發(fā)布時(shí)間：2018-03-06 14:18

  本文選題：偶氮基團(tuán)　切入點(diǎn)：金屬酞菁　出處：《遼寧大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：隨著激光技術(shù)的迅速發(fā)展,各種類型的激光光源在醫(yī)學(xué)、科研、工業(yè)生產(chǎn)和軍事等各個(gè)領(lǐng)域得到廣泛應(yīng)用。如何防止這些激光光源對(duì)人眼和光學(xué)器件造成傷害成為亟待解決的科學(xué)問題。基于非線性光學(xué)原理的光限幅材料成為了激光防護(hù)材料的熱點(diǎn)。光限幅材料能夠同時(shí)滿足高光強(qiáng)照射時(shí)低透過率和低光強(qiáng)照射時(shí)高透過率。理想的光限幅材料具有防護(hù)波段寬、非線性消光系數(shù)大、限幅閾值低、響應(yīng)速度快和損傷閾值高等特點(diǎn)。在過去的幾十年里,光限幅材料得到了迅速發(fā)展,人們已經(jīng)發(fā)現(xiàn)了許多不同類型的光限幅材料,比如碳納米管,石墨烯、偶氮聚合物,卟啉類化合物,酞菁類化合物、聚酰亞胺類材料等。相比于無機(jī)材料和有機(jī)小分子材料,高分子材料具有更優(yōu)異的機(jī)械性能和可加工性,有利于光限幅材料的進(jìn)一步器件化。另一方面,由于激光的熱效應(yīng),光限幅材料的熱穩(wěn)定性也是主要的考察指標(biāo)。聚芳醚類材料是一類應(yīng)用領(lǐng)域廣泛的特種工程塑料,具有優(yōu)異的熱穩(wěn)定性、化學(xué)穩(wěn)定性和良好的機(jī)械性能等優(yōu)點(diǎn)。近些年,將聚芳醚類材料功能化成為研究熱點(diǎn),其中最有效的方法就是將功能基團(tuán)引入到聚芳醚材料基體中,使功能基團(tuán)的功能性與聚芳醚材料優(yōu)異的綜合性能相結(jié)合。偶氮類聚合物和酞菁類材料,均是具有應(yīng)用潛力的光限幅材料。其中大多數(shù)酞菁類化合物在溶劑中的溶解性較差,且在高濃度下存在聚集現(xiàn)象,使酞菁類化合物在應(yīng)用的過程中受到了限制。將含酞菁基團(tuán)以共價(jià)接枝的方式引入聚合物體系中,以解決酞菁基團(tuán)在聚合物基體中的分散問題和自聚集問題。同時(shí),將偶氮基團(tuán)和酞菁基團(tuán)相結(jié)合,可以進(jìn)一步提高材料的非線性光學(xué)性能。本論文從分子設(shè)計(jì)角度出發(fā),合成了一種新型含偶氮二苯腈結(jié)構(gòu)的雙氟單體,再進(jìn)一步通過聚合反應(yīng),合成了側(cè)鏈含偶氮二苯腈聚芳醚均聚物。以所合成的側(cè)鏈含偶氮二苯腈聚芳醚均聚物為基體,通過后功能化,合成了側(cè)鏈含金屬酞菁偶氮聚芳醚材料。我們對(duì)所合成聚芳醚材料的熱學(xué)性能和非線性光學(xué)性能進(jìn)行了研究。(1)通過重氮偶聯(lián)反應(yīng)合成了一種新型含偶氮二苯腈結(jié)構(gòu)的單酚單體,再進(jìn)一步通過酯化反應(yīng)合成了含偶氮二苯腈結(jié)構(gòu)的雙氟單體。以所合成含偶氮二苯氰結(jié)構(gòu)的雙氟為單體,與六氟雙酚A進(jìn)行聚合反應(yīng),合成了一種新型側(cè)鏈含偶氮二苯腈聚芳醚均聚物,并通過核磁共振氫譜、紅外光譜、紫外-可見光譜確定其結(jié)構(gòu)。此外,我們對(duì)所合成聚合物的基本性能進(jìn)行了研究,結(jié)果表明該聚合物具有較高的玻璃化轉(zhuǎn)變溫度和良好的熱穩(wěn)定性。(2)以所合成的側(cè)鏈含偶氮二苯腈聚芳醚均聚物為基體,通過后功能化,與鄰苯二腈和無水氯化鈷反應(yīng),合成了側(cè)鏈含金屬酞菁偶氮聚芳醚材料,并通過核磁共振氫譜,紅外光譜、紫外-可見光譜和XRD確定其結(jié)構(gòu)。熱穩(wěn)定性測(cè)試結(jié)果表明所合成的側(cè)鏈含金屬酞菁偶氮聚芳醚材料具有良好的熱穩(wěn)定性。三階非線性光學(xué)測(cè)試結(jié)果表明,所制合成的側(cè)鏈含金屬酞菁偶氮聚芳醚材料具有較高的三階非線性極化率,在激光防護(hù)材料領(lǐng)域具有潛在的應(yīng)用價(jià)值。
[Abstract]:With the rapid development of laser technology, laser light source of various types of scientific research in medicine, is widely used in industrial production and various military fields. How to prevent these laser damage become a scientific problem to human eyes and optical devices. The nonlinear optical principle of optical limiting materials has become a hot spot of laser protective materials based on. Optical limiting materials can satisfy the high intensity irradiation of low transmittance and low light irradiation and high transmittance. The optical limiting materials with protective band width, nonlinear extinction coefficient, low limiting threshold, fast response speed and higher damage threshold. In the past few decades, optical limiting material has been developing rapidly, people have found many different types of optical limiting materials, such as carbon nanotubes, graphene, azo polymer, porphyrins, phthalocyanines, poly Imide materials. Compared to inorganic materials and organic small molecular materials, polymer materials with more excellent mechanical properties and processability, is conducive to further integration of optical limiting materials. On the other hand, due to the thermal effect of the laser, the thermal stability of optical limiting materials is also the main indexes. Polyarylether material is a kind of special engineering plastics used widely, has excellent thermal stability, mechanical properties and other advantages and good chemical stability. In recent years, the polyarylether functional materials have become a hot research topic, one of the most effective method is the functional groups introduced into poly aryl ether material matrix. The function of functional groups and poly aryl ether material with excellent comprehensive performance. The combination of azo polymer and phthalocyanine materials, both have potential applications in optical limiting materials. Most of phthalocyanine compounds in solution Poor solubility agent, and aggregation phenomenon at high concentration, the phthalocyanine compounds in the process of application is limited. With the phthalocyanine moiety into the polymer by covalent grafting method, to solve the phthalocyanine moiety in the polymer matrix and the dispersion problem of self aggregation problem. At the same time, the azo group and the combination of the phthalocyanine moiety, can further improve the nonlinear optical properties of materials. This paper from the perspective of molecular design, a new type of azo benzene nitrile two structure double fluorine monomer was synthesized by further polymerization of side chain azo containing two benzene nitrile homopolymer poly aryl ether nitrile polymer was synthesized. Aryl ether homopolymer matrix with side chain synthesis of azo benzene two, through the functional side chains containing azo phthalocyanine poly aryl ether material was synthesized. We synthesized poly aryl ether material thermal properties and nonlinear optics The performance was studied. (1) a new two azo benzene nitrile structure of single phenolic monomers were synthesized by diazo coupling reaction, and further through the esterification reaction of double fluorine monomer containing azo benzene nitrile two structure was synthesized. The synthesis of fluorine containing azo double two benzene cyanide monomer structure six, the polymerization reaction of bisphenol A and fluoride, a new type of side chain azo containing two benzene nitrile homopolymer poly aryl ether was synthesized by 1H NMR, IR, UV Vis spectroscopy to determine its structure. In addition, we studied the basic properties of synthetic polymers. The results show that the glass transition temperature of the polymer and has better thermal stability. (2) poly aryl ether nitrile homopolymer matrix with side chain synthesis of azo benzene two, after functionalization, reaction and phthalic nitrile and two anhydrous cobalt chloride, side chain containing azo phthalocyanine poly aryl ether material the synthesis of And, by 1H NMR, IR, UV Vis and XRD to determine its structure. The thermal stability test showed that the synthesized metal containing side chain azo phthalocyanine poly aryl ether material has good thermal stability. Three order nonlinear optical test results show that the synthesis of side chain of poly aryl ether material with high content of metal phthalocyanine azo three order nonlinear polarizability, has potential applications in the field of laser protective materials.

【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.24

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本文編號(hào)：1575196