【摘要】：大環(huán)聚合物有很多重要應(yīng)用,很多大環(huán)聚氨基酸具有抗菌作用,人工合成的大環(huán)化合物可以進(jìn)行分子/離子識(shí)別,廣泛應(yīng)用于傳感器、分子開關(guān)、清除放射性的離子或者原子等領(lǐng)域。因此探索和設(shè)計(jì)各種復(fù)雜結(jié)構(gòu)大環(huán)和多環(huán)的合成方法一直為人們所重視。本論文的工作主要包括兩方面,一是大環(huán)化合物的合成以及在光化學(xué)下多環(huán)結(jié)構(gòu)的構(gòu)筑和解構(gòu),此外還研究了在實(shí)驗(yàn)過程中發(fā)現(xiàn)的大環(huán)前軀體具有的熱響應(yīng)性行為;二是利用大環(huán)分子對(duì)離子的嵌合作用,使用18-冠醚-6(18C6)絡(luò)合共聚物的鉀鹽來強(qiáng)化聚合物在電場下的極化程度,研究了聚合物的介電常數(shù)的提高和聚合物半導(dǎo)體性質(zhì)的協(xié)同影響。為了適應(yīng)可穿戴電子器件的需求,聚合物半導(dǎo)體近年來備受關(guān)注,因?yàn)樗鼈兛梢杂糜谥苽淞畠r(jià),柔性,輕質(zhì)和可延展的有機(jī)電子器件。高介電常數(shù)(或相對(duì)介電常數(shù)εr)和低損耗的介電聚合物在各種高級(jí)電氣應(yīng)用方面是非常重要的。這些工作具體包括:(1)通過在極稀濃度下將含有四接枝聚乙二醇的大環(huán)前驅(qū)體和丙二酰氯用簡單的多組分一鍋法封端環(huán)化反應(yīng),制備了 "8"字形的大環(huán)化合物。這些"8"字形的大環(huán)化合物的古柯間二酸核心在254 nm的紫外照射下解二聚,形成環(huán)的相對(duì)位置含有兩個(gè)雙鍵的大環(huán),隨后在365 nm的紫外照射下,不同大環(huán)分子間的末端雙鍵重新加成,隨著365 nm紫外光照時(shí)間的不同,可以形成不同個(gè)數(shù)的連環(huán)拓?fù)浣Y(jié)構(gòu)。此研究首次使用光化學(xué)的方法實(shí)現(xiàn)了對(duì)復(fù)雜連環(huán)的構(gòu)筑和解構(gòu)。(2)在合成"8"字形的大環(huán)化合物的時(shí)候,首先合成了一種兩親性的不同長度聚乙二醇鏈接枝的古柯間二酸-聚乙二醇前驅(qū)體大分子。實(shí)驗(yàn)中我們發(fā)現(xiàn),這些對(duì)稱的分子在水中形成分散體系或穩(wěn)定的膠束,且分散體系或穩(wěn)定膠束呈現(xiàn)出對(duì)聚乙二醇鏈長度依賴的熱響應(yīng)行為。這種含有小而明確的疏水核心的兩親性聚合物在水中還具有形成囊泡的能力,這些性質(zhì)不但會(huì)引起學(xué)術(shù)研究的興趣,而且可能在生物和藥物應(yīng)用方面具有重要意義。(3)使用大環(huán)化合物18-冠醚-6絡(luò)合熒光素單鉀鹽接枝的無規(guī)共聚物上的K+離子,使用K+/18C6絡(luò)合物作為反陽離子的目的是為了增加分子中K+和-PhO-間距離,從而減小較強(qiáng)的靜電相互作用。我們預(yù)測當(dāng)K+離子和-PhO-離子之間具有合適的距離的時(shí)候,在足夠高的電場下,熒光素中共軛環(huán)上的電子將可以更容易朝向醌基方向發(fā)生極化。因此,驗(yàn)證這種設(shè)計(jì)方法是否能夠增加半導(dǎo)體聚合物的εr∞,進(jìn)而協(xié)同提升聚合物的半導(dǎo)體性能,將會(huì)引起人們很大的興趣。
[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，

本文編號(hào)：2253673