新型含醚基連接雙三苯胺結構之芳香族聚醯胺與聚醯亞胺的合成和電致變色性質

Synthesis and Electrochromic Properties of Novel Aromatic Polyamides and Polyimides Bearing Ether-linked Bis(triphenylamine) Units

鄭守倫(Shou-Lun Cheng)

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(2011年)

https://doi.org/10.6841/NTUT.2011.00558

摘要

本論文包含兩個研究主題，主要探討由一種具有醚基連接雙三苯胺結構的二胺單體所衍生的芳香族聚醯胺(polyamides)與聚醯亞胺(polyimides)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新型具有醚基連接雙三苯胺結構的二胺單體N,N-Di(4-aminophenyl)-N',N'-diphenyl-4,4'-oxydianiline 的合成，並藉由磷酸化聚縮合反應法將此二胺單體與各種芳香族二羧酸聚合成一系列新型的芳香族聚醯胺。這些聚醯胺的固有黏度在0.31-0.44 dL/g之間，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218-253 oC，在溫度超過500 oC才有10%的熱重量損失，並且在氮氣下溫度到達800 oC時還有65%以上的焦碳殘留率。塗佈在ITO玻璃上的聚醯胺薄膜在乙腈溶液中的循環伏安測定結果顯示出在0.80~0.82 V和0.96~0.98 V附近有兩個成對且可逆的氧化還原峰。這一系列的聚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1.2 V間薄膜顏色會從中性態的透明無色或淡黃色變成氧化態的綠色和紫色。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。
第二部分則在探討以上述具有醚基連接雙三苯胺結構的二胺單體為主體的聚醯亞胺的合成與特性。這些聚醯亞胺是由上述的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。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、具有可撓曲性的薄膜。聚醯胺酸的固有黏度範圍在0.47-0.88 dL/g之間。這一系列的聚醯亞胺展現出優異的熱穩定性，玻璃態轉移溫度範圍在227-273 oC之間，並且在溫度超過550 oC才會有10%熱重量損失。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 ； 三苯胺 ； 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 an aromatic diamine monomer bearing the ether-linked bis(triphenylamine) [O(TPA)2] unit and its derived aromatic polyamides and polyimides. The electrochemical, spectroelectrochemical and electrochromic properties of the polymers have been investigated.
In the first part of this thesis, a new diamine monomer with the O(TPA)2 unit, namely N,N-di(4-aminophenyl)-N',N'-diphenyl-4,4'-oxydianiline, was synthesized and reacted with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a series of novel redox-active aromatic polyamides. These polyamides exhibited inherent viscosities between 0.31 and 0.44 dL/g, and they were readily soluble in polar organic solvents like NMP and DMAc and could be solution-cast into amorphous and flexible films. The polyamides exhibited good thermal stability with glass-transition temperatures in the range of 218-253 oC, 10% weight-loss temperatures in excess of 500 oC and char yields at 800 oC in nitrogen higher than 65%. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.80~0.82 V and 0.96~0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent electrochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and purple oxidized forms at applied potentials ranging from 0 to 1.2 V. Electrochromic devices using these polymers as active materials were also fabricated, and they showed high coloration efficiency, high redox stability, and fast response time.
The second part describes the synthesis and properties of aromatic polyimides on the basis of the diamine monomer with the O(TPA)2 unit in the first part. These polyimides were prepared from the O(TPA)2 diamine monomer and various aromatic 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. The inherent viscosities of the poly(amic acid) precursors were in the range 0.47-0.88 dL/g. The series of polyimides exhibited excellent thermal stability, with glass-transition temperatures in the range of 227-273 oC and 10% weight-loss temperatures in excess of 550 oC. Cyclic voltammetry studies of the polymer films showed that these polyimides are both p and n dopable and have multicolored electrochromic states.

並列關鍵字

polyamides ； polyimides ； triphenylamine ； electrochromic ； spectroelectrochemical ； electrochromic device

參考文獻

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