两种酚类表面印迹聚合物的制备及其环境分析应用

发布时间：2018-06-06 02:24

本文选题：酚类污染物 + 表面分子印迹　；参考：《河南师范大学》2017年硕士论文

【摘要】：酚类化合物作为有机中间体和化学原料被广泛应用于煤气发生站、焦化、炼油、医药、农药、油漆、木材防腐等工业生产过程。尽管这些含酚类工业的发展给人类生活提供了便利,但由于酚类物质是一种环境激素,可以长时间在生物体内蓄积,并且可以通过呼吸道、皮肤组织以及消化系统进入到人体内,低浓度时可以经过生物蓄积引起慢性中毒,高浓度时可以导致急性中毒以及昏迷死亡。因此酚类物质以其生物毒性大及持久性强的特性对环境造成危害。酚类污染物在环境中大多以痕量存在,并且与多种物质共存,使得现有的检测技术很难进行直接准确定量。而借助于高效、便捷和抗干扰的前处理手段,是实现对复杂环境体系中痕量酚类污染物直接分析检测的有效途径,这对于保护人体健康和环境生态都有着重要的意义。分子印迹聚合物(Molecularly Imprinted Polymer,MIP)作为一种新型的吸附剂材料,具有特异识别性高、性能稳定、再生性良好、抗干扰能力强等优势,近年来作为有效的样品前处理材料,在多个领域得到了应用。但是,传统方法中分子印迹聚合物大多在高毒性有机溶剂中制备,对人体健康造成危害,同时污染环境。因此,近年来越来越多的学者致力于研究能够使用环境友好型溶剂、工艺简单的分子印迹聚合物制备方法。近年来发展起来的溶胶凝胶技术,可以在无水乙醇、水等强极性溶剂中反应,并且制备工艺简单、成本低廉。本文利用表面分子印迹与溶胶凝胶相结合的技术,分别以活化硅胶和磁性硅胶为载体,在无水乙醇中制备了2,4-二硝基苯酚和2,4,6-三氯苯酚表面分子印迹聚合物。采用红外光谱扫描、电镜扫描、比表面积分析、综合热分析等手段对聚合物的微观结构以及外貌形态进行了表征;通过静态吸附实验,探讨印迹聚合物的吸附模型与吸附性能;联合高效液相色谱检测技术,考察了两种印迹聚合物对实际环境样品中2,4-二硝基苯酚和2,4,6-三氯苯酚的选择性分离富集吸附性能。主要内容如下:1、概述了酚类化合物的用途、污染范围、危害以及分析检测方法;查阅分子印迹技术的发展以及现状,具体介绍了分子印迹聚合物的制备方法以及原理;介绍了表面分子印迹技术和溶胶凝胶技术的特点以及发展前景。2、采用表面分子印迹与溶胶凝胶技术相结合的技术,在无水乙醇中制备了2,4-二硝基苯酚(2,4-DNP)和2,4,6-三氯苯酚(2,4,6-TCP)两种酚类表面印迹聚合物。通过红外光谱扫描、电镜扫描、比表面积分析、综合热分析等手段对聚合物的外貌形态以及微观结构进行表征,并探讨两种酚类表面印迹聚合物对目标物的特异性识别机理。3、利用单因子变量法,考察了两种酚类表面印迹聚合物的吸附等温线、吸附动力学和选择性吸附性能等参数。结果显示,MIP_(2,4-DNP)和NIP2,4-DNP对2,4-二硝基苯酚吸附均符合Langmuir吸附模型,而MIP2,4,6-TCP和NIP_(2,4,6-TCP)对2,4,6-三氯苯酚的吸附过程分别符合Langmuir和Freundlich吸附模型,两种酚类表面印迹聚合物对模板底物的吸附过程均符合伪二级动力学模型,以化学吸附为主。4、通过静态吸附实验,对两种表面印迹聚合物的特异吸附性能进行了考察。结果显示,在复杂体系中,两种酚类表面印迹聚合物都具有很强的抗干扰能力,MIP_(2,4-DNP)对2,4-二硝基酚的去除率可以达到90%左右,而NIP2,4-DNP对2,4-二硝基酚的去除率小于48%;MIP2,4,6-TCP对2,4,6-三氯苯酚的去除率为25%左右,相应的NIP_(2,4,6-TCP)对2,4,6-三氯苯酚的去除率为15%左右。5、基于以上的研究内容,对本论文做出了总结,并针对分子印迹技术的局限性和发展空间进行了展望。
[Abstract]:Phenolic compounds are widely used as organic intermediates and chemical materials in the industrial production process of gas generating stations, coking, refining, medicine, pesticides, paints, and wood preservation. Although the development of these phenolic industries provides convenience for human life, the phenols are a kind of environmental hormone, which can be stored in organisms for a long time. Product, and can enter into the human body through the respiratory tract, skin tissue and digestive system. Low concentration can cause chronic poisoning through biological accumulation. High concentration can lead to acute poisoning and coma and death. Therefore, phenols are harmful to the environment with their biological toxicity and persistent strong characteristics. Phenols are in the ring. The existence of trace amounts and coexistence with a variety of substances makes the existing detection techniques difficult to direct and accurate quantitative. With the help of efficient, convenient and anti-interference pretreatment methods, it is an effective way to realize the direct analysis and detection of Trace Phenolic Pollutants in the complex environment system, which is to protect human health and environment. Molecularly Imprinted Polymer (MIP), as a new type of adsorbent material, has the advantages of high specificity, stable performance, good reproducibility and strong anti-interference ability. As an effective sample front material, it has been applied in many fields in recent years. However, the traditional method has been used in many fields. Most of the medium molecularly imprinted polymers are prepared in highly toxic organic solvents, causing harm to human health and polluting the environment. Therefore, in recent years, more and more scholars have been devoted to the study of the preparation methods of molecular imprinted polymers, which can be used to use environmentally friendly solvents and have simple processes. 2,4- two nitrophenol and 2,4,6- three chlorophenol surface molecularly imprinted polymer was prepared in anhydrous ethanol by using the technology of surface molecular imprinting and sol-gel, using activated silica gel and magnetic silica gel as the carrier, and the surface molecularly imprinted polymer of two nitrophenol and 2,4,6- chlorophenol was prepared in this paper. The microstructure and morphology of the polymer were characterized by spectral scanning, electron microscope scanning, specific surface area analysis and comprehensive thermal analysis. The adsorption model and adsorption properties of the imprinted polymers were investigated by static adsorption experiments. The combined high performance liquid chromatography (HPLC) was used to investigate two kinds of imprinted polymers on the actual environmental samples 2. The selective separation and adsorption properties of 4- two nitrophenol and 2,4,6- three chlorophenol are concentrated and enriched. The main contents are as follows: 1, the use of phenolic compounds, the scope of pollution, the damage and the analysis and detection methods are summarized. The development and present situation of molecular imprinting technology are reviewed, and the preparation methods and principles of the molecularly imprinted polymers are introduced and the tables are introduced. The characteristics and development prospect of surface molecularly imprinted technique and sol-gel technology.2, two kinds of phenols of 2,4- two nitrophenol (2,4-DNP) and 2,4,6- three chlorophenol (2,4,6-TCP) were prepared by combination of surface molecularly imprinting and sol-gel technology in anhydrous ethanol. Surface area analysis and comprehensive thermal analysis were used to characterize the morphology and microstructure of the polymer. The specific recognition mechanism of two phenols surface imprinted polymers on the target was investigated. The adsorption isotherm, adsorption kinetics and selective adsorption of two phenols were investigated by single factor variable method,.3. The results show that the adsorption of 2,4- two Nitrophenol by MIP_ (2,4-DNP) and NIP2,4-DNP conforms to the Langmuir adsorption model, while the adsorption process of MIP2,4,6-TCP and NIP_ (2,4,6-TCP) to 2,4,6- three chlorophenol is in accordance with the Langmuir and Freundlich adsorption model, and the adsorption process of the two phenolic surface imprinted polymers on the template substrate is all in character. The pseudo two kinetics model was used to study the specific adsorption properties of two kinds of surface imprinted polymers by chemical adsorption.4. The results showed that in the complex system, two kinds of phenolics surface imprinted polymers had strong anti-interference ability, and the removal rate of MIP_ (2,4-DNP) to 2,4- was reached. About 90%, the removal rate of NIP2,4-DNP for 2,4- is less than 48%, and the removal rate of MIP2,4,6-TCP for 2,4,6- three chlorophenol is about 25%, and the corresponding NIP_ (2,4,6-TCP) removal rate of 2,4,6- three chlorophenol is about 15%.5. Based on the above research content, this paper is summarized, and the limitations and development of molecular imprinting technology are discussed. The space is prospected.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ424;X830

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