博碩士論文 92223051 詳細資訊




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姓名 謝崇偉(Chong-Wei Sie)  查詢紙本館藏   畢業系所 化學學系
論文名稱 雙二噻吩環戊烷衍生物的合成與性質探討
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摘要(中) 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。
摘要(英) 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.
關鍵字(中) ★ 二噻吩環戊烷
★ 低能隙
關鍵字(英) ★ cyclopentadithiophene
★ low band-gap
論文目次 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
參考文獻 參考文獻
1. J. Roncali,, Chem. Rev. 1992, 92, 711
2. K. Hyodo, Electrochem Acta 1994, 39, 265
3. G. Gustafsson, Y. Cao, G. M. Treacy, F. Klavetter, N. Colaneri, Nature 1992, 357, 477
4. K. Yoshio, Y. Manda, H. Takahashi, Y. Nishioka, T. Kawai, M. Ohmori J. Apply. Phys. 1990, 68, 5976
5. R. D. McCullough, R. D. Lowe, S. Tristramnagle, S. P. Williams, M. Yayaraman, J. Am. Chem. Soc. 1993, 26, 4457
6. T. Osaka, S. Komada, K. Fujihana, N. Odamoto, N. Kanedo, Chem. Lett. 1995, 1023
7. A. Angli, Gazz. Chim. Ital. 1916, 46, II279
8. A. Dall Olio, G. Dascola, V. Varacca, V. Bocchi, Acad. Sci. Ser. 1968, 433, C267
9. Chen Tian-An, Wu Xiaoming, R. D. Rieke, J. Am. Chem. Soc. 1995, 117, 233-244
10. H. Naarmann, “Structure and conductivity of organic polymers”, Angew. Chem. Int. Ed. 1969, 8, 915
11. H. Shiradawa, S. Ikeda, Polym. J. 1971, 2, 231
12. C. K. Chiang, C. R. Fincher Jr, Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, A. G. MacDiarmid, Phys. Rev. Lett. 1977, 39, 1098
13. J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347, 539-541
14. D. Braun, A. J. Heeger, Appl. Phys. Lett. 1990, 58, 1982
15. K. Susan, E. S. Vanderkam, J. S. Gawalt, A. B. Bocarsly, Langmuir 1999, 15, 6598-6600
16. M. G. Kanatzids, “Conductive polymers”, C&EN, 1990, 3, 36
17. 李進昌, 1994, 國立清華大學化學工程研究所博士論文
18. 洪添燦, 1998, 國立清華大學化學工程研究所博士論文
19. C.Kittel, “Introduction to Solid State Physics”. 6th ed., John Wiley & Son, Singapore, 1986,
20. K. Y. Jen, G. G. Miller, R. L. Elsenbaumer, J. Chem. Soc.,Chem. Commun. 1986, 1346.
21. S. D. D. V. Rughooputh, M. Nowak, S. Hotta, A. J. Heeger, F. Wudl, Synth. Met. 1987, 21, 41.
22. 張淑美, 科學月刊 2001,第三十二卷第二期, 108
23. http://www.nobel.se/chemistry/laureates/2000/public.html
24. V. H. Houlding, A. Hahata, J. T. Yardley, R. L. Elsenbaumer, Chem. Mater. 1990, 2, 169.
25. T. Osaka, S. Komada, K. Fujihana, N. Okamoto, N. Kaneko, J. Electrochem. Soc. 1997, 114, 743.
26. D. R. Rosseinsky, R. J. Mortimer, Adv. Mater. 2001, 13,783.
27. M. Pomerantz, in Handbook of Conducting Polymers (Eds: T. A. Skotheim, R. L. Elsenbaumer, J. R. Reynolds), 2nd ed., Marcel Dekker, New York 1998, Ch. 5.
28. 陳丁洲, 2004, 國立中央大學化學研究所碩士論文, p22
29. 趙家錚, 2004, 國立中央大學化學研究所碩士論文, p20-21
30. A. J. Epstein, J. M. Ginder, R. W. Bigelow, A. G. MacDiamid, Synth. Met. 1987, 18, 303.
31. Zhenan Bao, Andrew J. Lovinger, Appl. Phys. Lett. 1996, 69, 26.
32. 麥啃錫季刊, 2002年第一季
33. Wenjie Li, *Howard E. Katz, Andrew J. Lovinger, Chem. Mater. 1999, 11, 458-265.
34. 圖解電子回路, 稻見辰夫 著, 葉隆吉 審訂, 世茂出版社
35. (a) H. Sirringhaus, N. Tessler, R. H. Friend, Science 1998, 280, 1741.
(b) http://www.itri.org.tw/chi/news_events/feature/2003/fe-0920915
36. J. P. Ferraris, T. L. Lambert, J. Chem. Soc., Chem. Commun. 1991, 1286.
37. M. Kobayashi, N. Colaneri, M. Boysel, F. Wudl, A. J. Heeger, J. Org. Chem. 1984, 49, 3382
38. M. Kertesz, Y. S. Lee, Synth. Met. 1989, 28, C545
39. J. M. Toussaint, J. L. Bredas, Macromolecules 1993, 26, 5240.
40. M. Baumgarten, K. H. Koch, K. Mullen, J. Am. Chem. Soc. 1994, 116, 7341.
41. R. Wegner, N. Beye, E. Fanghanel, U. Scherer, R. Wirschem, K. Mullen, 1993, 53, 353
42. T. W. Brockmann, J. M. Tour, J. Am. Chem. Soc.,1994, 116, 205.
43. J. M. Tousaint, B. Themans, J. M. Andre, J. L. Bredas, Synth. Met. 1989, 28, C205
44. J. Kurti, P. R. Suja’n, M. Kdtesz, J. Am. Chem. Soc. 1991, 113, 9865
45. M. V. Lakshmikantham, D. Lorcy, C. S. Kelley, X. L. Wu, J. P. Parakka, R. M. Metzger, M. P. Cava, Adv. Mater. 1993, 5, 723.
46. T. L. Lambert, J. P. Ferraris, J. Chem. Soc., Chem. Commun. 1991, 752
47. E. E. Havinga, T. W. Hoeve, H. Wynberg, Polym. Bull. 1992, 29, 119.
48. S. Yanagida, G.K.R. Senadeera, K. Nakamura, T. Kitamura, Y. Wada, Journal of Photochemistry and Photobiology A: Chemistry 166 (2004) 75-80
49. Christoph Winder, Niyazi Serdar Sariciftci, J. Mater. Chem., 2004, 14, 1077-1086
50. A. M. McDonagh, S. R, Bayly, D. J. Riley, M. D. Ward, J. A. McCleverty, M. A. Cowin, C. N. Morgan, R. Varrazza, R. V. Penty,I. H. White, Chem. Mater. 2000, 12, 2523.
51. (a)P. Chandrasekhar, G. C. Birur, P. Stevens, S. Rawel, E. A. Pierson, K. L. Miller, Synth. Met. 2001, 119, 293.
(b)P. Chandrasekhar, US Patent 5995273, 1999
52. John D. Tovar, Aimee Rose, Timothy M. Swager, J. Am. Chem. Soc. 2002, 124, 7762-7769.
53. D. Tourillon, F. Garnier, J. Electroanal. Chem. 1982, 135, 173-178.
54. H. Brisset, C. Thobie-Gauthier, A. Gorgues, M. Jubault, J. Roncali, J. Chem. Soc., Chem. Commun. 1994, 1305.
55. M. Boman, D. Stafstrom, Synth. Met. 55-57, 1993, 4616-4619.
56. P. A. Christensen,A. Hamnett, A. R. Hillman, M. J. Swann, J. Chem. Soc. 1993, 89, 921.
57. (a) J. Roncali, Chem. Rev. 1992, 92, 711. (b) F. Chen, P. G. Metha, L. Takiff, R. D. McCullough, J. Mater. Chem. 1996, 6, 1763. (c) S. A. Chen, C. C. Tsai, Macromolecules 1995, 28, 7525.
58. (a) D. Braum, G. Gustafsson, D. McBranch, A. G. Heeger, J. Appl. Phys. 1992, 72, 564. (b) F. Chen, P. G. Metha, L. Takiff, R. D. McCullough, J. Mater. Chem. 1996, 6, 1763.
59. (a) A. W. Gigli, G. Barbarella, L. Favaretto, F. Cacialli, R. Cingolani, Appl. Phys. Lett. 1999, 75, 439. (b) T. Granlund, M. Theander, M. Berggren, M. R. Andersson, A. Ruzeckas, V. Bjork, M. Granstrom, O. Inganas, Chem. Phys. Lett. 1998, 288, 879. (c) O. Inganas, T. Granlund, M. Theander, M. Berggren, M. R. Andersson, A. Ruzdckas, Vsundstrom, Opt. Mater. 1998, 9, 104. (d) E. Naudin, H. A. Ho, M. A. Bonin, L. Breau, D. Be’langer, Macromolecules 2002, 35, 4983-4987
60. (a) J. Pei, W. L. Yu, W. Huang, A. J. Heeger, Macromolecule 2000, 33, 2462. (b) J. Pei, W. L. Yu, W. Huang, A. J. Heeger, Macromolecule 2001, 34, 7241-7248. (c) J. Pei, W. L. Yu, W. Huang, A. J. Heeger, Synth. Met. 1999, 105, 43. (d) J. Pei, W. L. Yu, W. Huang, A. J. Heeger, Chem. Commun. 2000, 1631. (e) Y. Li, S. Holdcroft, Macromolecules 2002, 35, 6900-6906
61. M. Pomerantz, X. Gu, Macromolecules 2001, 34,1817-1822
62. H. Meng, F. Wudl, Macromolecules 2001, 34, 1810-1816
63. D. M. Welsh, L. J. Kloeppner, L. Madrigal, M. R. Pinto, B. C. Thompson, K. S. Schanze, K. A. Aboud, D. Powell, J. R. Reynolds, Macromolecules 2002, 35, 6517-6525.
64. A. Kraak, A. D. Wiersema, P. Jordens, Hans Wynberg, Tetrahedron 1967, 24, 3381-3398.
65. Kavithaa Loganathan, Eduardo G. Cammisa, Brent D. Myron, Peter G. Pickup, Chem. Mater. 2003, 15, 1918-1923.
66. R. Beyer, M. Kalaji, D. M. Taylor, Synth. Met. 1992, 92, 25.
67. Philippe Lucas, Naima El Mehdi, Hoang Anh Ho, Synthesis 2000, 9, 1253.
68. Jian Pei, Wang-Lin Yu, Jing Ni, Wee-Hing Lai, Wei Huang, Alan J. Heeger, Macromolecules 2001, 34, 7241-7248.
69. Shu Yoshida, Masanori Fujii, Yoshio Aso, Tetsuo Otsubo, Fumio Ogura, J. Org. Chem. 1994, 59, 3077-3081.
70. K.Peter C. Vollhardt, Neil E. Schore, Organic Chemistry, 3rd ed., W. H. Freeman and Company, New York, p446.
71. G. Zotti, G. Schiavon, A. Berlin, G. Fontana, G. Pagani, Macromolecules, 1994, 27, 1938
72. Jean Roncali, Chem. Rev., 1997, 97, 173-205.
73. Anna Berlin, Alberto Zaneli, Chem. Mater. 2004, 16, 3667-3676.
74. G. J. Heeres , H. Wynberg, Tetrahedron. 1972, 28, 5327-5246.
指導教授 吳春桂(Chun-Guey Wu) 審核日期 2005-7-22
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