蒙脱石复合固体碱的合成与表征及其催化Knoevenagel缩合反应研究

发布时间：2018-01-30 02:57

本文关键词： 蒙脱石合成与表征固体碱 Knoevenagel缩合反应　出处：《南昌航空大学》2016年硕士论文　论文类型：学位论文

【摘要】：蒙脱石是一种层状结构的铝硅酸盐粘土矿物,具有良好的电负性、离子交换性、分散悬浮性、吸附性和吸水性等特点,在催化领域得到广泛的应用。本文利用蒙脱石为原料,研发几种在Knoevenagel缩合反应中的固体碱催化剂,对催化剂的合成条件、结构关系和催化性能进行了系统的研究。既实现了该反应体系中的多相化,也实现了清洁工艺和生产,同时减少了环境污染。主要包括以下内容:(1)查阅大量文献,对固体碱催化剂材料和改性蒙脱石材料进行了综述,介绍了催化Knoevenagel缩合反应机理和改性蒙脱石的合成方法。(2)以蒙脱石、苯胺和FeCl3.6H2O为原料,合成蒙脱石/聚苯胺复合固体碱与磁性蒙脱石/聚苯胺复合固体碱,采用红外光谱、紫外可见漫反射光谱、XRD等对其结构进行了表征,利用熔点仪对催化反应后的产物熔点进行测定。利用蒙脱石/聚苯胺复合固体碱作为催化剂,通过催化Knoevenagel缩合反应的正交实验,从中找出最佳实验条件,并且对反应温度,催化剂用量,反应时间分别进行了研究实验。合成的2种催化剂在Knoevenagel缩合反应的重复实验中能够重复利用3次。(3)以蒙脱石和硝酸锂为原料,合成12种蒙脱石/硝酸锂复合固体碱,通过红外光谱、XRD、氮气等温吸附-脱附等对其结构进行了表征,通过熔点仪对催化Knoevenagel缩合反应后的产物熔点进行测定。利用400℃煅烧的蒙脱石/(0.2g)硝酸锂复合固体碱作为催化剂,通过催化Knoevenagel缩合反应的正交实验,从中找出最佳实验条件。对部分合成的蒙脱石/硝酸锂复合固体碱进行催化Knoevenagel缩合反应实验,其中400℃煅烧的蒙脱石/(0.2g)硝酸锂复合固体碱的催化效果最好,反应产物的收率为96.3%。利用合成的400℃煅烧的蒙脱石/(0.2g)硝酸锂复合固体碱催化剂对Knoevenagel缩合反应进行重复实验中,这种催化剂都可以重复利用3次。(4)以蒙脱石和氢氧化钠为原料,合成3种蒙脱石/NaOH复合固体碱,通过红外光谱、XRD、氮气等温吸附-脱附等对其结构进行了表征,通过熔点仪对催化Knoevenagel缩合反应后的产物熔点进行测定。当苯甲醛和丙二腈的物质的量比为10 mmol:10 mmol、反应时间1 h、反应温度60℃、催化剂用量0.1 g的条件下,利用合成的3种蒙脱石/NaOH复合固体碱作为催化剂,通过催化Knoevenagel缩合反应实验,其中550℃煅烧的蒙脱石/NaOH/CTAB固体碱的催化效果最好,反应产物的收率为88.2%。利用其中合成的2种催化剂对Knoevenagel缩合反应进行重复实验中,这2种催化剂都可以重复利用3次。(5)以蒙脱石、硫酸和3-氨丙基三甲氧基硅烷为原料,合成3种H-蒙脱石-NH2复合固体碱,通过红外光谱、XRD、热重分析等对其结构进行了表征,通过熔点仪对催化Knoevenagel缩合反应后的产物熔点进行测定。当苯甲醛和丙二腈的物质的量比为10 mmol:10 mmol、反应时间1 h、反应温度60℃、催化剂用量0.1 g的条件下,利用合成的3种H-蒙脱石-NH2复合固体碱作为催化剂,通过催化Knoevenagel缩合反应实验,其中(酸化2h)H-蒙脱石-NH2复合固体碱的催化效果最好,反应产物的收率为90.1%。利用其中合成的3种催化剂对Knoevenagel缩合反应进行重复实验中,这3种催化剂都可以重复利用3次。
[Abstract]:Aluminum silicate clay mineral montmorillonite is a layered structure, with good electronegativity, ion exchange, dispersed suspension, adsorption and absorption, has been widely used in the field of catalysis. Using montmorillonite as raw materials, in the development of several Knoevenagel and solid alkali catalyst reaction in the synthesis conditions the catalyst, catalytic performance and structure relationship were studied. The reaction system is realized in multi phase, also achieved a clean production process and at the same time, to reduce the environmental pollution. Mainly includes the following contents: (1) the literature review of solid base catalyst materials and modified montmorillonite materials the review introduces the synthesis method of Knoevenagel catalyzed condensation reaction mechanism and modified montmorillonite. (2) with montmorillonite, aniline and FeCl3.6H2O as raw materials, synthesis of montmorillonite / polyaniline composite with magnetic solid base The montmorillonite / PANI composite solid base, using infrared spectroscopy, UV Vis diffuse reflectance spectra and structure were characterized by XRD, the melting point after the catalytic reaction product was determined by melting point apparatus. Using montmorillonite as catalyst / polyaniline composite solid base, through the orthogonal experiment of catalytic Knoevenagel reaction, to find out the best experimental conditions from in the catalyst and the reaction temperature, dosage, reaction time were studied. Experiments can be repeatedly used 3 times repeated tests of 2 kinds of catalyst in Knoevenagel condensation reaction. (3) using montmorillonite and lithium nitrate as raw materials, synthesis of 12 kinds of lithium nitrate / montmorillonite composite solid base, through the infrared spectrum, XRD and nitrogen adsorption desorption were used to characterize its structure, the melting point of Knoevenagel catalytic condensation reaction after the products were determined by melting point apparatus using 400 calcined montmorillonite. Stone (0.2g) / lithium nitrate composite solid alkali as catalyst, through orthogonal experiment of catalytic Knoevenagel reaction, to find out the best experimental conditions from. On the part of the synthesis of lithium nitrate / montmorillonite composite solid alkali catalyst for Knoevenagel condensation reaction, including 400 calcined / montmorillonite (0.2g) had the best catalytic effect of lithium nitrate composite solid alkali reaction, the yield of the product was synthesized by montmorillonite 96.3%. 400 calcined / (0.2g) on Knoevenagel condensation reactions of lithium nitrate composite solid alkali catalyst repeated experiments, the catalyst can be reused 3 times. (4) using montmorillonite and sodium hydroxide as raw materials, synthesis of 3 kinds of montmorillonite /NaOH composite solid alkali and through the infrared spectrum, XRD, nitrogen adsorption desorption were used to characterize the structure of the product, melting point Knoevenagel after catalytic condensation reaction were determined by melting point meter when. Benzaldehyde and propylene nitrile two molar ratio of mmol:10 was 10 mmol, the reaction time is 1 h, the reaction temperature is 60 DEG C, the condition of catalyst is 0.1 g, as a catalyst synthesized by 3 kinds of montmorillonite /NaOH composite solid base, through the experiment of catalytic Knoevenagel condensation reaction, the catalytic effect of 550 calcined Montmorillonite Solid /NaOH/CTAB the best reaction products of alkali, the yield was 88.2%. with 2 kinds of catalysts on the synthesis of Knoevenagel condensation reaction to repeat the experiment, these 2 kinds of catalysts can be reused 3 times. (5) with montmorillonite, sulfuric acid and 3- aminopropyltrimethoxysilane as raw materials, synthesis of 3 kinds of H- montmorillonite -NH2 composite solid alkali and through the infrared spectrum, XRD and thermogravimetric analysis were used to characterize its structure, the melting point of Knoevenagel catalytic condensation reaction after the products were determined by melting point apparatus. When the benzaldehyde and propylene nitrile two molar ratio 10 mmol:10 mmol, the reaction time is 1 h, the reaction temperature is 60 DEG C, the condition of catalyst is 0.1 g, as a catalyst synthesized by 3 kinds of H- montmorillonite -NH2 composite solid base, through the experiment of catalytic Knoevenagel condensation reaction, in which (acidification 2H) had the best catalytic effect of H- montmorillonite -NH2 composite solid alkali, reaction product yield 90.1%. use the 3 kinds of catalysts on the synthesis of Knoevenagel condensation reaction to repeat the experiment, these 3 kinds of catalysts can be reused 3 times.

【学位授予单位】：南昌航空大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36

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