聚雙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：	陳丁洲 Ding-Chou Chen
論文名稱：	聚雙噻吩環戊烷衍生物的合成與性質探討 Synthesis and characterization of poly(4,4-Dioctylcyclopenta[2,1-b:3,4-b]dithio-phene) derivatives
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：	92
語文別：	中文
論文頁數：	105
中文關鍵詞：	塞吩衍生物、低能隙、導電高分子、有機場效電晶體
外文關鍵詞：	thiophene, low band gap, conducting polymer, OFET
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聚噻吩在共軛高分子系統中是結構型態最豐富的高分子之一，其結構上的多變性也同時使其性質，如半導體特性、導電性、發光性、熱穩定性…等之變化多采多姿。本實驗即藉由調變聚噻吩系統的結構來改變其能隙(band gap energy)以探討共軛高分子結構與能帶性質的關係。其中有潛力應用在藍光高分子發光二極體（PLED）與有機場效電晶體（OFET）的高、低能隙共軛高分子，將是強調的重點。利用有機合成策略在聚噻吩的主鏈或側鏈上接吡啶環(pyridine or phenanthroline)來減低聚噻吩的共軛長度，提高其能隙以合成高能隙聚噻吩衍生物；抑或形成環狀結構來降低能隙。本研究以低能隙之聚雙噻吩環戊烷（cyclopentadithiophene）為主體，並在環戊烷上引進烷基以增加高分子的溶解度，合成六種聚雙噻吩環戊烷衍生物，分別為poly(4,4-Dioctylcyclopenta[2,1-b:3,4-b]dithio-phene)
（PDOCP）Poly(4,4-Dioctylcyclopenta[2,1-b:3,4-b]dithiophene-
alt-pyri-dine)（PDOPy）、 poly(4,4-dioctyl-cyclopentadithio-
phene-alt-3,8-Phenanthrolin) （PDOPh）、poly(4,4-dioctylcyclo-
pentadithiophene-alt-Cyclopenta[2,1-b:3,4-b]dithiophene-4-
one) （PDOCK）、poly(4,4-dioctyl-cyclopentadithiophene-alt- 3-octyl-thiophene（PDOOT）及poly(4,4-dioctyl-cyclopentadi-
thiophene-alt-2-thio-phene)（PDOTh）。這些高分子除PDOCP是由氧化聚合合成外，其餘皆是利用不同單體進行A-B type Stille coupling共聚合而成的，共聚物之能隙與所組成之個別單一高分子之能隙有關，但不全然是介於個別單一高分子之間，顯示決定共聚高分子能隙的因素很複雜，無法單從其組成預測。

Polythiophenes are a series of conjugated polymers with diverse structure. The structure related properties, such as semiconducting, electric, luminescent properties, and thermal stability change accordingly. The objectives of this work are the preparation of polythiophenes with various band gap energies via structure modification. The target polymers for the applications in polymeric light emitting diode (PLED) and organic field effect transistor (OFET) were focused. The pyridine ring was added into the mail chain of polyalkylthiophenes to increase the band-gap energy of the polymer; or forming the fused-ring to reduce the band gap. We used the low band gap polymer polycyclopentadithiophene as a starting polymer and introducing an alkyl chain on the cyclopentane ring to increase its solubility, six A-B type copolymers of polycyclopentadi- thiophene derivatives such as poly(4,4-Dioctylcyclopenta[2,1-b:3,4-b] dithiophene) (PDOCP)、Poly (4,4-Dioctylcyclopenta [2,1-b:3,4-b] dithiophene)-Co-Py-ridine) (PDOPy)、poly (4,4-Dioctylcyclopenta-dithio-
phene-alt-3,8-Phe-nanthrolin) (PDOPh)、poly (4,4-Dioctylcyclo- penta-
dithiophene-alt-cyclopenta[2,1-b:3,4-b]dithio-phene-4-one) (PDOCK)、poly(4,4-Dioctyl-cyclopentadithiophene-alt-3-octyl-thiophene) (PDOOT) and poly (4,4-dioctyl-cyclopentadithiophene-alt-2-thiophene) (PDOTh) were synthesized. It was found that the band-gap energies of A-B type copolymers are not all fall inbetween its individual homopolymer. These results indicated that the band structure of A-B type copolymer is very complicated. It can not be predicted simply form just the structures of the polymers.

目  錄            頁次
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
1-1前言………………………………………………1
1-2有機共軛高分子…………………………………1
1 - 3導電高分子之發展歷史…………………………………………3
1-4導電高分子的導電機制……………………………8
1-4-1能帶結構……………………………………8
1 - 4–2 極子、雙偏極子和孤立子………………………………11
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低能隙導電高分子的介紹………………………32
1-6-1低能隙導電高分子的發展歷史……………………32
1-6-2低能隙導電高分子的種類………………………33
1-7聚3-烷基噻吩系統的介紹…………………………35
1-8研究動機…………………………………………………36
貳、實驗部分…………………………………………………………37
2-1藥品…………………………………………………………37
2-2合成實驗步驟………………………………………………41
2-2-1 聚二噻吩環戊烷衍生物之合成……………………41
2-2-1-a  Di-thiophen-3-yl-methanol的合成……………44
2-2-1-b  Dithiophen-3-yl-methanone的合成……………45
2-2-1-c  2,2-Dithiophen-3-yl-[1,3]dioxolane的合成…46
2-2-1-d  2,2-(2-iodo-thiophen-3-yl)-[1,3]dioxolan的合成…47
2-2-1-e  cyclopenta[2,1-b;3,4-b'']dithiophen-4-dioxolane的合成…48
2-2-1-f  4H-Cyclopenta[2,1-b;3,4-b'']dithiophene的合成…49
2-2-1-g  4,4-Dioctylcyclopenta[2,1-b:3,4-b’]dithiophene的合成…50
2-2-1-h  PDOCP的合成……………………………………………51
2-2-1-i  DTMSnDOCPDT 的合成…………………………………52
2-2-1-j  PDOPy 的合成…………………………………………53
2-2-1-k PDOPh 的合成………………………………………55
2-2-1-l PDOCK 的合成………………………………………56
2-2-1-m  PDOOT  的合成…………………………………………57
2-2-1-n  PDOTh  的合成…………………………………………58
2-3使用儀器與樣品的製備……………………………………66
2-3-1紅外光吸收光譜儀……………………………………66
2-3-2 紫外光/可見光/近紅外光吸收光譜…………………67
2-3-3螢光光譜儀………………………………………………68
2-3-4 核磁共振光譜儀………………………………………68
2-3-5化學分析電子分光儀(ESCA)………………………69
2-3-6掃描式電子顯微鏡(SEM)………………………………70
2-3-7 熱示差掃描卡量計(DSC)…………………………………70
2-3-8熱重分析儀(TGA)……………………………………….71
2-3-9膠體滲透層析儀(GPC)……………………………………72
參、結果與討論……………………………………………………74
3-1合成部份…………………………………………………74
3-1-1單體的製備……………………………………74
3-1-1-1不同溶劑比例製備3-Lithiumthiophene的探討……74
3-1-1-2 PCC氧化劑與分子篩的前處理………………………74
3-1-1-3 DIdioxolane製備之探討……………………………75
3-1-1-4 CPDT製備之探討………………………………………75
3-1-2 聚合物的合成……………………………………75
3-1-2-1 PDOCP之合成探討…………………………………75
3-1-2-2 含雜環之共聚雙噻吩環戊烷衍生物之合成探討……76
3-2聚合物的性質………………………………………76
3-2-1高分子的純度鑑定………………………………76
3-2-1-1 PDOCP的之純度鑑定…………………………………76
3-2-1-2 PDOPy、PDOPh、PDOCK及PDOTh的純度鑑定……………78
3-2-1-3 PDOOT的純度鑑定……………………………………80
3-2-2高分子之紅外光吸收光譜分析（FT-IR）…………82
3-2-3高分子的分子量………………………………………86
3-2-4 高分子的熱性質………………………………………87
3-2-4-1 熱重分析(TGA)…………………………………87
3-2-4-2 微分示差卡瞄計(DSC)…………………………88
3-3高分子之光學性質………………………………………90
3-3-1 UV/Vis/NIR吸收光譜……………………………90
3-3-2 共聚物與個別聚合物之能隙比較……………………92
3-3-3螢光光譜………………………………………………94
3-4高分子的表面型態…………………………………………95
肆、結論……………………………………………………………99
參考文獻……………………………………………………………100

                                

參考文獻
1. A. G. MacDiarmid, A. J. Epstein, Synth. Met. 1994, 65, 103-16.
2. J. Roncali, Chem. Rev. 1992, 92, 711.
3. K. Hyodo, Electrochem Acta 1994, 39, 265.
4. J. C. W. Chien, Academic Press, Orlando, (1984).
5. K. Y. Jen, G. G. Miller, R. L. Elsenbaumer, J. Chem. Soc., Chem. Commun. 1986, 1346.
6. M. Sato, S. Tanaka, K. Kderiydmd, J. Chem. Soc., Chem. Commum. 1986, 873.
7. J. Roncali, R. Garreau, D. Delabouglise, F. Garnier, M. Lemaire, Synth. Met. 1989, 28, C341.
8. S. D. D. V. Rughooputh, M. Nowak, S. Hotta, A. J. Heeger, F. Wudl, Synth. Met. 1987, 21, 41.
9. S. D. D. V. Rughooputh, S. Hotta, A. J. Heeger, F. Wudl, J. Polym. Sci., Polym. Phys. Ed. 1987, 25, 1071.
10. A. A. Gazz. Chim. Ital. 1916, 46, Ⅱ279.
11. G. Natta, G. Mazzanti, P. Corradini, Atti Accad. Naz. Lince Rend. Cl. Sci. Fis., Mat. Natur. 1958, 25, 3.
12. A. Dall, Olio, G. Dascola, V. Varacca, V. Bocchi, Acad. Sci. Ser. 1968, 433, C267.
13. H. Naarmann, "Structure and conductivity of organic polymers", Angew. Chem. Int. Ed. 1969, 8, 915.
14. H. shirakawa, S. Ikeda, Polym. J. 1971,2, 231
15. 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.
16. 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
17. D. Braun, A. J. Heeger, Appl. Phys. Lett 1990, 58, 1982-1984
18. K. Susan, E. S. Vanderkam, J. S. Gawalt, A. B. Bocarsly, Langmuir 1999, 15, 6598-6600.
19. M. G. Kanatzids, "Conductive polymers", C&EN, 1990, 3, 36.
20. 洪添燦, 1998, 國立清華大學化學工程研究所博士論文 .
21. C. Kittel, "Introduction to Solid State Physics". 6th ed., John Wiley & Son, Singapore, 1986.
22. K. Y. Jen, G. G. Miller, R. L. Elsenbaumer, J. Chem. Soc., Chem. Commun.1986, 1346.
23. S. D. D. V. Rughooputh, M. Nowak, S. Hotta, A. J. Heeger, F. Wudl, Synth. Met. 1987,21, 41.
24. 張淑美，科學月刊 2001,第三十二卷第二期,108.
25. A. S. Wood, "Tapping the power of intrinsic conductivity", Modern Plastics Int., Aug. 1991, 33.
26. 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.
27. M. Pope, H. P. kallmann, P. Magnante, J.Chem. Phys. 1963, 38, 2042
28. C. W. Tang, S. A. VanSlyke, Appl. Phys. Lett. 1987, 51, 913
29. T. Osaka, S. Komada, K. Fujihana, N. Okamoto, N. Kaneko, J. Electrochem. Soc. 1997, 114, 743.
30. A. J. Epstein, J. M. Ginder, R. W. Bigelow, A. G. MacDiamid, Synth. Met. 1987, 18, 303.
31. J. Lowe, S. Holdcroft, Marcromolecules 1995, 28, 4608.
32. 瞭解真空管及電晶體電路，黃鑑村編著，無線電界雜誌社印行
33. 材料科學與工程，William F. Smith 著，李春穎、許煙明、陳忠仁譯
34. 圖解電子回路，稻見辰夫著，葉隆吉審訂，世茂出版社
35. Wenjie Li,* Howard E. Katz, Andrew J. Lovinger, Chem. Mater. 1999, 11, 458-465
36. 麥肯錫季刊, 2002年第1季
37. (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
38. Zhenan Bao, Andrew J. Lovinger Appl. Phys. Lett.1996, 69, 26,
39. 洪添燦, 1998, 國立清華大學化學工程研究所博士論文 .
40. J. P. Ferraris, T. L. Lambert, J. Chem. Soc., Chem. Commun. 1991,
1286.
41. M. Kobayashi, N. Colaneri, M. Boysel, F. Wudl, A. J. Heeger, J. Org. chem. 1984, 49, 3382.
42. M. Kertesz, Y.-S. Lee, Synth. Met. 1989, 28 C545.
43. J. M. Toussaint, J. L. Bredas, Macromolecules, 1993, 26, 5240.
44. M. Baumgarten, K. H. Koch, K. Mullen, J. Am. chem. Soc. 1994, 116, 7341.
45. R. Wegner, N. Beye, E. Fanghanel, U. Scherer, R. Wirschem, K. Mullen, 1993, 53, 353.
46. T. W. Brockmann, J. M. Tour, J. Am. Chem. Soc., 1994, 116, 205.
47. J. M. Tousaint, B. Themans, J. M. Andre, J. L. Bredas, Synth. Met. 1989, 28, C205.
48. J. Kurti, P. R. Suja''n, M. Kdtesz, J. Am. Chem. Soc. 1991, 113, 9865.
49. 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.
50. T. L. Lambert, J. P. Ferraris, J. Chem. Soc, Chem. Commun., 1991, 752.
51. E. E. Havinga, T. W. Hoeve, H. Wynberg, Polym. Bull. 1992, 29, 119.
52. (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.
53. (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.
54. (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.Ruzeckas, V. Sundstrom, Opt. Mater. 1998, 9, 104. (d) E. Naudin, H. A. Ho, M.-A. Bonin, L. Breau, D. Be´langer Macromolecules 2002, 35, 4983-4987
55. (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, Synth. Met. 1999, 105, 43. (c) J. Pei, W. L. Yu, W. Huang, A. J. Heeger Chem. Commun. 2000, 1631. (d) J. Pei, W. L. Yu, J. Ni, Y.-H. Lai, W. Huang, A. J. Heeger Macromolecules 2001, 34, 7241-7248.
56. Y. Li, S. Holdcroft Macromolecules 2002, 35, 6900-6906.
57. J. Pei, W.-L. Yu, W. Huang, A. J. Heeger Macromolecules 2000, 33, 2462.
58. M. Pomerantz, X. Gu Macromolecules 2001, 34, 1817-1822
59. H. Meng, F. Wudl Macromolecules 2001, 34, 1810-1816
60. (a) M. Kozaki, S. anaka, Y. Yamashita J. Organ. Chem. 1994, 59, 442-450. (b)M. L. Brecque MOSAIC 1989, 20, 16-27.
61. D. M. Welsh, L. J. Kloeppner, L. Madrigal, M. R. Pinto, B. C. Thompson, K. S. Schanze, K. A. Abboud, D. Powell, J. R. Reynolds Macromolecules 2002, 35, 6517-6525.
62. (a) G. Zotti, S. Zecchin, A. Berlin, G. Schiavon, G. Giro Chem. Mater. 2001, 13, 43-52. (b) T. Benincori, V. Consonni, P. Gramatica,| T. Pilati, S. Rizzo, F. Sannicolo`, R. Todeschini, G. Zotti Chem. Mater. 2001, 13, 1665-1673. (c) H. Huang, P. G. Pickup Chem. Mater. 1999, 11, 1541-1545. (d) T. L. Lambert, J. P. Ferraris, J. Chem. Soc., Chem. Commun. 1991,752-754.
63. T. Kanbara, T. Kushida, N. Saito, I. Kuwajima, K. Kubota, T. Yamamoto, Chem. Lett. 1992, 583.
64. (a) Y. Z. Wang, D. D. Gebler, L. B. Lin, J. W. Blatchford, S. W. Jessen, H. L. Wang, A. J. Epstein, Appl. Phys. Lett. 1996, 68, 894. (b) Y. Z. Wang, D. D. Gebler, D. K. Fu, T. M. Swager, A. G. MacDiarmid, A. J. Epstein, Synth. Met. 1997, 85, 1179.
65. L. Trouillet, A. D. Nicola, S. Guillerez Chem. Mater. 2000, 12, 1611-1621.
66. P. Jordens, G, Rawson, H. Wynberg, J. Chem. Soc. (c), 1970, 273
67. Paolo Coppo, Domenico C. Cupertino, Stephen G. Yeates, Michael L. Turner Macromolecules 2003, 36, 2705-2711
68. R. Beyer, M. Kalaji, D. M. Taylor Synth. Met., 1992, 92, 25
69. Philippe Lucas, Naima El Mehdi, Hoang Anh Ho Synthesis 2000, 9, 1253
70. L.Trouillet, A. De Nicola, S. Guillerez, Chem. Mater. 2000, 12, 1611-1621.
71. 張榮華 , 鄭嘉 , 科儀新知 ,1988(77年), 9, 6, 22
72. 陳慶梁 , 科儀新知 , 1982(71年), 4, 1, 87.
73. 陳慶梁 , 科儀新知 , 1981(70年), 2, 4, 29.
74. 陳陵援 ,儀器分析特論 , 三民書局印行 .
75. X. Wu, T.-A. Chen, R. D. Rieke Tetrahedron Letters.1994, 35, 22, 3673
76.張信貞，科儀新知，1988（77年），10，1，44.
77. Paolo Coppo, Domenico C. Cupertino, Stephen G. Yeates, Michael L. Turner Macromolecules 2003, 36, 2705-2711
78. Skoog, Principles of Instrumental Analysis, fifth edition

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