大环拓扑高分子的光化学构筑和解构
发布时间：2018-10-05 14:02
【摘要】：大环聚合物有很多重要应用,很多大环聚氨基酸具有抗菌作用,人工合成的大环化合物可以进行分子/离子识别,广泛应用于传感器、分子开关、清除放射性的离子或者原子等领域。因此探索和设计各种复杂结构大环和多环的合成方法一直为人们所重视。本论文的工作主要包括两方面,一是大环化合物的合成以及在光化学下多环结构的构筑和解构,此外还研究了在实验过程中发现的大环前躯体具有的热响应性行为;二是利用大环分子对离子的嵌合作用,使用18-冠醚-6(18C6)络合共聚物的钾盐来强化聚合物在电场下的极化程度,研究了聚合物的介电常数的提高和聚合物半导体性质的协同影响。为了适应可穿戴电子器件的需求,聚合物半导体近年来备受关注,因为它们可以用于制备廉价,柔性,轻质和可延展的有机电子器件。高介电常数(或相对介电常数εr)和低损耗的介电聚合物在各种高级电气应用方面是非常重要的。这些工作具体包括:(1)通过在极稀浓度下将含有四接枝聚乙二醇的大环前驱体和丙二酰氯用简单的多组分一锅法封端环化反应,制备了 "8"字形的大环化合物。这些"8"字形的大环化合物的古柯间二酸核心在254 nm的紫外照射下解二聚,形成环的相对位置含有两个双键的大环,随后在365 nm的紫外照射下,不同大环分子间的末端双键重新加成,随着365 nm紫外光照时间的不同,可以形成不同个数的连环拓扑结构。此研究首次使用光化学的方法实现了对复杂连环的构筑和解构。(2)在合成"8"字形的大环化合物的时候,首先合成了一种两亲性的不同长度聚乙二醇链接枝的古柯间二酸-聚乙二醇前驱体大分子。实验中我们发现,这些对称的分子在水中形成分散体系或稳定的胶束,且分散体系或稳定胶束呈现出对聚乙二醇链长度依赖的热响应行为。这种含有小而明确的疏水核心的两亲性聚合物在水中还具有形成囊泡的能力,这些性质不但会引起学术研究的兴趣,而且可能在生物和药物应用方面具有重要意义。(3)使用大环化合物18-冠醚-6络合荧光素单钾盐接枝的无规共聚物上的K+离子,使用K+/18C6络合物作为反阳离子的目的是为了增加分子中K+和-PhO-间距离,从而减小较强的静电相互作用。我们预测当K+离子和-PhO-离子之间具有合适的距离的时候,在足够高的电场下,荧光素中共轭环上的电子将可以更容易朝向醌基方向发生极化。因此,验证这种设计方法是否能够增加半导体聚合物的εr∞,进而协同提升聚合物的半导体性能,将会引起人们很大的兴趣。
[Abstract]:Macrocyclic polymers have many important applications, many macrocyclic amino acids have antibacterial effect, synthetic macrocyclic compounds can be used for molecular / ion recognition, widely used in sensors, molecular switches, The removal of radioactive ions or atoms, etc. Therefore, the exploration and design of a variety of complex structure of large-ring and multi-ring synthesis methods have been paid attention to. The work of this thesis mainly includes two aspects. One is the synthesis of macrocyclic compounds and the construction and deconstruction of polycyclic structures under photochemistry. The second is to enhance the polarization degree of polymer under electric field by using the potassium salt of 18-crown-ether 6 (18C6) complex copolymer by using the chimeric interaction of macrocyclic molecules to ions. The synergistic effect of polymer dielectric constant and polymer semiconductor properties is studied. In order to meet the needs of wearable electronic devices, polymer semiconductors have attracted much attention in recent years because they can be used to fabricate cheap, flexible, lightweight and extensible organic electronic devices. High dielectric constant (or relative dielectric constant 蔚 r) and low loss dielectric polymer are very important in various advanced electrical applications. These work include: (1) A "8" macrocyclic compound was prepared by capping the macrocyclic precursor containing four grafted polyethylene glycol and malonyl chloride by a simple multicomponent one pot method at extremely dilute concentration. The coca dicarboxylic acid core of these "8" macrocyclic compounds is dimerized under UV irradiation of 254 nm to form a ring containing two double bond macrorings, which are then exposed to UV light at 365 nm. The end double bonds of different macrocyclic molecules are re-added. With the different UV irradiation time of 365 nm, different numbers of serial topologies can be formed. This study was the first to use photochemical methods to construct and deconstruct complex chains. (2) in the synthesis of "8" macrocyclic compounds, At first, a amphiphilic macromolecule of coca isophthalic acid-polyethylene glycol (PEG) precursor with different length of polyethylene glycol (PEG) was synthesized. It is found that these symmetric molecules form dispersed systems or stable micelles in water, and the thermal response of the dispersed or stable micelles is dependent on the length of the polyethylene glycol chain. This amphiphilic polymer, which contains small and clear hydrophobic cores, also has the ability to form vesicles in water, which not only arouses interest in academic research, It may also be of great significance in biological and pharmaceutical applications. (3) K ions in random copolymers grafted with mono-potassium fluorescein using macrocyclic compound 18-crown-ether -6, The purpose of using K / 18C6 complexes as antications is to increase the distance between K and -PhO- in the molecule and thus reduce the strong electrostatic interaction. We predict that when there is a suitable distance between K ion and -PhO- ion, the electrons on conjugated ring in fluorescein will be more easily polarized towards quinone group at a sufficiently high electric field. Therefore, it will be of great interest to verify whether this design method can increase 蔚 r 鈭，
本文编号：2253673
[Abstract]:Macrocyclic polymers have many important applications, many macrocyclic amino acids have antibacterial effect, synthetic macrocyclic compounds can be used for molecular / ion recognition, widely used in sensors, molecular switches, The removal of radioactive ions or atoms, etc. Therefore, the exploration and design of a variety of complex structure of large-ring and multi-ring synthesis methods have been paid attention to. The work of this thesis mainly includes two aspects. One is the synthesis of macrocyclic compounds and the construction and deconstruction of polycyclic structures under photochemistry. The second is to enhance the polarization degree of polymer under electric field by using the potassium salt of 18-crown-ether 6 (18C6) complex copolymer by using the chimeric interaction of macrocyclic molecules to ions. The synergistic effect of polymer dielectric constant and polymer semiconductor properties is studied. In order to meet the needs of wearable electronic devices, polymer semiconductors have attracted much attention in recent years because they can be used to fabricate cheap, flexible, lightweight and extensible organic electronic devices. High dielectric constant (or relative dielectric constant 蔚 r) and low loss dielectric polymer are very important in various advanced electrical applications. These work include: (1) A "8" macrocyclic compound was prepared by capping the macrocyclic precursor containing four grafted polyethylene glycol and malonyl chloride by a simple multicomponent one pot method at extremely dilute concentration. The coca dicarboxylic acid core of these "8" macrocyclic compounds is dimerized under UV irradiation of 254 nm to form a ring containing two double bond macrorings, which are then exposed to UV light at 365 nm. The end double bonds of different macrocyclic molecules are re-added. With the different UV irradiation time of 365 nm, different numbers of serial topologies can be formed. This study was the first to use photochemical methods to construct and deconstruct complex chains. (2) in the synthesis of "8" macrocyclic compounds, At first, a amphiphilic macromolecule of coca isophthalic acid-polyethylene glycol (PEG) precursor with different length of polyethylene glycol (PEG) was synthesized. It is found that these symmetric molecules form dispersed systems or stable micelles in water, and the thermal response of the dispersed or stable micelles is dependent on the length of the polyethylene glycol chain. This amphiphilic polymer, which contains small and clear hydrophobic cores, also has the ability to form vesicles in water, which not only arouses interest in academic research, It may also be of great significance in biological and pharmaceutical applications. (3) K ions in random copolymers grafted with mono-potassium fluorescein using macrocyclic compound 18-crown-ether -6, The purpose of using K / 18C6 complexes as antications is to increase the distance between K and -PhO- in the molecule and thus reduce the strong electrostatic interaction. We predict that when there is a suitable distance between K ion and -PhO- ion, the electrons on conjugated ring in fluorescein will be more easily polarized towards quinone group at a sufficiently high electric field. Therefore, it will be of great interest to verify whether this design method can increase 蔚 r 鈭，
本文编号：2253673
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