含金属酞菁偶氮聚芳醚的制备及其非线性光学性能研究

发布时间：2018-03-06 14:18

本文选题：偶氮基团　切入点：金属酞菁　出处：《辽宁大学》2017年硕士论文　论文类型：学位论文

【摘要】：随着激光技术的迅速发展,各种类型的激光光源在医学、科研、工业生产和军事等各个领域得到广泛应用。如何防止这些激光光源对人眼和光学器件造成伤害成为亟待解决的科学问题。基于非线性光学原理的光限幅材料成为了激光防护材料的热点。光限幅材料能够同时满足高光强照射时低透过率和低光强照射时高透过率。理想的光限幅材料具有防护波段宽、非线性消光系数大、限幅阈值低、响应速度快和损伤阈值高等特点。在过去的几十年里,光限幅材料得到了迅速发展,人们已经发现了许多不同类型的光限幅材料,比如碳纳米管,石墨烯、偶氮聚合物,卟啉类化合物,酞菁类化合物、聚酰亚胺类材料等。相比于无机材料和有机小分子材料,高分子材料具有更优异的机械性能和可加工性,有利于光限幅材料的进一步器件化。另一方面,由于激光的热效应,光限幅材料的热稳定性也是主要的考察指标。聚芳醚类材料是一类应用领域广泛的特种工程塑料,具有优异的热稳定性、化学稳定性和良好的机械性能等优点。近些年,将聚芳醚类材料功能化成为研究热点,其中最有效的方法就是将功能基团引入到聚芳醚材料基体中,使功能基团的功能性与聚芳醚材料优异的综合性能相结合。偶氮类聚合物和酞菁类材料,均是具有应用潜力的光限幅材料。其中大多数酞菁类化合物在溶剂中的溶解性较差,且在高浓度下存在聚集现象,使酞菁类化合物在应用的过程中受到了限制。将含酞菁基团以共价接枝的方式引入聚合物体系中,以解决酞菁基团在聚合物基体中的分散问题和自聚集问题。同时,将偶氮基团和酞菁基团相结合,可以进一步提高材料的非线性光学性能。本论文从分子设计角度出发,合成了一种新型含偶氮二苯腈结构的双氟单体,再进一步通过聚合反应,合成了侧链含偶氮二苯腈聚芳醚均聚物。以所合成的侧链含偶氮二苯腈聚芳醚均聚物为基体,通过后功能化,合成了侧链含金属酞菁偶氮聚芳醚材料。我们对所合成聚芳醚材料的热学性能和非线性光学性能进行了研究。(1)通过重氮偶联反应合成了一种新型含偶氮二苯腈结构的单酚单体,再进一步通过酯化反应合成了含偶氮二苯腈结构的双氟单体。以所合成含偶氮二苯氰结构的双氟为单体,与六氟双酚A进行聚合反应,合成了一种新型侧链含偶氮二苯腈聚芳醚均聚物,并通过核磁共振氢谱、红外光谱、紫外-可见光谱确定其结构。此外,我们对所合成聚合物的基本性能进行了研究,结果表明该聚合物具有较高的玻璃化转变温度和良好的热稳定性。(2)以所合成的侧链含偶氮二苯腈聚芳醚均聚物为基体,通过后功能化,与邻苯二腈和无水氯化钴反应,合成了侧链含金属酞菁偶氮聚芳醚材料,并通过核磁共振氢谱,红外光谱、紫外-可见光谱和XRD确定其结构。热稳定性测试结果表明所合成的侧链含金属酞菁偶氮聚芳醚材料具有良好的热稳定性。三阶非线性光学测试结果表明,所制合成的侧链含金属酞菁偶氮聚芳醚材料具有较高的三阶非线性极化率,在激光防护材料领域具有潜在的应用价值。
[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.

【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.24

【参考文献】