臺灣博碩士論文加值系統

本研究以Paal-Knorr反應將三氮唑、苯并噻唑、甲基噻唑和甲氧基雙苯醚連結於二噻吩一吡咯之吡咯環上，分別命名為TN、BT、MP及MT，並以電化學聚合法製備其對應之PTN、PBT、PMP及PMT電致變色陽極材料，以及成功合成出新穎POTP電致變色陰極材料。藉由對高分子薄膜施加電壓，使PMP顏色變化由中性態金菊色、暗金菊色、蘚苔綠到氧化態鐵灰色，具有可逆性的顏色變化，PMP膜在波長1270 nm處之光學對比值能達到60.0%，光學穩定性達到94.7%且著色效率能達到216.38 cm2/C。陰極材料POTP之顏色變化為深藍色、紫色、灰紫色及淺灰色，在波長1700 nm下之光學對比值達到75.9 %，其光學穩定性和著色效率也分別達92.8%及732.12 cm2/C。
PBT / PProDOT-Bz2元件在波長620 nm下光學對比值為52.3%，穩定性94.9%，著色效率為631.96 cm2/C，轉換時間達1.5秒以內，去色態至著色態之顏色變化為灰金菊、灰綠色、深灰綠、暗灰色、蔚藍色和礦藍色。

In this study, triazole, benzothiazole, methylthiazole, and methoxyphenoxy groups are incorporated to dithienylpyrroles using Paal-Knorr reaction, which are denominated as TN, BT, MP, and MT, respectively. Their corresponding polydithienylpyrroles (PTN, PBT, PMP, and PMT) are synthesized using electrochemical polymerization and are employed as the anodic coloring materials of electrochromic devices (ECDs). Moreover, a cathodic coloring material (POTP) is also synthesized electrochemically. PMP film is goldenrod in the neutral state, it turns into dark goldenrod, moss green, and iron gray at doped state upon oxidation, and it can be reversibly oxidized and reduced and this is accompanied by obvious color changes. The ∆Tmax of PMP film is 60.0% at 1270 nm in an ionic liquid solution, the optical stability of PMP film is 94.7% after 100 switching cycles, and the maximum coloration efficiency of PMP film is 216.38 cm2/C. The cathodic coloring film (POTP) is dark blue in the neutral state, it turns into purple, grayish purple, and light gray at doped state upon oxidation. The ∆Tmax of POTP film is 75.9% at 1700 nm, and the optical stability and maximum coloration efficiency of POTP film are 92.8% and 732.12 cm2/C, respectively. The ∆Tmax of PBT/PProDOT-Bz2 ECD is 52.3% at 620 nm, the optical stability and maximum coloration efficiency of PBT/PProDOT-Bz2 ECD are 94.9% and 631.96 cm2/C, respectively, and the switching time of PBT/PProDOT-Bz2 ECD is less than 1.5 s. In addition, PBT/PProDOT-Bz2 ECD is pale goldenrod in the bleached state, it turns into celadon, dark celadon, dark gray, cerulean, and sapphire blue from the bleached state to the colored state.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
表目錄 vii
圖目錄 ix
第一章 緒論 1
1-1前言 1
1-2研究動機 2
1-3 電致變色簡介 4
1-3-1 導電機制 4
1-3-2 電致變色的種類 5
1-3-3 電致變色材料之應用 6
1-3-4 電致變色元件結構 8
1-3-5 電致變色的基本參數 9
第二章 文獻回顧 11
2-1 陽極導電高分子 11
2-2 陰極導電高分子 17
第三章 實驗部分 20
3-1 研究架構 20
3-2 實驗藥品 21
3-3 實驗儀器 22
3-4 ITO玻璃前處理 22
3-5 實驗裝置 23
3-5-1 電化學聚合 23
3-5-2 薄膜在液態環境下的電化學與光學性質測試 24
3-5-3 薄膜在固態環境下的電化學與光學性質測試 25
3-6 實驗合成 26
3-6-1 陽極材料SNS系列導電高分子單體合成 26
3-6-2 陰極材料導電高分子單體合成 36
3-6-3 離子液體的合成 42
3-7 高分子電解質模的備製 44
第四章 結果與討論 45
4-1 電化學聚合 45
4-1-1 陽極材料之聚合 45
4-1-2 陰極材料之聚合 50
4-1-3定電位聚合 54
4-1-4. 導電高分子薄膜分析 55
4-2. 五種導電高分子薄膜在液態下之光學測試 58
4-2-1. 五種導電高分子薄膜之吸收光譜圖變化圖 59
4-2-2 五種導電高分子薄膜之穿透度變化 75
4-2-3. 探討五種高分子薄膜之穩定性、轉換時間及著色效率 86
4-3. SNS系列薄膜組成元件之光學性質探討 96
4-3-1. 十二組元件In-situ UV-vis 光譜吸收度 97
4-3-2. 十二組元件之電致變色轉換性質 133
4-3-3. 探討十二組元件穩定性、轉換時間和著色效率 142
4-3-4. 十二組元件之多圈循環電化學穩定性 150
4-3-5. 十二組元件之光學記憶效應 156
4-3-6 本研究SNS系列電致變色材料和元件與文獻比較 162
第五章 結論 164
參考文獻 165

1.Steinkopf, W.; Leitsmann, R.; Hofmann, K.H. Studien in der thiophenreihe. Lvii. über α-polythienyle. Justus Liebigs Annalen der Chemie 1941, 546, 180-199.
2.Kaya, İ.; Yıldırım, M.; Aydın, A. A new approach to the schiff base-substituted oligophenols: The electrochromic application of 2-[3-thienylmethylene] aminophenol based co-polythiophenes. Organic Electronics 2011, 12, 210-218.
3.Akpinar, H.Z.; Udum, Y.A.; Toppare, L. Spray-processable thiazolothiazole- based copolymers with altered donor groups and their electrochromic properties. Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 3901-3906.
4.Fei, J.; Lim, K.G.; Palmore, G.T.R. Polymer composite with three electrochromic states. Chemistry of Materials 2008, 20, 3832-3839.
5.Wang, G.; Fu, X.; Huang, J.; Wu, L.; Deng, J. Synthesis, electrochemical and fluorescence properties of three new dithienylpyrroles bearing aromatic amine units. Journal of Electroanalytical Chemistry 2011, 661, 351-358.
6.Platt, J.R. Electrochromism, a possible change of color producible in dyes by an electric field. The Journal of Chemical Physics 1961, 34, 862-863.
7.Deb, S. A novel electrophotographic system. Applied Optics 1969, 8, 192-195.
8.Recent process and application of electrochromism. Journal of aeronautical materials, 2016, 36(3): 108-123. 2016.
9.Pang, Y.; Li, X.; Ding, H.; Shi, G.; Jin, L. Electropolymerization of high quality electrochromic poly(3-alkyl-thiophene)s via a room temperature ionic liquid. Electrochimica acta 2007, 52, 6172-6177.
10.Tarkuc, S.; Sahin, E.; Toppare, L.; Colak, D.; Cianga, I.; Yagci, Y. Synthesis, characterization and electrochromic properties of a conducting copolymer of pyrrole functionalized polystyrene with pyrrole. Polymer 2006, 47, 2001-2009.
11.Leclerc, M.; Guay, J.; Dao, L. Synthesis and properties of electrochromic polymers from toluidines. Journal of electroanalytical chemistry and interfacial electrochemistry 1988, 251, 21-29.
12.Güneş, A.; Cihaner, A.; Önal, A.M. Synthesis and electro-optical properties of new conjugated hybrid polymers based on furan and fluorene units. Electrochimica Acta 2013, 89, 339-345.
13.Sotzing, G.A.; Reddinger, J.L.; Katritzky, A.R.; Soloducho, J.; Musgrave, R.; Reynolds, J.R.; Steel, P.J. Multiply colored electrochromic carbazole-based polymers. Chemistry of Materials 1997, 9, 1578-1587.
14.Maarouf, E.; Billaud, D.; Hannecart, E. Electrochemical cycling and electrochromic properties of polyindole. Materials research bulletin 1994, 29, 637-643.
15.Camurlu, P. Polypyrrole derivatives for electrochromic applications. RSC Advances 2014, 4, 55832-55845.
16.Gillaspie, D.T.; Tenent, R.C.; Dillon, A.C. Metal-oxide films for electrochromic applications: Present technology and future directions. Journal of Materials Chemistry 2010, 20, 9585-9592.
17.Novinrooz, A.; Sharbatdaran, M.; Noorkojouri, H. Structural and optical properties of WO3 electrochromic layers prepared by the sol-gel method. Open Physics 2005, 3, 456-466.
18.Kase, T.; Kawai, M.; Ura, M. A new electrochromic device for automotive glass-the development of adjustable transparency glass; 0148-7191; SAE Technical Paper: 1986.
19.泰特博旗濱股份有限公司. http://www.tintable.com.tw/cht/
20.Electrochromic sunglasses & goggles. https://ashwin-ushas.com/electrochromic-sunglasses-goggles/
21.電致變色後視鏡. https://cecas.clemson.edu/cvel/auto/systems/auto-dimming-mirror.html
22.智能車窗. https://www.aliexpress.com/item/PDLC-Power-Inverter-kit-car-Smart-film-EGlass-switchable-film-electrochromic-power-magic-film-smart-glass/1797050637.html
23.Beaujuge, P.M.; Reynolds, J.R. Color control in π-conjugated organic polymers for use in electrochromic devices. Chemical reviews 2010, 110, 268-320.
24.Akpınar, H.Z.; Udum, Y.A.; Toppare, L. Multichromic and soluble conjugated polymers containing thiazolothiazole unit for electrochromic applications. European Polymer Journal 2015, 63, 255-261.
25.Balan, A.; Baran, D.; Sariciftci, N.S.; Toppare, L. Electrochromic device and bulk heterojunction solar cell applications of poly 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-dodecyl-2H-benzo[1,2,3]triazole (PBEBT). Solar Energy Materials and Solar Cells 2010, 94, 1797-1802.
26.Balan, A.; Gunbas, G.; Durmus, A.; Toppare, L. Donor-acceptor polymer with benzotriazole moiety: Enhancing the electrochromic properties of the “donor unit”. Chemistry of Materials 2008, 20, 7510-7513.
27.Woodward, A.N.; Kolesar, J.M.; Hall, S.R.; Saleh, N.-A.; Jones, D.S.; Walter, M.G. Thiazolothiazole fluorophores exhibiting strong fluorescence and viologen-like reversible electrochromism. Journal of the American Chemical Society 2017, 139, 8467-8473.
28.Cihaner, A.; Mert, O.; Demir, A.S. A novel electrochromic and fluorescent polythienylpyrrole bearing 1,1′-bipyrrole. Electrochimica Acta 2009, 54, 1333-1338.
29.Sotzing, G.; Reddinger, J.; Reynolds, J.; Steel, P. Redox active electrochromic polymers from low oxidation monomers containing 3,4-ethylenedioxythiophene (edot). Synthetic metals 1997, 84, 199-201.
30.Wan, Z.; Zeng, J.; Li, H.; Liu, P.; Deng, W. Multicolored, low‐voltage‐driven, flexible organic electrochromic devices based on oligomers. Macromolecular rapid communications 2018, 39, 1700886.
31.Gaupp, C.L.; Welsh, D.M.; Reynolds, J.R. Poly(ProDOT-Et2): A high‐contrast, high‐coloration efficiency electrochromic polymer. Macromolecular rapid communications 2002, 23, 885-889.
32.Gunbas, G.; Toppare, L. Electrochromic conjugated polyheterocycles and derivatives—highlights from the last decade towards realization of long lived aspirations. Chemical Communications 2012, 48, 1083-1101.
33.Camurlu, P.; Bicil, Z.; Gültekin, C.; Karagoren, N. Novel ferrocene derivatized poly (2,5-dithienylpyrrole)s: Optoelectronic properties, electrochemical copolymerization. Electrochimica Acta 2012, 63, 245-250.
34.Söyleyici, H.C.; Ak, M.; Şahin, Y.; Demikol, D.O.; Timur, S. New class of 2,5-di (2-thienyl)pyrrole compounds and novel optical properties of its conducting polymer. Materials Chemistry and Physics 2013, 142, 303-310.
35.Soganci, T.; Soyleyici, S.; Soyleyici, H.C.; Ak, M. High contrast electrochromic polymer and copolymer materials based on amide-substituted poly(dithienyl pyrrole). Journal of The Electrochemical Society 2017, 164, H11-H20.
36.Camurlu, P.; Gültekin, C. A comprehensive study on utilization of N-substituted poly(2,5-dithienylpyrrole) derivatives in electrochromic devices. Solar Energy Materials and Solar Cells 2012, 107, 142-147.
37.Su, Y.-S.; Wu, T.-Y. Three carbazole-based polymers as potential anodically coloring materials for high-contrast electrochromic devices. Polymers 2017, 9, 284.
38.Soganci, T.; Kurtay, G.; Ak, M.; Güllü, M. Preparation of an edot-based polymer: Optoelectronic properties and electrochromic device application. RSC Advances 2015, 5, 2630-2639.
39.Arslan, A.; Türkarslan, Ö.; Tanyeli, C.; Akhmedov, İ.M.; Toppare, L. Electrochromic properties of a soluble conducting polymer: Poly(1-(4-fluorophenyl)-2,5-di (thiophen-2-yl)-1H-pyrrole). Materials chemistry and physics 2007, 104, 410-416.