臺灣博碩士論文加值系統

本論文包含兩個研究重點。第一個部分裡，我們利用transetherification合成了兩個3,4-propylenedioxythiophene 的衍生物，分別是benzyl 3,4-dihydro-3-methyl-2H-thieno[3,4-b][1,4] dioxepine -3-carboxylate (ProDOT-PH)和dodecyl 3,4-dihydro-3-methyl-2H-thieno [3,4-b][1,4]dioxepine-3-carboxylate (ProDOT-COOC12H25)。藉著使用氧化聚合反應，可以得到一個不溶於一般溶劑的PProDOT-PH以及一個可以溶於一般溶劑的PProDOT-COOC12H25。其中，我們利用1H-NMR證實PProDOT-COOC12H25結構，並由GPC測量PProDOT-COOC12H25之分子量及分子量分佈，利用UV測其吸收光譜特徵。我們並利用電化學聚合法來聚合兩種ProDOT衍生物，並得到良好的高分子薄膜。我們施加不同的電壓(分別是-0.1V— 0.6V以及-0.1V— 0.7V)來得到其氧化還原態，並得到不同的穿透度對比。
在第二個部分裡，我們並合成了一個星狀導電性共聚合物，這個共聚合物是以帶有12臂鏈poly(n-butyl acrylate) (12PBA) 以及 poly(2-dodecyl-2,3- dihydrothieno[3,4-b][1,4]dioxine)(PEDOT-C12H25)所構成。12PBA先以ATRP的方法合成後，末端基在改質成帶有thiophene的12PBA-TH。相關改質的結構以1H-NMR 和 GPC 分析鑑定。另一種單體則是利用transetherification合成2-dodecyl-2,3-dihydrothieno [3,4-b][1,4] dioxine (EDOT-C12H25)。兩者再以氧化聚合方式合成共聚合物。並利用IR、1H NMR和 GPC來分析。IR及1H NMR證實了有共聚合物的存在，但GPC則顯示尚有線性PEDOT-C12H25未分離乾淨，還需有進一步的純化分離。

This thesis mainly consists of two parts. In the first part, two 3,4-propylenedioxythiophene derivatives, benzyl 3,4-dihydro-3-methyl -2H-thieno[3,4-b][1,4]dioxepine-3-carboxylate (ProDOT-PH) and dodecyl 3,4-dihydro-3-methyl-2H-thieno[3,4-b][1,4]dioxepine-3- carboxylate (ProDOT-COOC12H25) were synthesized by transetherification. PProDOT-PH, which was polymerized by oxidative chemical polymerization, was insoluble in common solvents; however, PProDOT-COOC12H25 was soluble. Chemical structure and molecular weight characteristics of PProDOT-COOC12H25 was studied by IR, 1H NMR, GPC and UV-vis techniques. Both ProDOT-PH and ProDOT-COOC12H25 could form polymer films by electrochemically polymerization method. The oxidized form and reduced form of PProDOT-PH and PProDOT-COOC12H25 with different transmittance contrast were produced under applied certain potentials (-0.1V— 0.6Vand -0.1V— 0.7V).
In the second part, electro-active starburst copolymers of 12-arms poly(n-butyl acrylate)(12PBA) and poly(2-dodecyl-2,3-dihydrothieno [3,4-b][1,4]dioxine)(PEDOT-C12H25) were synthesized. 12PBA was synthesized by the ATRP (atom transfer radical polymerization) method, and the end groups of polymer arms were modified to generate thiophene-capped starburst 12PBA-TH. The corresponding structures were identified by 1H-NMR. The studies of molecular weight characteristics of these star polymers were performed on 1H-NMR and GPC instruments. The monomer of 3,4-ethylenedioxythiophene was prepared by transetherification to give 2-dodecyl-2,3-dihydrothieno [3,4-b][1,4]dioxine (EDOT-C12H25). The preparation of electroactive starburst 12PBA-b-PEDOT-C12H25 copolymers was carried out by growing PEDOT-C12H25 chains from the terminated thiophene unit of 12-armed stars via oxidative polymerization method. Chemical structure and molecular weight characteristics of these copolymers were studied by IR, 1H NMR and GPC techniques. It was confirmed by IR and 1H NMR that the copolymer was successfully synthesized. However, the GPC data implied the existence of plenty of linear PEDOT-C12H25, indicating the need of the development of further purification process.

中文摘要 ................................................Ⅰ
英文摘要 ................................................Ⅱ
誌謝 ....................................................Ⅴ
目錄 ....................................................Ⅵ
圖目錄 ..................................................Ⅷ
式目錄 ..................................................Ⅹ
第一章 緒論...............................................1
1-1 前言..................................................1
1-2 共軛高分子之能帶理論..................................4
1-3 Poly(3,4-ethylenedioxythiophene) (PEDOT)..............7
1-3-1 簡介................................................7
1-3-2 PEDOT的合成.........................................8
1-3-2-1 氧化聚合反應......................................8
1-3-2-2 電化學聚合反應...................................10
1-3-2-3 金屬錯化物偶合反應...............................11
1-3-3 EDOT的衍生物.......................................11
1-3-3-1 Poly（3,4-propylenedioxythiophene)（PProDOT）....13
1-3-4 PEDOT及其衍生物的應用..............................14
1-4 星狀高分子(star polymer）............................15
1-4-1 導電性高分子共聚物.................................16
1-5 研究目的 ............................................19
第二章 ProDOT衍生物的合成與分析..................... ....20
2-1 ProDOT衍生物之合成...................................20
2-2 PProDOT-PH之合成與分析...............................23
2-2-1 氧化聚合反應.......................................23
2-2-2 電化學聚合反應.................................... 24
2-2-3 電化學聚合裝置.....................................25
2-2-4 電化學聚合ProDOT-PH................................26
2-2-5 PProDOT-PH的光學性質...............................29
2-3 PProDOT-COOC12H25之合成與分析........................32
2-3-1 氧化聚合反應 ......................................32
2-3-2 電化學聚合ProDOT- COOC12H25........................34
2-3-3 PProDOT- COOC12H25的光學性質.......................36
第三章星狀嵌段式聚(12PBA-b-PEDOT-C12H25)共聚物之合成與分析...................................................... 41
3-1 EDOT-C12H25之合成與分析..............................41
3-2十二臂鏈星狀poly(butyl acrylate)之合成與改質..........42
3-2-1十二臂鏈星狀poly(butyl acrylate)(12PBA-Br)之合成與分析.......................................................42
3-2-2 十二臂鏈具羥基末端基星狀poly(butyl acrylate)之合成 與分析.....................................................45
3-2-3十二臂鏈具thiophene末端基星狀poly(butyl acrylate)之合成與分析.................................................47
3-3 星狀嵌段式12PBA與PEDOT-C12H25共聚物之合成與分析......49
第四章 結論..............................................54
第五章 實驗部分..........................................56
5-1 藥品與溶劑...........................................56
5-2 儀器.................................................62
5-3 ProDOT衍生物之合成 ..................................65
5-4 ProDOT衍生物的聚合反應...............................72
5-4-1 氧化聚合反應.......................................72
5-4-2 電化學聚合反應.....................................72
5-5 電化學分析...........................................73
5-6 十二臂鏈之星狀嵌段式聚(12PBA-b- PEDOT-C12H25)共聚物合成.......................................................74
5-6-1 EDOT衍生物之合成...................................74
5-6-2 十二臂鏈星狀poly(butyl acrylate)之合成與改質.......75
5-6-3 12PBA-b-PEDOT-C12H25之氧化聚合反應.................78
參考文獻.................................................80
附錄

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