新型含N,N’-雙(2-萘基苯基)對苯二胺結構之聚醯胺和聚醯亞胺的合成及其光電性質

Synthesis and Optoelectronic Properties of Novel Polyamides and Polyimides with N,N’-Di-2-naphthyl- N,N’-diphenyl-1,4-phenylenediamine Units

葉素蓉(Su-Jung Yeh)

指導教授 ： 蕭勝輝

國立臺北科技大學/工程學院/化學工程研究所/碩士(2013年)

摘要

本論文包含兩個研究主題，主要探討由具有N,N’-雙(2-萘基苯基)對苯二胺結構的二胺單體所衍生的聚醯胺(polyamides)與聚醯亞胺(polyimides)的合成及其光電性質，如吸收光譜、光致發光、電化學、光譜電化學、電致變色性質等。
論文的第一部分在探討一種具有三芳香胺基的二胺單體N,N’-bis(4-aminophenyl)-N,N’-di-2-naphthyl-1,4-phenylenediamine的合成及其與各種二羧酸進行磷酸化聚縮合反應製備一系列新型的聚醯胺。這些聚醯胺屬於非結晶性的材料，並且易溶於多種的有機溶劑，因此可經由它們的溶液塗佈及烘乾後製得具有可撓曲性的高分子薄膜。這些聚醯胺展現出好的熱穩定性，它們的玻璃態轉移溫度範圍在247-289 oC。由脂環族二羧酸所衍生的聚醯胺比其他由芳香族二羧酸所衍生者具有較強的螢光強度，並且它的發光波長也會因溶劑的不同而改變。所有的聚合物薄膜均表現出可逆的電化學氧化反應，並伴隨著明顯的電致變色現象，從中性狀態的透明無色變成氧化態的綠色和藍色。
論文的第二部分在探討以上述具有N,N’-雙(2-萘基苯基)對苯二胺結構的二胺單體所衍生的聚醯亞胺的合成和特性。這些聚醯亞胺是由上述的二胺單體與各種二酐先進行開環加成聚合得到聚醯胺酸，然後再經由化學閉環和熱閉環而得。大部分的聚醯亞胺可以溶於有機溶劑，並且可由它們的溶液塗製成非晶型薄膜。這些聚醯亞胺展現好的熱穩定性，它們的玻璃轉移溫度介於 288-329 oC 之間，並且在溫度超過大約500 oC以上才會產生較明顯的熱裂解。由高分子薄膜的循環伏安研究發現這些聚醯亞胺同時擁有p- 和 n-可摻雜的特性並且具有多顏色電致變色的現象。

關鍵字

聚醯胺 ； 聚醯亞胺 ； 三芳香胺 ； 電致變色 ； 光激發光 ； 光譜電化學

並列摘要

This thesis describes the synthesis and characterization of an aromatic diamine monomer bearing N,N’-di-2-naphthyl-N,N’-diphenyl-1,4-phenylenediamine segment and its derived polyamides and polyimides. Optoelectronic properties such as UV-vis absorption, photoluminescence, electrochemistry, spectroelectrochemistry and electrochromism of these polymers were investigated.
In the first part of this thesis, the diamine monomer N,N’-bis(4-aminophenyl)-N,N’-di-2-naphthyl-1,4-phenylenediamine was synthesized and reacted with various dicarboxylic acids via the phosphorylaton polyamidation technique leading to a series of new polyamides. These polyamides were amorphous with good solubility in many organic solvents and could be solution-cast into flexible and strong films. They exhibited moderately high thermal stability with glass transition temperatures in the range of 247-289 oC. The polyamide derived from 1,4-cyclohexanedicarboxylic acid revealed stronger fluorescence emission than those derived from aromatic ones, and it also showed a remarked solvent effect on the fluorescence profile. All the electroactive polymer films showed reversible electrochemical oxidation accompanied by strong color changes from colorless neutral state to green and blue oxidized states.
The second part of this thesis describes the synthesis and properties of polyimides on the basis of N,N’-bis(4-aminophenyl)-N,N’-di-2-naphthyl-1,4-phenylenediamine. The polyimides were prepared from the diamine monomer and various tetracarboxylic dianhydrides via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. Most of the polyimides were readily soluble in many organic solvents and could be solution-cast into tough and amorphous films. These polyimides showed a high level of thermal stability, with glass-transition temperatures of 288-329 oC and no significant decomposition before 500 oC. They showed well-defined and reversible redox couples during both p- and n-doping processes, together with multi-electrochromic behaviors.

並列關鍵字

polyamide ； polyimide ； triarylamine ； electrochromism ； photoluminescence ； spectroelectrochemistry

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