含雙?吩環戊烷之紅色與綠色共軛高分子用於電致變色材料上之研究

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研究生：	何銘軒 Ming-hsuan Ho
論文名稱：	含雙?吩環戊烷之紅色與綠色共軛高分子用於電致變色材料上之研究 Neutral State Red and Green Electrochromic Conjugated Polymers Based on DOCPDT
指導教授：	吳春桂 Chun-Guey Wu
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	98
語文別：	中文
論文頁數：	131
中文關鍵詞：	共軛高分子、電致變色材料、低能隙高分子
外文關鍵詞：	processable conducting polymer, low bandgap polymer, electrochromic materials
相關次數：	點閱：17 下載：0
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電致變色材料用於智慧型窗戶上時，可作為一新型節能材料。同時也能應用於在電子書與顯示器，共軛高分子因具有應答時間快、色彩多樣性與光學對比高，以及驅動電壓低，著色效率高與元件製備容易等優勢，成為一具有發展潛力的電致變色材料。本研究為新結構電致變色高分子的開發，發展出一系列應用在電致變色材料上的紅色與綠色共軛高分子，我們以DOCPDT做為基本單元，與芳香環Benzene (B)、Biphenyl (BP)，或兩個電子受體2,3-di(thiophen-2-yl)-2, 3-dihydroquinoxaline (DTQ)、2,3-di(benzen-2-yl)-2,3-dihydroquinoxaline (DBQ)進行偶合成含兩單元的單體後，再以化學氧化聚合方式聚合成共聚物，分別得到紅色與綠色高分子，以NMR鑑定其結構，再以TGA、SEM、GPC進行基本特性測量，之後再以電化學光學同步裝置測量高分子膜的電致變色特性，由實驗結果得知，共聚物PBDOCPDT-BP在中性態呈現紅色，應答時間可達次秒(0.5s)，具有高著色效率(550cm2/C)與高度穩定性(90%)，為一優良的紅色電致變色材料，而共聚物PBDOCPDT-DBQ在中性態時呈現綠色，而在氧化態時為穿透度高的淡綠色，在電變色行為方面，應答時間為1s左右，且在一千次顏色改變之後光學對比穩定性可維持90%以上，亦為一優良的綠色電致變色材料。

Electrochromic materials can be applied in Smart Windows to save energy. It also can be used in e-book and display. Conjugated polymers are potentially useful electrochromic materials due to their advantages of fast response time, multiple color, high optical contrast, high coloration efficiency and good processibility. In this study, we focus on the conjugated polymers with three primary color RGB (Red, Green, Blue) with DOCPDT in the polymer backbone. DOCPDT coupled with different moieties such as Benzene (B)、Biphenyl (BP) or electron acceptor such as 2,3-di(thiophen-2-yl)-2, 3-dihydroquinoxaline (DTQ) or 2,3-di(benzenyl)-2, 3-dihydroquinoxaline (DBQ) to form the monomer of the copolymer. The copolymers were obtained by chemical oxidative polymerization of the corresponding monomers. The structures of these copolymers were identified by 1H-NMR spectroscopy and their electrochromic properties were well studied. The copolymer PBDOCPDT-BP shows a beautiful red color in neutral state, with a fast response time (0.5s) high coloration efficiency (550cm2/C) and good stability (90%). PBDOCPDT-DBQ exhibits reversible electrochromic properties with color changes from deep green in the neutral state to light green in the oxidized state. After 1000 cycles of redox switches, the ΔT value more 90% of the original value, is a promising green electrochromic polymer.

摘要........................................................................................................i
Abstract................................................................................................ii
目錄......................................................................................................iii
圖目錄................................................................................................viii
表目錄.................................................................................................xii
第一章 序論
1-1 前言.....................................................................................................1
1-2 電致變色原理.....................................................................................2
1-3 電致變色材料的基本參數.................................................................4
1-4 電致變色材料的應用.........................................................................7
1-5 電致變色材料的種類.......................................................................10
1-6 以共軛高分子作為電致變色材料的優點.......................................13
1-7 調變共軛高分子顏色的方式...........................................................16
1-8 合成三原色電致變色共軛高分子...................................................22
1-9 基礎色彩學.......................................................................................22
1-10 研究動機...........................................................................................24
第二章 實驗部分
2-1 實驗藥品.............................................................................................26
2-2 PDOCPDT 共軛高分子與其衍生物合成之實驗流程圖..................30
2-2-1 4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]dithiophene (DOCPDT)之
合成路徑.....................................................................................30
2-2-2 4,7-dibromobenzo[c][1,2,5]thiadiazole (DiBr-BTDA)、5,8-
dibromo-2,3-di(thiophen-2-yl)-2,3-dihydroquinoxaline (DiBr-
DTQ)與5,8-dibromo-2,3-di(benzene-2-yl)-2,3-dihydro-
Quinoxaline (DiBr-DBQ)之合成路徑........................................31
2-2-3 共聚物單體之合成路徑............................................................32
2-2-4 共聚物高分子之合成路徑........................................................33
2-3 中間產物、單體及共聚物之結構、命名與簡稱.................................34
2-4 合成步驟.............................................................................................39
2-4-1 Di-thiophen-3-yl-methanol 的合成.........................................39
2-4-2 Di-thiophen-3-yl-methanone 的合成........................................40
2-4-3 2,2-Di-thiophen-3-yl-[1,3]dioxolane 的合成............................41
2-4-4 2,2-Bis-(2-iodo-thiophen-3-yl)-[1,3]dioxolane 的合成............42
2-4-5 Cyclopenta[2,1-b;3,4-b'']dithiophen-4-dioxolane 的合成.........43
2-4-6 Cyclopenta[2,1-b;3,4-b'']dithiophen-4-one 的合成...................43
2-4-7 4H-Cyclopenta[2,1-b;3,4-b'']dithiophene 的合成.....................44
2-4-8 4,4-Dioctyl-cyclopenta[2,1-b;3,4-b’]dithiophene 的合成........45
2-4-9 4,4-Dioctyl-2-trimethylstannanyl-4H-cyclopenta[2,1-b:3,4-b'']-
dithiophene 的合成....................................................................46
2-4-10 4,7-dibromobenzo[c][1,2,5]thiadiazole 的合成........................47
2-4-11 3,6-dibromocyclohexa-3,5-diene-1,2-diamine 的合成.............48
2-4-12 5,8-dibromo-2,3-di(thiophen-2-yl)-2,3-dihydroquinoxaline
的合成.............................................................................49
2-4-13 5,8-dibromo-2,3-di(thiophen-2-yl)-2,3-dihydroquinoxaline
的合成.............................................................................49
2-4-14 4,4-bis(2-(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithiophene)thienyl)-biphenyl 的合成......................................50
2-4-15 Poly4,4-bis(2-(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithiophene)thienyl)-biphenyl 的合成......................................51
2-4-16 1,4-bis(2-(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithiophene)thienyl)-benzene 的合成.......................................52
2-4-17 Poly[5,8-bis(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithienyl)-2,3-di(thiophen-2-yl)quinoxaline]的合成..............53
2-4-18 5,8-bis(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]dithienyl)-
2,3-di(thiophen-2-yl)quinoxaline 的合成..................................54
2-4-19 Poly[5,8-bis(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithienyl)-2,3-di(thiophen-2-yl)quinoxaline]的合成................56
2-4-20 5,8-bis(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]dithienyl)-
2,3-di(thiophen-2-yl)quinoxaline 的合成................................56
2-4-21 Poly[5,8-bis(4,4-Dioctyl-4H-Cyclopenta[2,1-b;3,4-b’]
dithienyl)-2,3-di(thiophen-2-yl)quinoxaline]的合成................57
2-5 共軛高分子衍生物純化方式.............................................................58
2-6 儀器分析與樣品製備...........................................................................59
2-6-1 核磁共振光譜儀 (Nuclear Magnetic Resonance Spectroscopy
( NMR ))..................................................................................................59
2-6-2 紫外光/可見光/近紅外光吸收光譜儀 (Cary 5E UV/VIS/NIR
Spectrometer)..........................................................................................60
2-6-3 膠體滲透層析儀( Gel Permeation Chromato graphy , GPC)..61
2-6-4 熱重分析儀 (Perkin Elmer TGA 7, TGA)..............................62
2-6-5 掃瞄式電子顯微鏡 (Hitachis-2300).......................................63
2-6-6 電化學與光學性質的測試......................................................64
第三章 結果與討論
3-1 PDOCPDT- BP 之合成、鑑定及電致變色性質探討........................68
3-1-1 PBOCPDT-BP 之合成與結構鑑定............................................68
3-1-2 PBDOCPDT-BP 之電致變色性質探討.....................................69
3-2 PBDOCPDT-B 之合成、鑑定及電致變色性質探討.........................77
3-2-1 PBDOCPDT-Bz 之合成與結構鑑定.........................................77
3-2-2 PBDOCPDT-Bz 之電致變色性質探討.....................................77
3-3 PBDOCPDT-DBQ 之合成、鑑定及電致變色性質探討.....................83
3-3-1 PBDOCPDT-DBQ 之合成與結構鑑定.....................................83
3-3-2 PBDOCPDT-DBQ 之電致變色性質探討.................................88
3-4 PBDOCPDT-DTQ 之合成、鑑定及電致變色性質探討.....................96
3-4-1 PBDOCPDT-DTQ之合成與結構鑑定......................................96
3-4-2 PBDOCPDT-DTQ之電化學性質探討......................................96
第四章 結論...................................................................................105
參考文獻...........................................................................................106
附錄...................................................................................................110

                                

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