目前，我国面临的水污染问题日益加剧，这已经成为影响社会经济发展和民生安全的一个重要难题。化学型污染物主要分为亲水型和疏水型，亲水型污染物会与水相互作用，很难彻底去除；而疏水型污染物主要为油类污染物，进入水体后浮于水面会破坏复氧条件。吸附由于操作简便、净化效果好和成本低等特点，被认为是废水处理领域最有潜力的技术之一。近几年，多孔材料由于其特殊的孔道结构，已被广泛用于污染物吸附方面。但目前开发的多孔材料吸附剂普遍存在着吸附速率慢和吸附容量低等问题，同时对不同类型的污染物实现高选择性的分离也面临着巨大挑战。

本论文旨在开发一种具有特定功能位点的超分子多孔材料，在小分子组装单体中引入特定的功能位点，以超分子定向识别作用构筑孔道，通过组装形成稳定的二维多孔框架，并通过交联聚合使二维框架卷曲形成稳定的囊泡有机框架以解决吸附技术中吸附速率慢和吸附容量低等问题。具体的研究内容如下：

小分子单体的合成。用酰氯法和酸胺缩合法成功制备了均苯三甲酰胺分子（TMPTA）；设计了一种由聚乙二醇单甲醚（mPEG）修饰的苯三甲酰胺分子。改变了TMPTA分子骨架的疏水性，增加了分子与水的亲和性。并通过六步有机合成反应调控聚乙二醇的嵌段长度成功合成了两种聚乙二醇单甲醚修饰的均苯三甲酰胺甲基吡啶分子:（mPEG-TMPTA），一种是（四乙二醇单甲醚）-TMPTA分子（mPEG4-TMPTA），一种是（三乙二醇单甲醚）-TMPTA分子 (mPEG3-TMPTA）；通过核磁共振（NMR）/质谱（MS）等表征手段，进行了结构分析，确认已经将设计分子成功合成。

将合成的mPEG-TMPTA与TMPTA在乙腈（ACN）溶剂中进行共组装。通过核磁滴定的方法，调控mPEG-TMPTA与TMPTA共组装比例，发现两者比例为1：5时结构最稳定性能最佳；通过加入交联剂，二维平面的共组装胶体表面电荷排斥作用聚合得到稳定的超分子多孔囊泡结构。

利用聚合物的空心囊泡、高的比表面积以及表面密集的阳离子吸附位点和高亲水性，对水中阴离子污染物甲基橙（MO）和直接橘黄（CP）以及油性物质苯乙酮（AP）和石油醚（PE）进行吸附实验。结果表明相较均苯三甲酰胺分子聚合物（P-TMPTA），由两种分子共组装胶体所得到的不同嵌段长度的聚合物（P-PEGTT）对阴离子污染物的吸附效率更高，特别是由mPEG4-TMPTA与TMPTA分子组装聚合得到的聚合物（P-PEG⁴TT）不仅具有较大的吸附容量，并且吸附亲水性速率显著提高，是P-TMPTA的10倍。而由mPEG3-TMPTA与TMPTA分子组装聚合得到的聚合物（P-PEG³TT）的吸附速率是P-TMPTA的 6

 

倍。说明通过调节小分子的嵌段长度会对吸附亲水性污染物速率产生影响。该材料（P-PEGTT）的结构上带有亲疏水性质的PEG链段，实现了对亲水性阴离子污染物的高吸附速率和高吸附容量；另外对油类污染物也具备吸附性能以及存储功能。吸附MO和CP更符合伪二阶动力学模型和Langmuir模型，粒子内扩散模型指出吸附过程受到多种因素控制。

综上，这种具有聚乙二醇嵌段的聚合物吸附剂在亲水性污染物的吸附中具有较为优异的性能，对于油性物质的吸附也具有较好的应用前景，为超分子聚合物作为吸附剂应用于水污染的处理和发展提供了理论依据和实际应用意义。

At present, China is facing increasing water pollution problems, which has become an important problem affecting socio-economic development and livelihood security. Chemical pollutants are mainly divided into hydrophilic and hydrophobic, hydrophilic pollutants will interact with water, it is difficult to completely remove; while hydrophobic pollutants are mainly oil pollutants, enter the water body floating on the water surface will destroy the conditions of reoxygenation. Adsorption is considered to be one of the most promising technologies in the field of wastewater treatment due to its easy operation, good purification effect and low cost. In recent years, porous materials have been widely used in pollutant adsorption due to their special pore structure. However, the currently developed adsorbents with porous materials generally suffer from slow adsorption rates and low adsorption capacities, as well as the great challenge of achieving highly selective separation of different types of pollutants.

The aim of this thesis is to develop a supramolecular porous material with specific functional sites, introduce specific functional sites in small molecule assembled monomers, construct pore channels by supramolecular directed recognition, form stable two-dimensional porous frameworks by assembling, and curl the two-dimensional frameworks to form stable vesicular organic frameworks through cross-linking polymerization to solve the problems such as low adsorption efficiency, adsorption rate and adsorption capacity in adsorption technology. The specific research contents are as follows:

Synthesis of small molecule monomer. TMPTA was successfully prepared by acyl chloride method and acid amine condensation method；a phenyltrimethoxyamine molecule modified by polyethylene glycol monomethyl ether (mPEG)was designed. It changes the hydrophobicity of the molecular backbone of TMPTA and increases the affinity of the molecule for water. And two kinds of polyethylene glycol monomethyl ether modified phenyltrimethoxyamine methyl pyridine molecules were successfully synthesized through modulating the block length of poly(ethylene glycol)through a six-step organic synthesis reaction: (mPEG-TMPTA), one is(tetraethylene glycol monomethyl ether)-TMPTA molecule (mPEG4-TMPTA), and the other is( triethylene glycol monomethyl ether)-TMPTA molecule (mPEG3-TMPTA)；through nuclear magnetic resonance (NMR)/mass spectrometry (MS) and other characterization means, the structure analysis was carried out to confirm that the designed molecule has been successfully synthesized.

The synthesized mPEG-TMPTA was co-assembled with TMPTA in acetonitrile (ACN) solvent. The co-assembly ratio of mPEG-TMPTA and TMPTA was regulated by NMR titration, and it was found that the structure was most stable with the best performance when the ratio of the two was 1:5；by adding cross-linking agent, the surface charge repulsion of the co-assembled colloid in the two-dimensional planes polymerized to obtain the stabilized supramolecular porous vesicle structure.

Adsorption experiments were carried out on the anionic pollutants methyl orange (MO) and direct cellulite (CP) as well as the oily substances acetophenone (AP) and petroleum ether (PE) in water, taking advantage of the polymers' hollow vesicles, high specific surface area, and the dense cationic adsorption sites on the surfaces as well as their high hydrophilicity. The results showed that the polymers with different block lengths (P-PEGTT) obtained from the co-assembled colloids of the two molecules had higher adsorption efficiencies for the anionic pollutants than the polymer of homotrimethylene tricarboxamide molecule (P-TMPTA), especially the polymer obtained by the assembly and polymerization of the mPEG4-TMPTA and TMPTA molecules (P-PEG⁴TT), which not only had a larger capacity, but also had a significantly higher rate of hydrophilic adsorption. In particular, the polymer obtained by the assembly and polymerization of mPEG4-TMPTA and TMPTA molecules (P-PEG⁴TT) not only had a larger adsorption capacity, but also had a significantly higher adsorption hydrophilicity rate, which was 10 times that of P-TMPTA. The polymer (P-PEG³TT) obtained by the assembly polymerization of mPEG3-TMPTA and TMPTA molecules had a 6-fold higher adsorption rate than that of P-TMPTA. This suggests that the rate of adsorption of hydrophilic pollutants is affected by adjusting the block length of small molecules. This material (P-PEGTT) is structured with hydrophilic and hydrophobic PEG chain segments, which achieves high adsorption rate, and high adsorption capacity for hydrophilic anionic pollutants, as well as adsorption performance and storage for oil pollutants. Adsorption MO and CP are more consistent with the pseudo-second-order kinetic model and the Langmuir model, and the intraparticle diffusion model states that the adsorption process is controlled by multiple factors.

In conclusion, this polymer adsorbent with polyethylene glycol block has more excellent performance in the adsorption of hydrophilic pollutants, and also has better application prospects for the adsorption of oily substances, which provides a theoretical basis and practical application significance for the application of supramolecular polymers as adsorbents in the treatment and development of water pollution.

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