束后催化剂自分离性较差。催化剂[AC1870-CH_2COOH]H_2PW_(12)O_(40)在无辅助催化剂的条件下,达到68.1%的转化率和25.5%的α-松油醇选择性。为聚醚型羧酸功能化离子液体催化α-蒎烯的水合反应提供了依据。本文旨在探寻无需氯乙酸等有机酸辅助催化的α-蒎烯水合反应清洁化催化体系,为生物质松节油资源的环境友好催化工艺提供了新思路。
[Abstract]:In the high value utilization of natural biomass pines and turpentine, the reaction of alpha pinene hydration to produce pine oleol has important industrial value and research significance. In order to abandon the traditional mineral acid catalysis to produce a large amount of waste acid waste water, the control conditions are harsh, the product is tedious and so on. Based on the concept of "environmental friendly catalysis", this paper is based on the concept of "environmental friendly catalysis" The effectiveness of the reaction and the simplicity of the separation are combined with the reaction system characteristics of alpha pinene one step water method to synthesize alpha pinyl alcohol. Carboxyl functional group (-COOH) is introduced into the ionic liquid structure to optimize its catalytic performance in the hydration reaction of alpha pinene. At the same time, the acidity is modulated with heteropoly anions, and a variety of concurrently is designed and synthesized. The carboxyl functionalized ionic liquid catalyst with the structural characteristics of ionic liquids and heteropoly salts was used in the reaction of alpha pinene one step water to synthesize alpha pinicol. Three new green catalytic process routes were developed. The function of carboxyl group by nuclear magnetic resonance spectroscopy (~1HNMR), Fu Li Ye Hongwai transform spectroscopy (FT-IR) and other methods The structure of the ionic liquid catalyst was characterized. The stability was measured by TG (TGA). The acid strength and acid content of the ionic liquid catalyst were measured by n-BuNH_2 potentiometric titration. The solubility of various catalysts in water / alpha pinene was tested, and the anion / cation part of the catalyst was investigated. A series of alkyl imidazole carboxylic functionalized ionic liquids were used to catalyze the hydration reaction of alpha pinene. The experimental results showed that the introduction of carboxyl and halogen groups increased the selectivity of the olefinol. [N-C_ (14), N '- (CO_2H) _2-C_2H_2-I m-Br]_2HPW_ (12) O_ (40) catalyzed by carboxylic acid with high acid strength, with 0.25 mmol, 0.30 mol, 0.06 mol for alpha pinene and 8 h for 70 - C reaction, the conversion of alpha pinene is 89.4%, and the selectivity of alpha pinyl alcohol is 30.1%, hydration is 30.1%. The total selectivity of the product is 38.7%. and the catalyst is stationary after the end of the reaction. The catalyst is insoluble in the water and oil phases. After a simple dipping separation, the catalyst can be reused and reused, and a certain reuse performance is shown. A variety of benzimidazole carboxylic functionalized ionic liquids are used to modulate their catalytic properties by regulating the length and structure of the alkyl chain on the parent ring, and applied to the hydration reaction of alpha pinene. The results show that the short alkyl chain long [C_6H_4-CH (Et) N_2-C_2H_3- (CO_2H) _2]H_2PW_ (12) O_ (40) has a better catalytic effect and the conversion of alpha pinene. The conversion rate is 95.2%, the selectivity of alpha pininol is 24.8%, the total selectivity of the hydrated product is 31.6%.. The catalyst has good reusability and remains high catalytic activity after 5 cycles. Based on the insoluble specificity of water oil two in the hydration reaction of alpha pinene, this paper also designs and syntheses the surface activity at the same time. With the acidic eighteen amine polyether carboxylic functionalized ionic liquid catalyst, a series of carboxyl functionalized ionic liquid catalysts with different degrees of polymerization, n (number of central ethoxy units in ionic liquids), were synthesized with halogenated carboxylic acids as carboxyl donors and phosphotungstic acid / sulfuric acid as anionic group. The reaction system is microemulsion at the reaction temperature (80 C), increasing the effective collision probability between the substrate molecules and obtaining a higher conversion rate, but the catalyst has a poor self separability after the reaction. The catalyst [AC1870-CH_2COOH]H_2PW_ (12) O_ (40) reaches 68.1% conversion and 25.5% under the condition of no auxiliary catalyst. The selectivity of alpha pinool provides a basis for the hydration of alpha pinene catalyzed by polyether carboxylic acid functional ionic liquids. The purpose of this paper is to explore a clean catalytic system for the hydration of alpha pinene without the aid of organic acids such as chloroacetic acid, which provides a new idea for the friendly catalytic process of the environment of biomass turpentine.

【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.3

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