【作者】 张栓红；

【导师】 曲荣君；

【作者基本信息】 鲁东大学 ， 高分子化学与物理， 2011， 硕士

【摘要】 聚合物包覆硅胶是一类新型有机-无机复合材料,同时具有硅胶和聚合物的优良性能及某些新特性,在材料领域尤其是吸附材料领域中有重要的用途。用分子印迹技术在硅胶表面包覆聚合物,可以得到对金属离子及有机物具有特异性吸附性能的新型吸附材料。本文采用硅胶表面聚合法及硅胶表面分子印迹技术制备了八种新型聚合物包覆硅胶吸附材料。利用扫描电镜、红外光谱、孔结构分析、热重分析等方法对材料的结构和性质进行了系统表征,并系统研究了其对有机化合物的吸附性能。以乙烯基三乙氧基硅烷改性硅胶为中心核,分别以苯乙烯(St)和4-乙烯吡啶(4-VP)为功能单体,二乙烯基苯(DVB)为交联剂,通过硅胶表面的交联聚合,得到四种核-壳结构的聚合物包覆硅胶材料——聚苯乙烯包覆硅胶(PS/SG)、聚硝基化苯乙烯包覆硅胶(PS-NO2/SG)、聚胺基化苯乙烯包覆硅胶(PS-NH2/SG)和聚乙烯吡啶包覆硅胶(PVP/SG)。考察了四种新型吸附材料在水溶液中对有机小分子苯胺及苯酚的静态饱和吸附,着重研究了其对苯胺的吸附性能。结果表明,在本实验条件下,四种吸附材料对苯胺的吸附优于对苯酚的吸附;PS/SG,PS-NO2/SG,PVP/SG对苯胺的吸附符合Freundlich等温吸附方程式;四种吸附剂对苯胺的吸附均可以用拟二级动力学方程进行较好描述,吸附过程中存在粒内扩散,但不是唯一的控制因素,吸附可能同时受液膜扩散的影响。研究了上述四种聚合物包覆硅胶吸附材料在水体系和非水体系(包括无水乙醇溶液、苯溶液、环己烷溶液等)中对酚类(苯酚、对甲基苯酚、对硝基苯酚)和胺类(苯胺、N-甲基苯胺、对硝基苯胺)的吸附性能,分析了其吸附性能之间的差异及原因。考察了不同温度下PS/SG对水溶液中N-甲基苯胺的吸附性能,实验结果表明,其吸附过程能较好的用拟二级动力学方程进行描述,并符合Freundlich吸附等温方程式;热力学参数分析结果表明,吸附是自发的、放热的吸附过程,降低温度有利于吸附的进行。以乙烯基改性硅胶为中心核,DVB为交联剂,4-乙烯吡啶为功能单体,分别以N-甲基苯胺及甲基苯丙胺(冰毒)为模板分子,通过表面分子印迹技术,合成了硅胶表面分子印迹聚合物材料。实验结果表明,印迹材料对目标分子表现出优异的吸附性能。尤其是甲基苯丙胺分子印迹材料,将其作为固相萃取柱,可以从氯胺酮、甲基苯丙胺和咖啡因等兴奋剂混合体系中有效提取甲基苯丙胺,为新型提取苯丙胺类兴奋剂担体材料的研制提供了新思路。更多还原

【Abstract】 Polymer coated silica adsorption materials, with excellent performance of silica gel and polymer, and even some new properties, are a kind of organic-inorganic composite material. These materials have potential applications in material fields, especially in adsorption fields. Using molecular imprinting technique can obtain novel polymer-coated silica that has specificity adsorption for metal ions and organic compounds. This thesis has designed and prepared eight novel polymer-coated adsorption materials by means of surface polymerization and molecular imprinting on silica. These adsorption materials were systematically characterized by Scanning electron microscopy（SEM）, infrared spectroscopy （FT-IR）, porous analysis, and thermogravimetry analysis. And adsorption properties of these materials towards organic compounds were investigated.Using modified silica as core, 4-vinylpyridine as functional monomer,divinylbenzene as crosslinking agent, respectively, four novel polymer-coated silica materials, including polystyrene-coated silica （PS/SG）, poly（p-nitrostyrene）-coated silica （PS-NO2/SG）, poly（p-aminostyrene）-coated silica （PS-NH2/SG） and poly（4-vinylpyridine）-coated silica （PVP/SG）, were synthesized by means of polymerization on the surface of silica. Some organic compouds, such as phenol and aniline, were chosen as representatives to investigate static saturated adsorption. The main research focuses on the adsorption properties of aniline. The experimental results showed that the adsorption of aniline prior to phenol for the four adsorption materials in the range of the experiment. The adsorption isotherms results showed that linear Freundlich isotherm models could be well interpret the adsorption of three adsorption materials, PS/SG, PS-NO2/SG, PVP/SG, for aniline. The kinetics data indicated that the adsorption process was governed by the film diffusion and the intraparticle diffusion and well followed pseudo-second-order rate model.Adsorption performance of PS/SG, PS-NO₂/SG, PS-NH₂/SG, PVP/SG to phenolic substances （including phenol, p-methyl phenol, p-nitrophenol） and amine compounds（including aniline, N - methyl aniline, p- nitroaniline） from aqueous solution and nonaqueous solutions（including anhydrous alcohol solution, benzene solution and cyclohexane solution） was investigated in order to analysis the reason of the differences among these adsorption materials. The adsoption towards N- methyl aniline of PS/SG in different temperature was studied. The kinetic adsorption results showed that the adsorption process of PS/SG for N-methyl aniline was well followed pseudo-second-order rate model. The adsorption isotherms results showed that Freundlich models could be well interpret the adsorption of PS/SG for N- methyl aniline. Thermodynamic analysis revealed that the adsorption behaviors of N- methyl aniline on PS/SG could be considered as spontaneous,exothermic sorption process, resulting in their higher adsorption capacities at lower temperature.Using vinyl modified silica as the core, divinylbenzene as crosslinking agent, 4-vinylpyridine as functional monomer, N- methyl aniline and methamphetamine as the template, respectively, molecularly imprinted polymers were synthesed by surface of molecular imprinting technique. The experiments results showed that molecularly imprinted polymers showed excellent adsorption performance to the template, especially methamphetamine molecular imprinted on surface of silica. Using it as solid-phase extraction materials, the methamphetamine can be extracted from the complex system, including ketamine, caffeine exist and methamphetamine, which provides novel supporter materials for extracting amphetamine-derived drugs.更多还原