臺灣博碩士論文加值系統

本論文首先以4-胺基三苯胺與均苯四甲酸二酐(PMDA)進行縮合反應合成具有雙三苯胺的化合物N,N’-Bis(4-diphenylaminophenyl)pyromellitimide，藉由三苯胺自由基陽離子之間的偶聯反應在電極表面電聚合成電活性的高分子薄膜(PI-E)，這高分子薄膜具有可逆的電化學氧化還原反應，並且會伴隨著明顯的電致變色現象，PI-E高分子薄膜可由無色的中性態變為橙黃色和藍色的氧化態，也可以在還原時變成淺綠色和粉紅色的陰極變色，並使用PI-E薄膜作為電致變色材料製作成電致變色元件作為電致變色應用的初步研究，並利用N,N’-bis(4-aminophenyl)-N,N’-diphenyl-4,4’-biphenydiamine與PMDA進行兩步驟聚合反應製備出結構相似的聚醯亞胺(PI-C)，並將其電化學和電致變色性能與電聚合合成的PI-E進行比較。
在論文第二部分中合成了一系列含三苯甲基取代的三苯胺結構的聚醯胺與聚醯亞胺，分別由4,4’-diamino-4”-trityltriphenylamine與二羧酸和二酸酐進行縮聚合反應合成，此一系列的高分子皆具備良好的溶解性，在常溫皆可溶解在大部分的極性溶劑中，並導入脂肪族的二羧酸和四羧酸二酸酐，降低因電荷轉移所產生的顏色，這些高分子的玻璃轉移溫度在206~336 oC之間，呈現可逆的氧化還原過程，並伴隨著明顯的顏色變化，由無色的中性態轉變成藍綠色的氧化態，其中聚醯胺因具有較低的氧化電位，因此比聚醯亞胺有更高的電致變色穩定性與著色效率。

In the first part of this thesis, a bis(triphenylamine)-pyromellitic diimide compound (TPA-PMDI) was synthesized from the condensation reaction of 4-aminotriphenylamine with pyromellitic dianhydride (PMDA). The dicarboximide TPA-PMDI could be electrochemically polymerized into ambipolar, redox-active polyimide films on the electrode surface in an electrolyte solution via the coupling reactions between triphenylamine radical cations. The electro-generated polyimide films (coded as PI-E) exhibit reversible redox processes and stable color changes upon electro-oxidation, changing from colorless neutral form to orange-yellowish and blue oxidized states. The film also could display pale green and pink cathodic coloring upon electro-reduction. Electrochromic devices using the electropolymerized film as an active layer were also fabricated as preliminary investigations for electrochromic applications. For a comparative study, a structurally similar polyimide (PI-C) was prepared by a conventional two-step condensation from N,N’-bis(4-aminophenyl)-N,N’-diphenyl-4,4’-biphenydiamine with PMDA, and its electrochemical and electrochromic properties were compared with those of the electro-synthesized PI-E.

In the second part of this thesis, two series of polyamides and polyimides containing trityl (triphenylmethyl)-substituted triphenylamine units were synthesized from condensation reactions of 4,4’-diamino-4”-trityltriphenylamine with various dicarboxylic acids and tetracarboxylic dianhydrides, respectively. All the polymers were readily soluble in many organic solvents. The use of aliphatic diacid or dianhydride reduces interchain charge transfer complexing and leads to colorless polyamide and polyimide films. These polymers showed glass-transition temperature in the range of 206-336 °C. Cyclic voltammograms of the polyamide and polyimide films cast onto the indium-tin oxide (ITO)-coated glass substrate revealed reversible electrochemical oxidation processes accompanied with strong color changes from the colorless neutral state to blue-green or blue oxidized forms at applied potentials ranging from 0 to 1.0 V or 1.3 V. As compared to the polyimide counterparts, the polyamides showed lower oxidation potentials and thus higher electrochromic stability and coloration efficiency.

摘要 i
ABSTRACT iii
ACKNOWLEDGEMENTS v
CONTENTS vi
LIST OF SCHEMES x
LIST OF TABLES x
LIST OF FIGURES xii
Part I
ABSTRACT 2
CHAPTER 1 3
CHAPTER 2 5
2.1 Materials and Instrumentation 5
2.1.1 Materials 5
2.1.2 Instrumentation 5
2.2 Monomer Synthesis 7
2.2.1 N,N’-Bis(4-diphenylaminophenyl)pyromellitimide (TPA-PMDI) 7
2.2.2 N,N’-Bis(4-nitrophenyl)-N,N’-diphenyl-4,4’-biphenyldiamine (2) 7
2.2.3 N,N’-Bis(4-aminophenyl)-N,N’-diphenyl-4,4’-biphenyldiamine (3) 8
2.2.4 N-(4-Diphenylaminophenyl)phthalimide (M1) 9
2.2.5 N,N’-Bis(phthalimide)-N,N’-bis(4-aminophenyl)-N,N’-diphenyl-4,4’-Biphenyldiamine (M2) 10
2.3 Conventional Synthesis of Polyimide PI-C 11
2.4 Electrochemical Polymerization 12
2.5 Fabrication of Electrochromic Devices 12
CHAPTER 3 13
3.1 Synthesis of Monomers and Model Compounds 13
3.2 Conventional synthesis of PI-C 15
3.3 Electrochemical Activity of Monomer and Model Compounds 27
3.4 Polymer Properties 32
3.4.1 Thermal Properties of PI-C 32
3.4.2 Optical Properties 34
3.4.3 Electrochemical Properties 35
3.4.4 Spectroelectrochemical and Electrochromic Properties 39
3.5 Surface Morphology 45
3.6 Electrochromic Switching 46
3.7 Electrochromic Devices 54
CHAPTER 4 56
REFERENCES 57
Part II
ABSTRACT 63
CHAPTER 1 64
CHAPTER 2 66
2.1 Materials and Instrumentation 66
2.1.1 Materials 66
2.1.2 Instrumentation 67
2.2 Monomer Synthesis 68
2.2.1 4-Tritylaniline (1) 68
2.2.2 4,4’-Dinitro -4”-trityltriphenylamine (2) 68
2.2.3 4,4’-Diamino -4”-trityltriphenylamine (3) 69
2.3 Synthesis of Polyamides 71
2.4 Synthesis of Polyimides 72
2.5 Preparation of the Polymer films 73
2.6 Instrumentation and Measurements 73
CHAPTER 3 75
3.1 Monomer Synthesis 75
3.2 Synthesis of Polyamides 81
3.3 Synthesis of Polyimides 85
3.4 Properties of Polyamides and Polyimides 89
3.4.1 Solubility 89
3.4.2 Thermal Properties 91
3.4.3 Electrochemical Properties 95
3.4.4 Spectroelectrochemical and Electrochromic Properties 101
3.4.5 Electrochromic Switching and Stability 108
CHAPTER 4 115
REFERENCES 116

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