共价有机聚合物的合成及其性能研究

发布时间：2018-06-06 06:13

本文选题：共价有机聚合物 + 卟啉　；参考：《江南大学》2017年硕士论文

【摘要】：共价有机聚合物具有结构可控、功能可调、稳定性高等优异的物理化学性质,有望在气体储存、吸附、分离和催化、能源、传感器、生物医药等领域发挥重要作用。本课题首先合成了多个新颖的卟啉氨基构筑单元,再将其设计合成多种卟啉基共价有机聚合物。将其分别按照“后修饰”(Au纳米粒子负载至聚合物载体上)和“自下而上”(金属-卟啉类物质嵌入聚合物)的合成方法,依次得到了Au@CPF-1和Mn-PPOPs两类具有优异催化性能的卟啉基共价有机聚合物。主要内容如下:(1)合成了3种卟啉氨基化合物,5,15-二(4-氨基苯基)-10,20-二苯基卟啉,5,10,15,20-四氨基苯基卟啉和5,10,15,20-四(4-氨基联苯基)-21H,23H-卟啉,其中有2种为全新设计的卟啉氨基化合物。并在此基础上结合超分子化学和晶体工程的策略,构筑了2个卟啉超分子化合物Zn-TAPP和Dimer-1,并借助晶体学的手段对其结构进行了表征,将配位化学的手段引入构筑共价有机聚合物构筑单元,进一步丰富了共价有机聚合物反应构筑单元的多样性,为本论文后续工作的开展奠定了良好的基础。(2)以1,3,5-三甲酰间苯三酚和5,15-二(4-氨基苯基)-10,20-二苯基卟啉为构筑单元,合成出共价有机聚合物CPF-1,并负载Au纳米粒子得到材料Au@CPF-1。红外光谱表明反应物反应完全,光电子能谱和X射线衍射图谱表明新材料的成功合成和Au纳米粒子的成功负载,扫描电子显微镜和透射电子显微镜图谱表明材料的形态学结构和Au纳米粒子的分散状态,BET比表面积测试和热重分析表明材料的永久微孔隙度特性和热稳定性。再利用其对硝基苯酚的还原反应,证实Au@CPF-1具有良好的催化性能,并且该非均相催化剂具有优异的稳定性和可循环性,能连续使用三次同时保持高的催化效率。证明卟啉基多孔共价有机聚合材料能够被用来做为Au NPs的良好载体。(3)以5,10,15,20-四氨基苯基卟啉和5,10,15,20-四(4-氨基联苯基)-21H,23H-卟啉作为配体,分别与Mn金属配位形成两种Mn-卟啉类物质,再将两种金属卟啉直接与1,3,5-三甲酰间苯三酚聚合,成功构筑了两种金属卟啉基多孔有机聚合物Mn-PPOP-1和Mn-PPOP-2。通过傅立叶转换红外光谱和固体核磁表明反应物反应完全,扫描电子显微镜图像和透射电镜图像表征了材料的微观结构。这些材料表现出永久的孔隙率和优异的热和化学稳定性。Mn-PPOP-1和Mn-PPOP-2都显示出对烯烃和芳基烷烃优异的催化氧化能力。在催化活性和稳定性方面,这些非均相的Mn-PPOPs明显优于均相锰卟啉类似物。更显著的是,与Mn-PPOP-1相比,Mn-PPOP-2由于具有较高表面积的和较大的卟啉构建单元显示出优异的催化效率。这些结果表明,积极的表面积效应对于开发多孔非均相催化剂是重要的,并且在设计基于POPs的催化结构中扮演着重要的角色。此外,催化剂经过回收利用,仍能保持较高催化活性,具备潜在的应用价值。
[Abstract]:Covalent organic polymers have excellent physical and chemical properties with controllable structure, adjustable function and high stability. It is expected to play an important role in the fields of gas storage, adsorption, separation and catalysis, energy, sensors, biological medicine and other fields. Covalent organic polymers are synthesized in accordance with the "post modification" (Au nanoparticles loaded on the polymer carrier) and the "bottom-up" (metal porphyrin imbedded polymer). The two classes of porphyrin covalent organic polymers with excellent catalytic properties, Au@CPF-1 and Mn-PPOPs, are obtained in turn. The main contents are as follows: (1) 3 kinds of porphyrin amino compounds, 5,15- two (4- amino phenyl) -10,20- two phenyl porphyrin, 5,10,15,20- four amino phenyl porphyrin and 5,10,15,20- four (4- amino biphenyl) -21H, 23H- porphyrin, have 2 New Porphyrin amino compounds. Based on this, the strategy of binding supramolecular chemistry and crystal engineering has been constructed, and 2 Porphyrins are constructed. The structure of supramolecular compounds, Zn-TAPP and Dimer-1, was characterized by the means of crystallography, and the method of coordination chemistry was introduced into the building unit of covalent organic polymer, which further enriched the diversity of the reactive building units of covalent organic polymers. It laid a good foundation for the development of the later work of this paper. (2) 1,3, 5- trimetholyl benzene three phenol and 5,15- two (4- amino phenyl) -10,20- two phenyl porphyrin were used as building units to synthesize covalently organic polymer CPF-1, and Au nanoparticles were loaded with Au@CPF-1. infrared spectra to show that the reaction was complete. The photoelectron spectroscopy and X ray diffraction patterns showed the successful synthesis of new materials and the formation of Au nanoparticles. The work load, the scanning electron microscope and the transmission electron microscope map showed the morphology structure of the material and the dispersion state of the Au nanoparticles. The BET specific surface area test and thermogravimetric analysis showed the permanent porosity and thermal stability of the material, and the reduction reaction of p-nitrophenol proved that Au@CPF-1 had good catalytic performance. And the heterogeneous catalyst has excellent stability and recyclability, and can be used for three times at the same time to maintain high catalytic efficiency. It is proved that porphyrin based covalent organic polymeric materials can be used as a good carrier for Au NPs. (3) 5,10,15,20- four amino phenyl porphyrin and 5,10,15,20- four (4- amino biphenyl) -21H, 23H- porphyrin As ligands, two kinds of Mn- porphyrins are formed by coordination with Mn metal, and then two metalloporphyrins are polymerized directly with 1,3,5- trimethylbenzene three phenol. Two metalloporphyrin porous organic polymers, Mn-PPOP-1 and Mn-PPOP-2., are successfully constructed by Fu Liye transform infrared spectroscopy and solid NMR, and the reaction is completely reacted and scanned. The microstructures of the materials are characterized by the submicroscopic and transmission electron microscopy images. These materials show that permanent porosity and excellent thermal and chemical stability.Mn-PPOP-1 and Mn-PPOP-2 show excellent catalytic oxidation capacity for olefin and aryl alkanes. These heterogeneous Mn-PPOPs are obviously superior in catalytic activity and stability. More significantly, compared with Mn-PPOP-1, Mn-PPOP-2 shows excellent catalytic efficiency due to the high surface area and the larger porphyrin construction units. These results show that the active surface area effect is important for the development of porous heterogeneous catalysts and in the design of a POPs based catalytic structure. It plays an important role. In addition, the catalyst can still maintain high catalytic activity after recycling and has potential application value.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O631

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