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  • 學位論文

具芘基胺發色團之高性能聚合物的合成及其光電性質研究

SYNTHESIS AND OPTOELETRONIC PROPERTIES OF HIGH PERFORMANCE POLYMERS BEARING PYRENYLAMINE CHROMOPHORE

指導教授 : 蕭勝輝
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摘要


本論文論及兩種具有芘基胺結構之單體: N,N-di(4-aminophenyl)-1-aminopyrene 及 N,N-di(4-carboxyphenyl)-1-aminopyrene 及其衍生的高性能聚合物[包含聚醯胺、 聚醯亞胺、聚醯肼及聚(1,3,4-噁二唑)]的合成,並探討它們的光電性質如吸收光譜、 光致發光、電化學及電致變色性質等。 在論文的第一部分,首先由新製得的之二胺單體N,N-di(4-aminophenyl)- 1-aminopyrene 與芳香族或脂肪族二羧酸經由磷酸化聚縮合方法合成出一系列新型 具二苯基芘基胺發色團的聚醯胺。這些聚醯胺很容易溶解在多種有機溶劑並可經由 他們的溶液塗佈鑄成強韌、非晶型的薄膜。他們具有良好的熱穩定性,其玻璃轉移 溫度(Tgs)在246 與326 oC 之間, 10%重量損失的溫度超過500 oC。這些聚醯胺的 NMP 的稀薄溶液顯示螢光最強的波長值在522 及544 nm 之間而量子效率最高可達 30.2%。這些聚醯胺在不同溶劑下亦顯示出溶液色變(solvatochromism)現象。這些聚 合物的薄膜顯示出可逆的電化學氧化及還原反應,並伴隨明顯的顏色變化,它們會 由黃色的中性態轉變成紫色的氧化態及橘色的還原態。這些陽極電致變色薄膜具有 高的變色效率(在834 nm 的值可達172 cm2/C),它們在長時間的氧化還原循環之後 依舊保有高的電化學活性。 在第二部分,我們由二胺單體N,N-di(4-aminophenyl)-1-aminopyrene 與芳香族及 脂環族二酸酐合成出一系列新型的聚醯亞胺。這些聚醯亞胺在多種極性的有機溶劑 中展現良好的溶解性,並可經由溶液塗佈法鑄成強固的薄膜。由芳香族二酸酐衍生 的聚醯亞胺具有優異的熱穩定性及高的玻璃轉移溫度(Tg 值 > 333 oC)。聚合物薄膜 的循環伏安分析結果顯示這些聚醯亞胺兼具p-及n-可掺雜的特性並具有多顏色電致 變色現象。由脂環族二酸酐所衍生之聚醯亞胺顯示具有高的量子效率(ΦFL > 45%)的 強藍光放射現象及明顯的溶液色變行為。 在第三部分當中,我們利用新合成之二羧酸單體N,N-di(4-carboxyphenyl)- 1-aminopyrene 與芳香族二胺經由磷酸聚縮合反應製備另一個系列主鏈具二苯基芘 基胺鏈段的新型聚醯胺。這些聚醯胺可立即溶於許多有機溶劑,並可經由它們的溶 液塗製成強韌及非結晶型的薄膜。他們具有不錯的熱穩定性,其玻璃轉移溫度(Tgs) 在276~342 oC 之間,10%重量損失的溫度超過500 oC。這些聚醯胺的NMP 的稀薄 溶液顯示最大螢光放射的波長範圍在455~540 nm 之間,並具有高達56.9%的量子效 率,它們在不同的溶劑中也會表現出顯著的溶液色變行為。這些聚合物的薄膜顯示 出可逆的電化學氧化及還原反應,並伴隨著明顯的顏色改變,它們會由無色的中性 態轉變成紫色的氧化態及黃色的還原態。二羧酸及二胺的組成都具有二苯基芘基胺 結構的聚醯胺兼具p-及n-掺雜特性並可呈現多種顏色電致變色行為,其薄膜可由淡 黃色的中性態氧化轉變成灰綠色及紫灰色的全氧化態,以及經由深黃色的半還原態 轉變成橘紅色的全還原態。 此論文的最後一部分則在描述由N,N-di(4-carboxyphenyl)-1-aminopyrene 分別與 兩種二醯肼單體terephthalic dihydrazide 及 isophthalic dihydrazide 進行磷酸化聚縮 合反應合成出兩個帶有氧化還原活性的二苯基芘基胺結構的新型聚醯肼。這兩個聚 醯肼可進而經由加熱脫水環化轉變成聚(1,3,4-噁二唑)。如此製得的聚(1,3,4-噁二唑) 具備高的玻璃轉移溫度及高的熱穩定性。這些聚合物的稀薄溶液受到紫外光的激發 會產生中等至高強度的藍色到黃色的螢光。除了由二苯基芘基胺結構所引起的氧化 電變色之外,循環伏安分析結果顯示這些聚(1,3,4-噁二唑)的薄膜在還原過程中會因 為芘基及噁二唑的自由基陰離子的形成而由淡黃色轉變成橘色、橘紅色或深藍色。

並列摘要


This dissertation deals with the synthesis and characterization of two new pyrenylamine-containing monomers, named as N,N-di(4-aminophenyl)-1-aminopyrene and N,N-di(4-carboxyphenyl)-1-aminopyrene, and their derived high performance polymers that include polyamides, polyimides, polyhydrazides, and poly(1,3,4- oxadiazole)s. Optoelectronic properties such as absorption, photoluminescent, electrochemical, and electrochromic properties of these pyrenylamine-based polymers were investigated. First, a series of novel polyamides with diphenylpyrenylamine chromophore in the backbone were prepared from the newly synthesized diamine monomer, N,N-di(4-aminophenyl)-1-aminopyrene, and aromatic or aliphatic dicarboxylic acids via the phophorylation polyamidation technique. These polyamides were readily soluble in many organic solvents and could be solution-cast into tough and amorphous films. They had useful levels of thermal stability with glass-transition temperatures in the range of 246-326 oC and 10 % weight loss temperatures in excess of 500 oC. The dilute NMP solutions of these polyamides exhibited fluorescence maxima around 522-544 nm with quantum yields up to 30.2%. These polyamides also showed remarkable fluorescence solvatochromism in various solvents. The polymer films showed reversible electrochemical oxidation and reduction accompanied by strong color changes from yellow neutral state to purple oxidized state and to orange reduced state. The anodically electrochromic films had high coloration efficiency (up to 172 cm2/C at 834 nm) and good redox stability, which still retained a high electroactivity after long-term redox cycles. Second, a new family of polyimides based on N,N-di(4-aminophenyl)-1- aminopyrene and aromatic or alicyclic tetracarboxylic dianhydrides were synthesized. These polyimides exhibited good solubility in many polar organic solvents and could afford robust films via solution casting. The polyimides derived from aromatic dianhydrides exhibited high thermal stability and high glass transition temperatures (333-364 oC). Cyclic voltammetry studies of the polymer films showed that these polyimides are both p and n dopable and have multicolored electrochromic states. For the polyimides derived from alicyclic dianhydrides, they revealed a strong blue-light emission with high fluorescence quantum yields (ΦFL > 45%) and a marked solvatochromic behavior. Thirdly, another series of novel polyamides with diphenylpyrenylamine segments in the backbone were prepared from the newly synthesized dicarboxylic acid monomer, N,N-di(4-carboxyphenyl)-1-aminopyrene, and various aromatic diamines via the phophorylation polyamidation technique. These polyamides were readily soluble in many organic solvents and could be solution-cast into tough and amorphous films. They had useful levels of thermal stability with glass-transition temperatures in the range of 276-342 oC and 10 % weight loss temperatures in excess of 500 oC. The dilute NMP solutions of these polyamides exhibited fluorescence maxima around 455-540 nm with quantum yields up to 56.9%. These polyamides also showed remarkable fluorescence solvatochromism in various solvents. The polymer films showed reversible electrochemical oxidation and reduction accompanied by strong color changes from colorless neutral state to purple oxidized state and to yellow reduced state. The polyamide bearing diphenylpyrenylamino unit in both diacid and diamine components exhibited both p- and n-doping electrochemical processes, and showed a multicolored electrochromic behavior with color change from pale yellow neutral state to greenish gray then purplish gray fully oxidized state and to dark yellow semi-reduced state then reddish orange fully reduced state. Finally, two new polyhydrazides bearing redox-active diphenylpyrenylamine unit were prepared from the phosphorylation polycondensation reaction of N,N-di(4-carboxyphenyl)- 1-aminopyrene with terephthalic dihydrazide and isophthalic dihydrazide, respectively. These two polyhydrazide prepolymers could be further thermally cyclodehydrated into the corresponding poly(1,3,4-oxadiazole)s in the solid state. The resulting poly(1,3,4-oxdiazole)s had high glass-transition temperatures and high thermal stability. The dilute solutions of all the hydrazide and oxadiazole polymers showed a medium to strong fluorescence in the blue to yellow region. Additionally, cyclic voltammetry studies of the oxadiazole polymers also showed reduction processes accompanied by strong color changes from pale yellow to orange, orange-red or deep blue due to the formation of radical anions of the oxadiazole and pyrene units.

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