【作者】 王辉；

【导师】 徐铜文；

【作者基本信息】 中国科学技术大学 ， 应用化学， 2010， 硕士

【摘要】 有机-无机杂化是通过共混法、原位聚合法、溶胶-凝胶法等在有机网络中引入无机质点,从而将有机组分与无机组分良好的结合起来。因此有机-无机杂化膜兼具了有机膜与无机膜的优点,膜的机械性能得到增强,热稳定性和耐溶剂性能都大大提高。另一方面,将有机-无机杂化材料应用于离子膜领域,改善了离子膜在高离子交换容量时,高溶胀的性质。同时由于无机组分的引入,膜的渗透、选择性也可能得到很大程度的改进。因此近年来得到快速发展。本文利用溶胶-凝胶（sol-gel）以及共混法,制备了有机-无机杂化非离子膜和有机-无机杂化阳离子交换膜,并测试了膜的一些基本物理化学性能,特别的对于杂化阳离子交换膜,首次将其应用于扩散渗析回收碱的应用方面。主要的实验过程和实验数据如下:（1）以乙二胺（EDA）、氯甲基三乙氧基硅烷（CMTES）和聚乙烯醇（PVA）为原料,首先通过EDA和CMTE制备小分子多硅化合物,之后通过溶胶-凝胶法与PVA反应制备杂化膜。考察了CMTES的含量以及溶剂、催化剂对成膜性能的影响。通过热分析仪（TG-DSC）、扫描电子显微镜（SEM）和机械性能等测试了膜的物理化学性能和热稳定性,并将膜尝试应用在渗透汽化分离乙醇/水体系中。实验结果表明,选用KOH作为催化剂,乙醇作为溶剂制得的杂化膜表现出较好的物理化学性能。（2）以丙烯酸（AA）、γ-甲基丙烯酰氧基丙基三甲氧基硅烷（γ-MPS）和聚乙烯醇（PVA）为原料通过溶胶-凝胶反应制备多硅共聚杂化阳离子交换膜,考察了不同含量的共聚物poly（AA-co-γ-MPS）对膜性能的影响。该系列膜具有较好的热稳定性（热降解温度为264-270℃）和机械性能。并且随着共聚物含量的增加,膜的亲水性逐渐下降（81.6 - 70.8%）,离子交换容量却逐渐上升（0.76– 0.90 mmol/g）。最后将膜应用于扩散渗析分离NaOH和Na₂WO₄体系,表现出了较好的分离效果（渗析系数:0.010-0.042m/h）。在35℃时,使用含poly（AA-co-γ-MPS）质量分数50%的杂化膜进行扩散渗析试验,分离因子达到95.7。（3）以丙烯酸（AA）、γ-甲基丙烯酰氧基丙基三甲氧基硅烷（γ-MPS）和磺化聚苯醚（SPPO）为原料通过共混法制备阳离子交换膜,考察不同SPPO含量对膜性能的影响。探讨膜在分离碱体系方向上的应用可行性。更多还原

【Abstract】 There have been many methods for introducing the inorganic particles into organic network to achieve hybrid, such as blending, sol-gel and in-situ polymerization. In this hybrid, organic components and inorganic components can combine with each other well. Thus, the hybrid materials may own the merits of both the organic and inorganic material, such as high mechanical, chemical and thermodynamic stabilities. When hybrid materials are used for preparation of ion-exchange membranes, the high swelling performance following with high ion exchange capacities （IEC_p） should be settled. On the other hand, the membrane permeability and selectivity can be improved because of the introduction of inorganic components. Therefore, organic-inorganic hybrid materials are developing rapidly these years.In the thesis, we have prepared several organic-inorganic non-ion exchange hybrid membranes, as well as some cation exchange hybrid membranes, through the sol-gel process and blending. Some physical and chemical properties of test were carried out. Especially for the cation exchange hybrid membranes, they were firstly used to recover sodium hydroxide from the mixture of NaOH and Na2WO4 through diffusion dialysis （DD）. The main experiment and data are as following:（1） A type of hybrid membranes were prepared using the ethylenediamine （EDA）, chloromethyl triethoxysilane （CMTES） and poly （vinyl alcohol） （PVA）. Firstly, multi-alkoxy silicon small molecular was synthesized through EDA and CMTES. Then the sol-gel process was carried out between PVA and the multi-alkoxy silicon small molecular. The experimental conditions, such as the content of the silicon, the solvent and catalyst, have been investigated. The thermal, mechanical and chemical stabilities of the membranes, as well as the pervapration performance, were investigated. As a result, the membrane produced with catalyst potassium hydroxide and solvent ethanol exhibited the better properties.（2） Organic-inorganic cation exchange hybrid membranes have been prepared through sol-gel reaction of poly (acrylic acid -co-methacryloxypropyl trimethoxy silane （poly （AA-co-γ-MPS）） in presence of poly （vinyl alcohol） （PVA）. The effect of the content of the polymer poly （AA-co-γ-MPS） to the membrane was investigated. The membranes have good thermal stabilities and the Td values are in the range of 264 - 270°C. With increasing poly（AA-γ-MPS） content, water content （W_R） gradually decreases from 81.6% to 70.8% while the practical cation exchange capacities （IEC_P） increases from 0.76 mmol/g to 0.90 mmol/g. The hybrid membranes have been used to recover sodium hydroxide from the mixture of NaOH and Na₂WO₄ through diffusion dialysis （DD）. The dialysis coefficient of OH^- （UOH）, as well as the separation factor （S）, is at high level （ UOH: 0.010– 0.042m/h）. The hybrid membrane containing 50wt% poly（AA-co-γ-MPS） has the highest separation factor of 95.7 at 35°C.（3） A type of hybrid membrane were prepared using acrylic acid （AA）, methacryloxypropyl trimethoxy silane （γ-MPS） and sulfonated poly （2,6-dimethyl-1,4-phenylene oxide） （SPPO）. The effect of the blending mode and the content of SPPO were investigated. Some test was carried out, and the feasibility of application in alkali recovery was discussed.更多还原