臺灣博碩士論文加值系統

本研究首先合成以吡咯結構為主的衍生物N-(3hydroxypropyl)pyrrole (HPPY)，並以1H-核磁共振光譜儀(1H-NMR)、13C-核磁共振光譜儀(13C-NMR)、霍式紅外線光譜儀(FT-IR)與氣相層析質譜儀(GC-Mass)來鑑定其合成之結構，並以電化學方法將poly(3-hexylthiophene)(P3HT)、poly N-(3hydroxypropyl)pyrrole (PHP)及poly(3-hexylthiophene-co-N-3-hydroxy) pyrrole (Copolymer)聚合在ITO玻璃上，並以光譜電化學探討此種塗佈於ITO玻璃上之共聚合物的電變色性質,再以霍式紅外線光譜儀(FT-IR) 與元素分析儀(EA)來鑑定其結構及特徵。
共聚物組成在熱穩定性、光學性質、電化學、結晶度和表面型態的影響是以熱重分析儀(TGA) 、微差掃描式熱分析儀(DSC) 、紫外-可見光光譜儀(UV-vis )、循環伏特安培儀(CV)、廣角X-Ray繞射儀(Wild-angle XRD)、掃描式電子顯微鏡 (SEM)來評估。

In this research, the derivative of pyrrole, N-(3-hydroxypropyl) pyrrole (HPPY) has been synthesized and identified by 1H-NMR, 13C-NMR, FT-IR, UV-vis and GC-Mass spectroscopies.The homopolymers of poly(3-hexylthiophene) (P3HT) and poly N-(3-hydroxypropyl)pyrrole (PHP) and their copolymer poly(3-hexylthiophene-co-N-3-hydroxy)pyrrole have been prepared by electrochemical polymerization on the ITO glass. The electrochromic properties as-prepared copolymer coated ITO glass was innestigated by spectrum electrochemistry studies. The as-prepared copolymer was characterized by Fouier Transform Infrared (FT-IR) and Element analysis (EA). Effect of copolymer composition on the thermal stability, optical properties, electrochemistry, crystallinity. and surface morphology was evaluated by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC),UV-Uisible absorption spectroscopy, cyclic voltaminetry (CV) studies,powder X-ray diffraction (XRD)pattern and scanning electron microscopy(SEM).

目錄
中文摘要................................................ Ⅰ
英文摘要................................................ Ⅱ
謝誌.................................................... Ⅲ
目錄.................................................... Ⅳ
圖目錄.................................................. Ⅴ
表目錄.................................................. Ⅵ
第一章 緒論...............................................1
1-1導電高分子簡介.......................................1
1.1.1導電高分子之發展................................2
1.1.2 導電高分子的導電機理—基本能帶理論與參雜理論...4
1.1.3共軛高分子導電理論..............................8
1.1.4導電高分子之應用...............................12
1-2 電變色材料簡介....................................14
1.2.1 電變色材料定義.................................14
1.2.2 電變色材料.....................................14
1.2.3 電變色原件.....................................17
1.2.4 電變色材料之應用...............................18
1.2.5聚吡咯高分子之介紹..............................19
1.2.5.1聚吡咯高分子製備方式........................20
1.2.5.2 聚吡咯高分子之聚合機構.....................22
1-2-6 聚塞吩之簡介...................................34
1-3研究動機...........................................37
第二章 研究使用之儀器與藥品..............................39
2-1藥品部分............................................39
2-2儀器部分............................................40
第三章 合成與鑑定........................................43
3-1 合成與鑑定.........................................43
3-1-1 N-(3-hydroxypropyl)pyrrole (HPPY)的合成與鑑........ 44
3-2聚合物之製備........................................49
第四章 結果與討論.......................................54
4-1 P3HT，PHP與共聚物之結構分........................54
4-1-1 紅線光譜分析（Fourier Transform Infrared ，FT-IR）
.....................................................54
4-1-2 元素分析儀測試（Elemental Analysis，EA）
.....................................................57
4-1-3 導電度測試 (Conductivity)........................58
4-1-4 電化學測試 (Cyclic Voltammegram)................ 59
4-1-5 光譜儀之光學測試（UV-Vis Spectrophotometer）
.....................................................62
4-1-5-1電變色機制探討...................... 62
4-1-5-2 UV-Vis Spectrophotometer.......................67
4-1-5-3共聚合物的型態.............................. 70
4-1-6掃描式電子顯微鏡 (SEM) ....................... 75
4-1-7廣角X-Ray繞射儀 (Wide-angle XRD) .............. 79
4-1-8 探討三種有機聚合物在ITO玻璃上之熱性質分析.... 80
4-1-8-1熱重分析儀(TGA) ......................... 80
4-1-8-2微差掃描式熱分析儀(DSC) .................. 81
第五章 結論..............................................82
參考文獻.................................................83

圖目錄
圖1-1、不同材料之屬性分界與其導電度………………………………5
圖1-2、軌域能階成長能帶圖………………………………………….. 6
圖1-3、金屬、半導體與絕緣體的能隙與能帶圖………………………..7
圖 1-4、本質型半導體的能帶模型……………………………………..8
圖 1-5、非本質型半導體的能帶模型 (a) P-型參雜 (b) N-型參雜…...8
圖 1-6、隨分子大小的遞增的PA,(CH)n其pMOs之能階示意圖…….10
圖 1-7、Trans-(CH)n的Soliton模型 (a) S0 (b) S+ (c) S-……………..11
圖 1-8、polaron與bipolaron之能帶示意圖…………………………..12
圖 1-9、Viologens的變色反應機制…………………………………...16
圖 1-10、Matellopolymer的變色機制與其顏色變化……...…………17
圖 1-11、典型的電變色元件示意圖.......................................................18
圖 1-12、polypyrrole結構圖...................................................................20
圖 1-13、Head to tail的結構...................................................................35
圖 1-14、Head to Head & tail to tail的結構...........................................35
圖 3-1、單體合成反應圖........................................................................43
圖3-2、N-(2-hydroxyethyl)pyrrole (HEPY) 合成之流程圖.................48
圖3-3、電聚合之裝置圖..........................................................................49
圖3-4、HPPY 1H-NMR 光譜圖.............................................................51
圖 3-5、HPPY 13C-NMR 光譜圖............................................................51
圖 3-6、HPPY 紅外線光譜圖.................................................................52
圖 3-7、HPPY 質譜圖.............................................................................52
圖 3-8、電聚合之循環伏安圖(a) P3HT (b) PHP (c) 共聚合物............53
圖 4-1、聚合物之霍式紅外線光譜圖 (a) P3HT (b) PHP (c)共聚合物
..................................................................................................................56
圖 4-2、四點碳針示意圖.........................................................................58
圖 4-3、聚合物之循環伏安測試圖 (a) P3HP (b) PHP (c) 共聚合物
..................................................................................................................61
圖 4-4、 2-Butenal之UV-Vis 吸收光譜.........................63
圖4-5、2-Butenal之能階圖..........................................63
圖4-6、化合物A 共振之UV-Vis吸收光譜圖................................66
圖 4-7、cis-trans stilbene之UV-Vis 吸收光譜圖..................................66
圖 4-8、共聚合物在不同氧化態下結構通式表示圖............................70
圖 4-9、不同氧化狀態下共聚合物結構示意圖.....................................71
圖 4-10、 P3HT在不同電位之可見光吸收光譜圖...............................72
圖 4-11、PHP在不同電位之可見光吸收光譜圖..................................72
圖 4-12、共聚合物在不同電位之可見光吸收光譜圖..........................73
圖 4-13、放大倍率10下，不同的有機聚合物的SEM圖。(a)P3HP
(b)PHP (c) 共聚合物..................................................................76
圖 4-14、放大倍率50K下，不同的有機聚合物的SEM圖。(a)P3HP
(b)PHP (c) 共聚合物...................................................................77
圖 4-15、不同有機聚合物側面SEM圖。(a)P3HP (b)PHP (c) 共聚合物............................................................................................................. 78
圖 4-16、塗佈在ITO玻璃上的有機聚合物...........................................79
圖 4-17、不同有機聚合物的TGA圖.....................................................80
圖 4-18、不同有機聚合物的DSC圖.....................................................81


表目錄
表1-1、常見導電高分子種類...................................................................3
表1-2、不同Poly(3-alkylthiophene)寡聚體的顏色變化.........................36
表4-1、P3HT、PHP與共聚合物之紅外線吸收峰對照表......................55
表4-2、三種導電高分子的導電度值..................................................... 59
表4-3、Woodward-Fieser rules for calculating λmax...............................64
表4-4、P3HT、PHP與共聚合物波長吸收顏色變化..............................74

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