【摘要】：高嶺石納米插層復(fù)合材料的研究成為材料科學(xué)中一個(gè)極富生命力的領(lǐng)域。一些極性小分子可以通過插層反應(yīng)進(jìn)入高嶺石層間并與其形成氫鍵,具有特定的空間取向,可實(shí)現(xiàn)分子的定向排列和自組裝。因此研究高嶺土插層反應(yīng)機(jī)理及復(fù)合物的微觀結(jié)構(gòu)在材料學(xué)和礦物學(xué)及物理、化學(xué)領(lǐng)域具有極大的實(shí)際意義和研究空間。但由于高嶺石特殊的層間結(jié)構(gòu)使其插層困難,目前國(guó)內(nèi)外的研究基本上還只是停留在制備和結(jié)構(gòu)表征階段,缺乏對(duì)于插層機(jī)理及機(jī)制的系統(tǒng)研究,對(duì)同種高嶺石采用多種插層劑制備得到的復(fù)合物進(jìn)行分析,便于系統(tǒng)的探討復(fù)合的熱分解過程,對(duì)插層機(jī)理進(jìn)一步補(bǔ)充和完善。本文以液相懸浮法直接插層得到高嶺石/甲酰胺和高嶺石/二甲基亞砜插層復(fù)合物,以機(jī)械力化學(xué)插層法和液相懸浮法制備得到高嶺石/乙酰胺插層復(fù)合物,以液相懸浮法和二次插層制備得到高嶺石/苯甲酰胺和高嶺石/甲醇插層復(fù)合物。采用X射線衍射(XRD)、傅立葉變換紅外光譜(FTIR)、熱分析(TG-DSC)等技術(shù)對(duì)復(fù)合物進(jìn)行結(jié)構(gòu)及性能的表征,探討復(fù)合物的熱分解過程,研究復(fù)合物的兩個(gè)分解階段與插層劑的分子量和沸點(diǎn)等的聯(lián)系,并對(duì)五種復(fù)合物的熱分析數(shù)據(jù)進(jìn)行對(duì)比,從而尋找插層劑屬性對(duì)復(fù)合物的影響規(guī)律。結(jié)果表明,插層的有機(jī)小分子與高嶺石內(nèi)表面形成氫鍵,高嶺石層間距擴(kuò)大,不同的插層劑形成的氫鍵結(jié)合方式以及層間距不同。有機(jī)酰胺插層劑分子與高嶺石層間的鍵合作用相同,胺基的H原子與高嶺石內(nèi)表面羥基上的O原子形成氫鍵;二甲基亞砜S=O鍵的氧原子與鋁氧八面體的氫原子形成氫鍵;甲醇中羥基的H原子與鋁氧八面體的氧原子形成氫鍵。插層劑脫嵌階段,不同基團(tuán)插層劑分子脫嵌溫度從大到小排列為:羥基成鍵氨基成鍵S=O成鍵。相同基團(tuán)的插層劑分子,分子量越大,脫嵌溫度越高,即苯甲酰胺乙酰胺甲酰胺。脫羥基階段,插層劑分子量越大,復(fù)合物脫羥基溫度越低,苯甲酰胺插層復(fù)合物脫羥基溫度最低,甲醇最高,但低于純高嶺石的脫羥基溫度。插層劑的脫嵌包含2個(gè)過程,氫鍵的打破和插層劑的擴(kuò)散。脫嵌反應(yīng)吸收熱與插層劑分子量大小成正比,苯甲酰胺分子量最大,反應(yīng)吸收熱最多,甲醇分子量最小,反應(yīng)吸收熱最少。
[Abstract]:The research of kaolinite nanointercalation composites has become a vital field in material science. Some polar small molecules can intercalate into kaolinite layers and form hydrogen bonds through intercalation reaction. They have special spatial orientation and can realize the orientation and self-assembly of molecules. Therefore, the study of the mechanism of kaolin intercalation reaction and the microstructure of the composite has great practical significance and research space in the fields of materials, mineralogy, physics and chemistry. However, because of the special interlayer structure of kaolinite, the intercalation of kaolinite is difficult. At present, the research at home and abroad is still mainly at the stage of preparation and structure characterization, and there is no systematic study on intercalation mechanism and mechanism. The composite prepared from the same kaolinite with various intercalators is analyzed, which is convenient to discuss the thermal decomposition process of the composite, and to further supplement and perfect the intercalation mechanism. In this paper, kaolinite / formamide and kaolinite / dimethyl sulfoxide intercalation complexes were prepared by liquid suspension method, and kaolinite / acetamide intercalation complexes were prepared by mechanochemical intercalation and liquid suspension. Kaolinite / benzoamide and kaolinite / methanol intercalation composites were prepared by liquid suspension and secondary intercalation. The structure and properties of the composites were characterized by X-ray diffraction (XRD), (XRD), Fourier transform infrared spectroscopy (TG-DSC) and (FTIR), thermal analysis (TG-DSC), and the thermal decomposition process of the composites was discussed. The relationship between the two decomposition stages of the complex and the molecular weight and boiling point of the intercalant was studied, and the thermal analysis data of the five complexes were compared to find out the influence of the properties of the intercalation agent on the complex. The results show that the intercalated organic small molecules form hydrogen bonds with the inner surface of kaolinite, and the interlayer spacing between kaolinite and kaolinite is enlarged, and the hydrogen bonding modes and interlayer spacing of different intercalators are different. The bond between organic amide intercalator molecule and kaolinite layer is the same. The H atom of amino group forms hydrogen bond with O atom on the inner surface of kaolinite, and the oxygen atom of dimethyl sulfoxide is formed hydrogen bond with hydrogen atom of aluminum oxide octahedron. The H atom of the hydroxyl group in methanol forms a hydrogen bond with the oxygen atom of the aluminium octahedron. In the deintercalation stage of the intercalator, the molecular desorption temperature of different group intercalators ranged from large to small as follows: hydroxyl bonding, amino bonding, Schio bonding. The higher the molecular weight and the higher the desorption temperature of the intercalator molecule of the same group, namely benzamide acetamide formamide. In the dehydroxylation stage, the higher the molecular weight of the intercalant, the lower the dehydroxyl temperature of the complex, the lowest and the highest methanol, but lower than the pure kaolinite. The deintercalation of intercalator consists of two processes, hydrogen bond breaking and intercalant diffusion. The absorption heat of deintercalation reaction is proportional to the molecular weight of the intercalant, the molecular weight of benzoamide is the largest, the absorption heat of reaction is the most, the molecular weight of methanol is the least, and the heat of reaction absorption is the least.
【學(xué)位授予單位】：中國(guó)礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB332

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