基于噻吩基膦的微孔有机聚合物的合成及性能表征

QIBEBT-IR > 先进有机功能材料研究组

	基于噻吩基膦的微孔有机聚合物的合成及性能表征
	陈祥会
导师	阳仁强
	2013-07
学位授予单位	中国科学院研究生院
学位授予地点	北京
学位专业	化学工程
关键词	微孔有机聚合物气体吸附后修饰三噻吩基膦
摘要	微孔有机聚合物具有较高的比表面积和永久孔道,在气体存储与分离、非均相催化、光电学等领域都有着广泛的应用。微孔有机材料具有低密度、高物理和化学稳定性、合成策略多样性等特点，而且通过将特殊的官能团或功能分子引入材料表面进行改性,从而增加了材料在气体吸附和催化等方面的应用，极大拓宽了应用范围。在本论文中将富电子的噻吩基团和极性的P=O, P=S键引入聚合物骨架，采用三噻吩基膦衍生物作为构筑单元，以1,3,5-三炔基苯为刚性连接单元合成了新型的功能化的含磷元素的微孔有机聚合物，并对其结构、孔道性质和气体吸附能力进行了表征。随后，在此基础上，以三聚硫氰酸和季戊四醇四(巯基乙酸)酯为交联剂，通过“点击”化学对已形成的聚合物网络结构进行后修饰，同时对其孔道性能和气体吸附能力进行了表征，探索了不同交联剂对聚合物孔道性质和气体吸附性能的影响，为以后对该类聚合物材料的后修饰提供了一定的试验和理论指导。本论文主要包括以下几个部分:第一章:关于微孔有机材料的文献综述。主要是对当前该领域研究的概述,介绍了微孔有机材料的研究背景，分类方法以及聚合物后修饰的方法。第二章:构建含有三噻吩基膦单元的微孔有机聚合物，对其结构进行了红外和固体核磁表征，着重对聚合物的孔道性质和气体吸附能力进行了深入探索。第三章:在上章构筑的微孔有机骨架基础上，应用硫醇-炔加成反应对已形成的聚合物进行后修饰，讨论了硫醇对聚合物骨架结构、孔道性质和气体吸附能力的影响。第四章:本论文总结。
其他摘要	Microporous organic polymers (MOPs) have potential applications as heterogeneous catalysts, gas storage and separation owing to their permanent porosity and large surface area. Compared with inorganic porous materials, MOPs have low density, high physiochemical stability and various synthetic stratergy. Additionally, microporous organic polymers can easily be modified by introducing of special functional groups or functional molecules to change their surface properties. As a result, the applications of MOPs including catalyst and gas storage have been greatly broadened. In this thesis, a new kind microporous organic polymer centered on phosphorus atom was synthesized with tri(2-thienyl)phosphine derivatives as building unit and 1,3,5-triethynylbenzene as rigid molecular linker. These polymers were designed by introducing polar organic groups (P=O and P=S) and electron-rich heterocyclic into the framework and their porosity characteristics and gas adsorption properties were also investigated. In addition, these polymer networks were modified with trithiocyanuric acid and pentaerythritol tetrakis(2-mercaptoacetate) by "click" chemistry and their porosity characteristics and gas adsorption properties were also explored. This provided a strategy to modify the polymer materials. The thesis mainly includes the following parts:Part 1. A general overview of the microporous organic materials was given, including the research background in this field, the classification of MOPs and the postmodification strategy for polymers.Part 2. Two novel functional porous polymers were synthesized from tris(2-bromo-5-thienyl)phosphine derivatives to give the corresponding networks, and their structure were characterized by FT-IR and Solid-State NMR. Besides, the porosity characteristics and gas capture properties were also explored.Part 3. Based on the polymer networks synthesized in part 2, the polymers were modified by thiol-yne reaction and the changes about porosity characteristics and gas adsorption properties after postmodification studied were also studied in detail.Part 4. The conclusions of the thesis.
作者部门	先进功能有机材料
学科领域	先进功能有机材料
公开日期	2013-07-13
学位类型	硕士
语种	中文
文献类型	学位论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/1514
专题	先进有机功能材料研究组
推荐引用方式 GB/T 7714	陈祥会. 基于噻吩基膦的微孔有机聚合物的合成及性能表征[D]. 北京. 中国科学院研究生院,2013.

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