聚酰亚胺和聚炔高分子液晶的合成及性质研究
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摘要
高分子液晶材料的诞生至今还不到60年。但是它以其优异的性能,巨大的应用价值和发展空间而受到人们越来越多的关注。因此,这个热门的研究领域得到了迅猛的发展,尤其近年来,有关高分子液晶的报道数量惊人,涉及种类也非常广泛,使这门科学迅速的形成了一个庞大的家族,并成为最热门的学科之一。
高分子液晶飞速的发展,使其拥有众多不同的类型,大致可以归纳为两种类型:侧链高分子液晶和主链高分子液晶。不过,分子结构的纷繁使有些高分子液晶自立门派,如甲壳型高分子液晶等。
高分子液晶的发展潜力主要来源于其分子结构的多样性,这种多样性是因为主链和侧链的结构千变万化,这也使其性能与众不同又难以把握。研究证明,侧链结构的合理设计和引入方式对其性能的改良有着决定性作用.但目前这方面的研究仍处于初期阶段,有待深化。
本文设计并合成三种较有代表性的高分子液晶:一类聚酰亚胺高分子液晶,两类聚乙炔高分子液晶和一例甲壳型聚炔高分子液晶。高分子化合物的结构表征涵盖了核磁共振、红外光谱、质谱、液相色谱、元素分析等,性质研究涉及了液晶相态行为(POM)、液晶相温度及焓变(DSC)、聚合度(GPC)、热稳定性(TGA)、溶解性、力学性能等研究。最后,经过对研究结构的思考和讨论得出结论.本文的研究将为高分子液晶的分子设计和实际应用打下一些基础。
本硕士论文主要包括四部分:
第一章简要介绍了高分子和液晶方面的基础知识,从而引出高分子液晶并列举了几种有代表性的类型,并简要介绍了本文的研究内容和特色。
第二章报道了一类聚酰亚胺高分子液晶。聚酰亚胺高分子的主链刚性大,提供分子设计,可以改善其液晶性。我们经过分子设计,通过向侧链和主链分别引入柔性基团并控制其比例,制备了两个系列的聚酰亚胺高分子薄膜。最后从液晶相态行为、液晶相温度、热稳定性和材料的力学性能等方面对薄膜进行了较为详尽的研究。
第三章研究了聚乙炔高分子液晶。为改良聚乙炔液晶的性能,通过侧链介晶基团的设计,合成了四种聚乙炔高分子液晶,对其结构进行了表征,构型通过计算机模拟。通过液晶性、热稳定性的研究,总结了聚乙炔高分子及其单体结构-性能规律:不同种类棒状液晶基元对液晶性的影响,分子内氢键对此类高分子液晶的性质有重要影响。
第四章研究了聚乙炔苯并菲盘状高分子液晶。聚乙炔的侧链引入苯并菲盘状液晶基元。苯乙炔基的聚合活性大大高于乙炔基,探索了聚合方法,优化了聚合体系。研究了聚合物和单体的液晶性和热稳定性。本文首次报道了一例苯并菲盘状甲壳型聚炔高分子液晶。
盘状聚乙炔液晶和盘状甲壳型高分子液晶的研究才刚起步.单体的结构对聚合反应的影响,聚合物结构与液晶相态的关系都是我们正研究和思考的问题.希望本文的研究对高分子液晶材料的进一步深入研究和将来的发展起到一定的促进作用。
High molecular weight liquid crystalline materials have been only 60 years from its origin and increasing attentions have been paying to it. Liquid crystal polymers have exhibited special properties, great values of applications, and huge development spaces.
Liquid crystalline polymers mainly consist of two types: main chain and side-chain liquid crystalline polymers. There are some exceptions, such as the mesogen-jacketed liquid crystalline polymers.
The science of liquid crystalline polymers is still young, and more research and development on it are needed. The physical properties and practical applications depend on both side chain and main chain. The side chain mesogen modification and polymer chain characters determine their properties. The molecular designing, synthesis, structure-property relationship in this field still need more research.
This thesis reported three kinds of liquid crystalline polymers: polyimides, polyacetylene and mesogen-jacketed liquid crystalline polymers. The structure characterization of the monomers and polymers was carried out with NMR, IR, MS, GPC. The properties have been investigated with POM, DSC, TGA. The discussion on the results led to the conclusions of the thesis.
The thesis consists of four chapters:
Chapter One briefly introduced the elementary knowledge about polymers and liquid crystal materials, then liquid crystalline polymers and several representative types was introduced. The content and feature of the thesis were pointed out.
Chapter Two reported novel polyimide liquid crystals. As polyimide main chain is rigid, it is difficult to show liquid crystalline properties. Through molecular designing of connecting the mesogen to the polyimide main chain by a flexible spacer, two series to polyimide polymer films were prepared. Finally, the liquid crystal behavior, phase transition temperature, thermal stability and mechanical properties were studied.
Chapter Three carried out the research on polyacetylene liquid crystals. Through the designing of side chain mesogens, four series of polyacetylene liquid crystals were synthesized and characterized. The molecular structure configuration was simulated by computer calculation. The liquid crystalline properties, thermal stability, and the influence of intrachain hydrogen bonding on mesomorphism were summarized and discussed.
Chapter Four reported the synthesis and characterization of polyacetylene with triphenylene discogens. The acetylene monomers with triphenylene discogens have been polymerized by [Rh(nbd)Cl]_2. The activity of fuctional group for polymerization, the influence of organic base and the solvent system on polymerization have been investigated, and some big breakthroughs have been made in this field. A triphenylene discotic mesogen-jacketed polyacetylene liquid crystalline polymer was reported first time.
The primary research on polyacetylene discotic liquid crystals and discogen-jacketed liquid crystalline polymers in this thesis are interesting and intriguing. It is worth further more and deep investigation.
高分子液晶飞速的发展,使其拥有众多不同的类型,大致可以归纳为两种类型:侧链高分子液晶和主链高分子液晶。不过,分子结构的纷繁使有些高分子液晶自立门派,如甲壳型高分子液晶等。
高分子液晶的发展潜力主要来源于其分子结构的多样性,这种多样性是因为主链和侧链的结构千变万化,这也使其性能与众不同又难以把握。研究证明,侧链结构的合理设计和引入方式对其性能的改良有着决定性作用.但目前这方面的研究仍处于初期阶段,有待深化。
本文设计并合成三种较有代表性的高分子液晶:一类聚酰亚胺高分子液晶,两类聚乙炔高分子液晶和一例甲壳型聚炔高分子液晶。高分子化合物的结构表征涵盖了核磁共振、红外光谱、质谱、液相色谱、元素分析等,性质研究涉及了液晶相态行为(POM)、液晶相温度及焓变(DSC)、聚合度(GPC)、热稳定性(TGA)、溶解性、力学性能等研究。最后,经过对研究结构的思考和讨论得出结论.本文的研究将为高分子液晶的分子设计和实际应用打下一些基础。
本硕士论文主要包括四部分:
第一章简要介绍了高分子和液晶方面的基础知识,从而引出高分子液晶并列举了几种有代表性的类型,并简要介绍了本文的研究内容和特色。
第二章报道了一类聚酰亚胺高分子液晶。聚酰亚胺高分子的主链刚性大,提供分子设计,可以改善其液晶性。我们经过分子设计,通过向侧链和主链分别引入柔性基团并控制其比例,制备了两个系列的聚酰亚胺高分子薄膜。最后从液晶相态行为、液晶相温度、热稳定性和材料的力学性能等方面对薄膜进行了较为详尽的研究。
第三章研究了聚乙炔高分子液晶。为改良聚乙炔液晶的性能,通过侧链介晶基团的设计,合成了四种聚乙炔高分子液晶,对其结构进行了表征,构型通过计算机模拟。通过液晶性、热稳定性的研究,总结了聚乙炔高分子及其单体结构-性能规律:不同种类棒状液晶基元对液晶性的影响,分子内氢键对此类高分子液晶的性质有重要影响。
第四章研究了聚乙炔苯并菲盘状高分子液晶。聚乙炔的侧链引入苯并菲盘状液晶基元。苯乙炔基的聚合活性大大高于乙炔基,探索了聚合方法,优化了聚合体系。研究了聚合物和单体的液晶性和热稳定性。本文首次报道了一例苯并菲盘状甲壳型聚炔高分子液晶。
盘状聚乙炔液晶和盘状甲壳型高分子液晶的研究才刚起步.单体的结构对聚合反应的影响,聚合物结构与液晶相态的关系都是我们正研究和思考的问题.希望本文的研究对高分子液晶材料的进一步深入研究和将来的发展起到一定的促进作用。
High molecular weight liquid crystalline materials have been only 60 years from its origin and increasing attentions have been paying to it. Liquid crystal polymers have exhibited special properties, great values of applications, and huge development spaces.
Liquid crystalline polymers mainly consist of two types: main chain and side-chain liquid crystalline polymers. There are some exceptions, such as the mesogen-jacketed liquid crystalline polymers.
The science of liquid crystalline polymers is still young, and more research and development on it are needed. The physical properties and practical applications depend on both side chain and main chain. The side chain mesogen modification and polymer chain characters determine their properties. The molecular designing, synthesis, structure-property relationship in this field still need more research.
This thesis reported three kinds of liquid crystalline polymers: polyimides, polyacetylene and mesogen-jacketed liquid crystalline polymers. The structure characterization of the monomers and polymers was carried out with NMR, IR, MS, GPC. The properties have been investigated with POM, DSC, TGA. The discussion on the results led to the conclusions of the thesis.
The thesis consists of four chapters:
Chapter One briefly introduced the elementary knowledge about polymers and liquid crystal materials, then liquid crystalline polymers and several representative types was introduced. The content and feature of the thesis were pointed out.
Chapter Two reported novel polyimide liquid crystals. As polyimide main chain is rigid, it is difficult to show liquid crystalline properties. Through molecular designing of connecting the mesogen to the polyimide main chain by a flexible spacer, two series to polyimide polymer films were prepared. Finally, the liquid crystal behavior, phase transition temperature, thermal stability and mechanical properties were studied.
Chapter Three carried out the research on polyacetylene liquid crystals. Through the designing of side chain mesogens, four series of polyacetylene liquid crystals were synthesized and characterized. The molecular structure configuration was simulated by computer calculation. The liquid crystalline properties, thermal stability, and the influence of intrachain hydrogen bonding on mesomorphism were summarized and discussed.
Chapter Four reported the synthesis and characterization of polyacetylene with triphenylene discogens. The acetylene monomers with triphenylene discogens have been polymerized by [Rh(nbd)Cl]_2. The activity of fuctional group for polymerization, the influence of organic base and the solvent system on polymerization have been investigated, and some big breakthroughs have been made in this field. A triphenylene discotic mesogen-jacketed polyacetylene liquid crystalline polymer was reported first time.
The primary research on polyacetylene discotic liquid crystals and discogen-jacketed liquid crystalline polymers in this thesis are interesting and intriguing. It is worth further more and deep investigation.
引文
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