臺灣博碩士論文加值系統

本研究4-(N-Pyrroyle)aniline之合成首先使用 pyrrole 與 4-fluoronitrobenzene，於DMSO溶劑中，以氫化鈉 (NaH)為媒介，進行芳香親核氟取代反應，隨後再進行聯胺和Pd/C催化還原反應，再者其4-(N-Pyrroyle)aniline與4-fluoronitrobenzene的胺化反應以及其後的二硝基中間體之還原進而製得一個種新型具有三苯胺結構的芳香族二胺單體4,4’-diamino-4”-(N-pyrrolyl)triphenylamine (4)。之後，再利用上述製得的二胺單體和一系列芳香族二羧酸進行磷酸化直接聚縮合反應，製備一系列新型、具有pyrrole基取代的三苯胺結構的芳香族聚醯胺。這些聚醯胺呈現非晶形結構，可溶在 NMP 極性等有機溶劑中，並可由它們的溶液鑄成深色且具有可撓曲性的強韌薄膜。這些聚合物的玻璃轉移溫度介於 286 到 317 oC 之間，在氮氣或空氣下的10%重量損失溫度皆在 531 oC 以上，在氮氣下加熱至 800 oC 時的焦炭殘餘率超過66％，顯示具有良好的熱安定性。這些聚醯胺的 NMP 溶液在406~456 nm 附近具有強的 UV-Vis 吸收。此外，我們也利用電化學及光譜電化學來探討它們的電動傳輸及電致變色的特性。塗佈在 ITO 玻璃上的聚醯胺與聚醯亞胺薄膜的循環伏安圖在半波電位(E1/2)分別為 0.88~0.94 V 與1.14~1.28 V之間顯示一對可逆的氧化還原峰，而且這些聚醯胺薄膜在 0.0 V 至 2.0 V之間至少連續12次的變換施加電壓後，大部分薄膜仍呈現穩定的電致變色特性，顏色會從中性態的淺黃色變化成氧化態的綠色。

4-(N-Pyrroyle)aniline was synthesized by the nucleophilic fluoro-displacement reaction of 1-fluoro-4-nitrobenzene with pyrrole from sodium hydride medium in DMSO solvent, followed by palladium-catalyzed hydrazine reduction. Further amination reaction between 4-(N-pyrroyle)aniline and 1-fluoro-4-nitrobenzene and subsequent reduction of dinitro intermediate led to a new triphenylamine-containing aromatic diamine monomer, 4,4’-Diamino-4”-(N-pyrrolyl)triphenylamine. This newly synthesized diamine monomer was polycondensed with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine-based polyamides and polyimides with pendent pyrrolyl substituents. Almost all the studied polymers could afford amorphous and tough films. These polymers showed high glass transition temperatures between 286 and 317 ℃, and they were stable up to a temperatue above 450℃ (for polyamides) or 500℃ (for polyimides). These polymers exhibited UV-Vis absorption maxima around 316 to 363 nm in NMP solution. The photoluminescence spectra of most of the polyamides in NMP exhibited a peak emission wavelength in the blue at 380-452 nm. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamides and polyimides showed a half-wave oxidation potential (E1/2) 0.88-0.94 V and 1.14-1.28 V (versus Ag/AgCl), respectively, in an acetonitrile solution. The polyamide films revealed good stability of electrochromic characteristics, with a coloration change of the film from the pale yellow neutral form to the green oxidized form. The coloration change was followed by UV-Vis spectroscopy.

ACKNOWLEDGEMENTS ii
ABSTRACT (in English) iii
ABSTRACT (in Chinese) v
TABLE OF CONTENTS vii
LIST OF TABLES ix
LIST OF FIGURES x
LIST OF SCHEMES xii
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENT 5
2.1 Materials 5
2.2 Monomer Synthesis 6
2.2.1 4-(N-Nitrophenyl)pyrrole (1) 6
2.2.2 4-(N-Pyrrolyl)aniline (2) 8
2.2.3 4,4’-Dinitro-4”-(N-pyrrolyl)triphenylamine (3) 9
2.2.4 4,4’-Diamino-4”-(N-pyrrolyl)triphenylamine (4) 10
2.3 Polymer Synthesis 11
2.3.1 Synthesis of Polyamides 11
2.3.2 Synthesis of Polyimides 12
2.4 Preparation of Polyamide Films 14
2.5 Measurements 14
CHAPTER 3 RESULTS AND DISCUSSION 17
3.1 Monomer Synthesis 17
3.2 Polymer Synthesis 23
3.3 Properties of Polymers 30
3.3.1 X-ray Diffraction Data and Organo-solubility 30
3.3.2 Tensile Properties 35
3.3.3 Thermal Properties 36
3.3.4 Optical and Electrochemical Properties 42
3.3.5 Spectroelectrochemical and Electrochromic Properties 52
CHAPTER 4 CONCLUSIONS 57
REFERENCES 58

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