雙二噻吩環戊烷衍生物的合成與性質探討｜國立中央大學博碩士論文系統

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研究生：	謝崇偉 Chong-Wei Sie
論文名稱：	雙二噻吩環戊烷衍生物的合成與性質探討
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：	93
語文別：	中文
論文頁數：	105
中文關鍵詞：	二噻吩環戊烷、低能隙
外文關鍵詞：	cyclopentadithiophene, low band-gap
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摘要
導電高分子由於具有低成本，可低溫製成及可溶劑加工等優點，故在應用上備受矚目。近年來以噻吩(thiophene)為主的低能隙高分子更是主要的研究對象之一。本實驗目的是在Δ4,4´-dicyclopenta[2,1-b:
3,4-b´]dithiophene（DCPDT;DCP）單體上，於不同位置上修飾長碳鏈取代基提供高分子溶解度，主要合成出四種單體： 2,6-dioctyl-
Δ4,4´-dicyclopenta[2,1-b:3,4-b´]dithiophene (DODCP)、2,2´-di- octyl-Δ4,4´-di-cyclopenta[2,1-b:3,4-b´]di-thiophene(cis- DODCP)、2,6´-dioctyl-Δ4,4´-dicyclopenta[2,1-b:3,4-b´]dithio -phene(trans-DODCP)、及2,2´-ditetradecyl-Δ4,4´-dicyclo- penta[2,1-b:3,4-b´] dithiophene (cis-DTDDCP)，探討取代基位置不同對聚合所得高分子之能隙的影響。實驗發現化學聚合所得高分子不溶於一般有機溶劑，故無法做成薄膜做以探討不同結構對能隙的影響，但由IR證實確有合成出高分子。而由電化學聚合高分子膜的UV圖發現，三種高分子膜的能隙皆小於1.5 eV，其中PDODCP能隙小於1.3 eV。可知影響高分子能隙的原因除了取代基位置的立體障礙效應（steric effect），主鏈結構的不同也是影響因素之一。

Abstract
Low band-gap conjugated polymers have attracted a great attention recently due to their high intrinsic conductivity as well as the optical transparent in the visible light in the doped state. The structure of lots of low band-gap polymer is based on polythiophenes because of their high environmental stability, superior conductivity, processability, and easy for structure modification.Δ4,4´-dicyclopenta[2,1-b:3,4-b´] dithiophene (DCPDT) is one of the monomers for low band-gap polymers. By adding the alkyl substitute groups at different positions to increase the solubility, four derivatives: 2,6-dioctyl-Δ4,4´-dicyclopenta- [2,1-b:3,4-b´] dithiophene (DODCP), cis-2,2´- dioctyl-Δ4,4´-dicyclopenta[2,1-b:3,4-b´] dithiophene (cis-DODCP), trans-2,6´-dioctyl-Δ4,4´-dicyclopenta [2,1-b:
3,4-b´]dithiophene (trans-DODCP), and 2,2´-ditetradecyl-Δ4,4´ -dicyclo
-penta[2,1-b:3,4-b´]-dithiophene (cis-DTDDCP) were synthesized. The corresponding polymers prepared by chemical polymerization in FeCl3/CHCl3 were not soluble in organic solvents. Therefore, polymer films were obtained from electrochemical polymerization using LiClO4/CH3CN as electrolyte solution in a typical three-electrode cell. The optical data of the polymer films showed that PDODCP has the lowest band gap (< Eg=1.3 eV) for all polymer films prepared in this study. It is found that band-gap of polymer is affected by the steric effect of substitute groups and main-chain configurations of the polymers.

中文摘要…………………………………………………………………I
英文摘要 ………………………………………………………………II
目錄……………………………………………………………………III
圖目錄…………………………………………………………………VII
表目錄 …………………………………………………………………XI
壹、緒論
1-1、前言 ………………………………………………………………1
1-2、有機導電高分子 …………………………………………………1
1-3、有機導電高分子之發展歷史 ……………………………………5
1-4、有機導電高分子之導電機制 ……………………………………7
1-4-1、能帶結構.………………………………………………………7
1-4-2、極子、雙偏極子和孤立子……………………………………12
1-4-3、導電高分子的摻雜原理………………………………………14
1-5、導電高分子的應用………………………………………………16
1-6、低能隙導電高分子………………………………………………25
1-6-1、低能隙導電高分子的發展歷史………………………………25
1-6-2、低能隙導電高分子的種類……………………………………26
1-6-3、低能隙導電高分子的應用……………………………………27
1-7、聚3-烷基噻吩系統………………………………………………29
1-7-1、聚3-烷基噻吩發展沿革………………………………………29
1-7-2、聚噻吩高分子能隙的調變 ……………………………………31
1-7-3、聚噻吩低能隙導電高分子的種類 ……………………………32
1-8、研究動機 …………………………………………………………33
貳、實驗部分
2-1、實驗藥品 …………………………………………………………34
2-2、合成步驟 …………………………………………………………38
2-2-1、聚雙二噻吩環戊烷衍生物之合成 ……………………………38
2-2-1-1、Di-thiophen-3-yl-methanol的合成 ……………………43
2-2-1-2、Di-thiophen-3-yl-methanone的合成……………………44
2-2-1-3、2,2-Di-thiophen-3-yl-[1,3]dioxolane的合成 ………44
2-2-1-4、2,2-Bis-(2-iodo-thiophen-3-yl)-[1,3]dioxolane的合         成……………………………………………………………45
2-2-1-5、Cyclopenta[2,1-b;3,4-b´]dithiophen-4-dioxolane的合
成……………………………………………………………46
2-2-1-6、Cyclopenta[2,1-b;3,4-b´]dithiophen-4-one的合成…47
2-2-1-7、4H-Cyclopenta[2,1-b;3,4-b´]dithiophene的合成……48
2-2-1-8、2-Octyl-cyclopenta[2,1-b;3,4-b´]dithiophen-4-one的         合成…………………………………………………………49
2-2-1-9、2,6-Dioctyl-cyclopenta[2,1-b;3,4-b´]dithiophen-4- one的合成 …………………………………………………50
2-2-1-10、2-Tetradecyl-cyclopenta[2,1-b;3,4-b´]dithiophen-
4-one的合成……………………………………………51
2-2-1-11、2,6-Dioctyl-△4,4´-dicyclopenta[2,1-b:3,4-b´] dithio phene………………………………………………………52
2-2-1-12、2,2´-Dioctyl-△4,4´-dicyclopenta[2,1-b:3,4-b´]di- thiophene與2,6´-Dioctyl-△4,4´-dicyclopenta[2,1-b:
3,4-b´] dithiophene的合成 …………………………54
2-2-1-13、2,2´-Ditetradecyl-△4,4´-dicyclopenta[2,1-b: 3,4-b´] dithiophene與2,6´-Ditetradecyl-△4,4´-dicyclopenta [2,1-b:3,4-b´]dithiophene的合成 …………………55
2-2-1-14、2´-Bromo-2,6-Dioctyl-Δ4,4´-dicyclopenta [2,1-b: 3,4
-b´]-dithiophene的合成………………………………56
2-2-1-15、2,6-Dioctyl-Δ4,4´-dicyclopenta[2,1-b:3,4-b´]dithio -phene Dimer的合成 ……………………………………57
2-2-1-16、2,2´,6,6´-Tetraoctyl-Δ4,4´-dicyclopenta[2,1-b: 3,4- b´]-dithiophene的合成…………………………………58
2-2-2、雙二噻吩環戊烷衍生物之聚合
2-2-2-1、化學聚合……………………………………………………59
2-2-2-2、電化學聚合…………………………………………………59
2-3、	合成中間產物及目標產物之1H-NMR結構鑑定…………………61
2-4、儀器分析與樣品製備……………………………………………72
2-4-1、紫外光/可見光/近紅外光吸收光譜儀………………………72
2-4-2、紅外光吸收光譜儀……………………………………………73
2-4-3、核磁共振光譜儀………………………………………………73
2-4-4、熱示差掃描卡量計……………………………………………74
2-4-5、電化學循環伏安法……………………………………………75
2-4-6、X-光粉末繞射儀 ………………………………………………76
參、結果與討論
3-1、合成部分
3-1-1、CDT的還原反應 ………………………………………………77
3-1-2、2,6-Dioctyl-4,4´-dicyclopenta[2,1-b:3,4-b´]dithio- phene的合成探討……………………………………………77
3-1-3、單體產物的分離與判別 ………………………………………78
3-1-4、TODCP的合成……………………………………………………79
3-2、目標單體的性質探討
3-2-1、微分示差卡描計………………………………………………79
3-2-2、X光繞射分析 …………………………………………………82
3-2-3、目標單體之Uv/Vis光譜分析…………………………………83
3-2-4、目標單體之電化學分析 ………………………………………83
3-3、高分子性質
3-3-1、目標單體的化學聚合反應 ……………………………………87
3-3-2、化學聚合高分子的IR分析……………………………………88
3-3-3、目標單體的電化學聚合反應 …………………………………91
3-3-4、電化學聚合高分子之IR分析…………………………………91
3-3-5、高分子與單體之UV/Vis光譜分析……………………………93
3-4、目標單體Dimer的合成 …………………………………………96
肆、結論 ………………………………………………………99
參考文獻………………………………………………………………100

                                

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