新型含三苯胺結構之芳香族聚醚醯胺與聚醚醯亞胺的合成和電致變色性質

Synthesis and Electrochromic Properties of Novel Aromatic Polyetheramides and Polyetherimides Bearing Triphenylamine Units

張佩琦(Pei-Chi Chang)

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(2012年)

https://doi.org/10.6841/NTUT.2012.00467

摘要

本論文包含三個研究主題，主要探討由具有三苯胺結構的二醚二胺及二醚二酸酐單體所衍生的芳香族聚醚醯胺(polyetheramides)與聚醯亞胺(polyetherimides)的合成及其電化學、光譜電化學和電致變色等性質。
第一部分在探討一種具有雙苯氧基連接三苯胺結構的二胺單體4,4’-Bis(p-aminophenoxy)triphenylamine的合成，此二醚二胺單體與各種芳香族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到聚醚醯亞胺。這一系列的聚醚醯亞胺展現出優異的熱穩定性，玻璃態轉移溫度範圍在234-281 oC之間，並且在溫度超過540 oC才會有10%的重量損失。由高分子薄膜的循環伏安研究發現這些聚醚醯亞胺同時擁有p- 和 n-可摻雜的特性並且具有多顏色電致變色的現象。在與沒有苯氧基結構取代的聚合物來比較，他們有著明顯較佳的電化學穩定性。
第二部分則在探討以上述具有雙苯氧基連接三苯胺結構的二胺單體為主體的聚醚醯胺的合成與特性。一系列新型的芳香族聚醚醯胺是由上述的二醚二胺單體與各種芳香族二羧酸進行磷酸化聚縮合反應而得。這些聚醯胺屬於非結晶性的材料，並且易溶於極性的有機溶劑如NMP、DMAc，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227-234 oC，在溫度超過530 oC才有10%的重量損失。這一系列的聚醚醯胺薄膜展現出優異的電化學和電致變色穩定性，施加電壓範圍在0到1.06 V間薄膜顏色會從中性態的透明無色變成氧化態的淡黃色或藍色。
第三部分在探討一種新型具有三苯胺結構的二醚二酸酐單體4,4’-Bis(3,4-dicarboxyphenoxy)triphenylamine dianhydride及其聚醚醯亞胺的合成及性質。這一系列的聚醚醯亞胺的玻璃態轉移溫度範圍在211-299 oC之間。由高分子薄膜的循環伏安研究發現這些聚醚醯亞胺同時擁有p- 和 n-可摻雜的特性並且具有多顏色電致變色的現象。在進行循環伏安實驗的過程中，這些聚醚醯亞胺電氧化產生的三苯胺自由基陽離子結構單元會進行偶合反應而形成交聯型的電致變色聚合物。這些高分子薄膜做成的電致變色元件具有高的變色效率和電致變色穩定度以及快速的顏色變化。

關鍵字

聚醚醯胺 ； 聚醚醯亞胺 ； 三苯胺 ； 電聚合 ； 電致變色 ； 光譜電化學 ； 電致變色元件

並列摘要

This thesis is aimed to synthesize and characterize two triphenylamine (TPA)-based bis(ether amine) and bis(ether anhydride) monomers and their derived aromatic polyetheramides and polyetherimides. The electrochemical, spectroelectrochemical and electrochromic properties of these polymers will be investigated.
In the first part of this thesis, a TPA-bis(ether amine) monomer, namely bis(p-aminophenoxy)triphenylamine, was successfully synthesized and reacted with aromatic tetracarboxylic dianhydrides via a conventional two-step technique leading to a series of TPA-containing polyetherimides. These polyetherimides showed a high level of thermal stability, with glass-transition temperatures of 234-282 oC and decomposition temperatures in excess of 540 oC. They showed well-defined and reversible redox couples during both p- and n-doping processes, together with multi-electrochromic behaviors. They exhibited enhanced redox-stability and electrochromic performance as compared to the corresponding analogs without the phenoxy spacer between the TPA and imide units.
The second part reports the synthesis and properties of aromatic polyetheramides on the basis of the TPA-bis(ether amine) monomer as described in the first part. These polyetheramides were prepared via the direct phosphorylation polycondensation from bis(p-aminophenoxy)triphenylamine and aromatic dicarboxylic acids. These polyamides were amorphous with good solubility in many organic solvents, such as NMP and DMAc, and could be solution-cast into flexible polymer films. The polyetheramides had useful levels of thermal stability with glass-transition temperatures in the range of 227-234 oC and 10% weight loss temperatures in excess of 530 oC. The polymer films revealed excellent electrochemical and electrochromic stability, with a color change from a colorless neutral form to yellow and blue oxidized forms at applied potentials ranging from 0 to 1.06 V.
The third part of this thesis deals with the synthesis and characterization of a new TPA-bis(ether anhydride) monomer, 4,4’-bis(3,4-dicarboxyphenoxy)- triphenylamine dianhydride, and its derived polyetherimides. The polyetherimides exhibited glass-transition temperatures in the range 211–299 oC. They showed well-defined and reversible redox couples during both p- and n-doping processes, together with multicolored electrochromic behaviors. During the n-doping process, a cross-linked polymer structure may be formed due to the coupling reaction between the TPA radical cations in the polymer chain. These polymers can be used to fabricate electrochromic devices with high coloration efficiency, high redox stability, and fast response time.

並列關鍵字

polyetheramides ； polyetherimides ； triphenylamine ； electrochemistry ； electrochromism ； spectroelectrochemistry ； electrochromic devices

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