具有3,5-二甲基或雙三氟甲基取代之三苯胺結構的新型芳香族聚醯胺及聚醯亞胺之合成與光電性質之研究

Synthesis and Optoelectronic Properties of Aromatic Polyamides and Polyimides Bearing 3,5-Dimethyl- or Bis(trifluoromethyl)- substituted Triphenylamine Moieties

巫建楠(Chien-nan Wu)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2006年)

摘要

本篇論文內容主要包含三個研究主題，第一部分描述3,5-雙三氟甲基取代之芳香族二胺(3a)及二羧酸(3b)，分別與市售之八種芳香族二羧酸及五種芳香族二胺，進行磷酸化聚縮合反應生成兩系列的聚醯胺5a-h和7a-e。這兩系列的聚醯胺在常用的極性的有機溶劑下，皆有相當好的溶解性，並且擁有273~305 ℃高的玻璃軟化溫度(glass-transition temperatures)及良好的的熱重量殘餘率。其中7a-7e高分子稀薄溶液(10-5 M)的紫外-可見光吸收光譜(UV-vis absorption spectra)的最大吸收的波長介於310~350 nm之間，光激發光光譜(Photoluminescence spectra)的最強放光波長在421~443 nm之間，是屬於藍色的可見光。將5a-5h等高分子塗佈在氧化銦(ITO)導電玻璃做為工作電極，參考電極為Ag/AgCl 電極，輔助電極為白金絲，於TBAP 的0.1 M acetonitrile溶液中所測得的半波電位E1/2在1.15 V左右，將電壓由0 V增加到1.52 V其高分子薄膜將由淡黃色轉變成褐色。
第二部分描述3,5-雙甲基取代之芳香族二胺(10a)及二羧酸(10b)，經由磷酸化聚縮合反應生成兩系列新型聚醯胺11a-h和12a-e。這兩系列的聚醯胺在常用的極性的有機溶劑下，皆有相當好的溶解性，並且擁有245~322 ℃高的玻璃軟化溫度及10%的熱重量損失溫度都超過500 ℃。這兩系列高分子稀薄溶液(10-5 M)的紫外-可見光吸收光譜顯示最大吸收波長介於314~363 nm附近，其中7e的光激發光光譜之最大放光波長在426 nm左右，是屬於可見光區中的藍光，與這兩系列的其他聚合物相較下有較高的量子效率。將11-11h等高分子塗佈在氧化銦(ITO)導電玻璃進行氧化還原電位測定，所測得的半波電位E1/2在0.95 V左右，將電壓由0 V增加到1.25 V其高分子薄膜將由淡黃色轉變成綠色。
第三部分是利用第一部分及第二部分所合成的芳香族二胺單體(3a) 及(10a)，與六種市售的二酐先聚合成聚醯胺酸後再以熱閉環或化學閉環的兩步驟法，製成聚醯亞胺16a-f及17a-f。這兩系列的聚醯亞胺擁有271~303 ℃高的玻璃軟化溫度及10%的熱重量損失溫度都超過500 ℃。這兩系列高分子稀薄溶液(10-5 M)在紫外光-可見光吸收光譜下所吸收的波長介於300 nm左右，光激發光光譜所激發的波長在450~487 nm是屬於藍色的可見光。將17-17h等高分子塗佈在ITO導電玻璃上，在TBAP 的0.1 M acetonitrile電解液中所測得的半波電位E1/2在1.2 V左右，且將電壓由0 V增加到1.70 V其高分子薄膜將由淡黃色轉變成藍色。

關鍵字

三苯胺 ； 聚醯胺 ； 聚醯亞胺

並列摘要

This thesis consists of three parts. In the first part, we describe the preparation and characterization of aromatic polyamides 5a-h and 7a-e with main-chain triphenylamine units and trifluoromethyl substitutente from 3,5-bis(trifluoromethyl)-4’,4’’-diaminotriphenylaimine (3a) with various aromatic dicarboxylic acids and from 3,5-bis(trifluoromethyl)-4’,4’’-dicarboxytriphenylamine (3b) with various aromatic diamines, respectively. Most of the 5 and 7 series polymers were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent, tough, and flexible films with good mechanical properties. All the poly(amine-amide)s had useful levels of thermal stability associated with high glass-transition temperatures of 273~305 ℃ and 10% weight-loss temperatures in excess of 500 ℃. The poly(amine-amide)s 5a~5h and 7a~7e exhibited a UV-vis absorption maximum at around 310~350 nm in N-methyl-2-pyrrolidone (NMP) solutions. The poly(amine-amide)s 7a~7e were optically transparent in the visible region and fluoresced violet-blue at 421~443 nm in NMP. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the films of poly(amine-amide)s 5a~5h on the indium-tin oxide (ITO)-coated glass substrates exhibited one oxidation redox couples with E1/2 around 1.15 V versus Ag/AgCl in dry acetonitrile solution and revealed electrochromic characteristics with a color change from colorless to reddish brown at applied potentials switched between 0 and 1.52 V.
In the second part, two newly triphenylamine-containing aromatic diamine and dicarboxylic acid monomers, 3,5-dimethyl-4’,4’’-diaminotriphehylamine (10a) and 3,5-dimethyl-4,’4’’-dicarboxytriphenylamine (10b), were successfully synthesized. Two series of novel poly(amine-amide)s 11a-11h and 12a-12e with 3,5-dimethyl-substituted triphenylamine units having inherent viscosities of 0.56~1.43 dL/g were respectively prepared from the newly synthesized diamine monomer 10a and eight commercially available aromatic dicabroxylic acids and from the dicabroxylic acid monomer 10b and five commercially available aromatic diamines via direct phosphorylation polycondensation technique. Most of these polymers were amorphous and most of them could be solution-cast into flexible, transparent, and tough films. All the poly(amine-amide)s exhibited useful levels of thermal stability, such as high glass-transition temperatures (245~322 ℃), 10% weight-loss temperatures in excess of 500 ℃, and char yields at 800 oC in nitrogen higher than 63%. The poly(amine-amide)s 11a~11h and 12a~12e exhibited UV-vis absorption maximum at around 314~363 nm in NMP solutions. The poly(amine-amide) 12e derived from an aromatic 9,9-bis(4-aminophenyl)fluorene fluoresced violet-blue at 426 nm in NMP with 12% quantum yield higher than other poly(amine-amide)s. Cyclic voltammograms of the 11a~11h series poly(amine-amide)s exhibited a reversible oxidation wave with E1/2 around 0.95 V versus Ag/AgCl in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from neutral pale yellowish to green doped form at applied potentials ranging from 0.00 to 1.25 V.
In the third part, two series of novel poly(amine-imide)s 16a~16f and 17a~17f dL/g were prepared from the newly synthesized diamine monomers 3a nd 10a and six commercially available 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. The polymers of these two series were amorphous and most of them could afford flexible, transparent, and tough films with good mechanical properties. All the poly(amine-imide)s had useful levels of thermal stability associated with high glass-transition temperatures (271~303 ℃), 10% weight-loss temperatures in excess of 501 ℃, and char yields at 800 ℃ in nitrogen higher than 55%. The poly(amine-imide)s exhibited a ultraviolet-visible (UV-vis) absorption maximum at around 300 nm in NMP solutions, and their photoluminescence showed emission peaks around 450~487 nm in NMP solution. Cyclic voltammograms of the poly(amine-imide)s 17a~17h with E1/2 around 1.2 V versus Ag/AgCl in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from neutral pale yellowish to blue doped form at applied potentials ranging from 0.00 to 1.70 V.

並列關鍵字

Triphenylamine ； Aromatic Polyamides ； Aromatic Polyimides

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