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研究生:陳威冶
研究生(外文):Wei-Ye Chen
論文名稱:髮-桿狀共軛高分子之合成與物性探討
論文名稱(外文):Studies on the synthesis and physical properties of hair-rod conjugated copolymer
指導教授:廖建勛
指導教授(外文):Chien-Shium Liao
學位類別:碩士
校院名稱:元智大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
中文關鍵詞:共軛高分子髮-桿狀
外文關鍵詞:conjugated polymerhair-rod
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本研究以Wittig reaction 製備具短鏈乙氧基團側鏈的全反式構形共聚高分子,極性側鏈增加共軛高分子剛硬主鏈的溶解性,且能提昇與有機鹽類分子的相容性,所合成的共聚高分子結構,分為主鏈上苯環對位-對位和對位-間位交替鍵結的兩種共聚高分子。藉由DSC和TGA分析共聚高分子的熱穩定性,對位-對位連結的共聚高分子具有較高的熔點和結晶性,此種差異主要在於對位共聚高分子在結構上的有序性和全共軛構象。DSC和偏光顯微鏡影像結果,顯示出對位-對位共聚高分子因結構的剛硬性致使有液晶性質的顯現。在光譜分析比較上,藉由UV-Vis 和PL 光譜量測可發現主鏈結構上的差異對於高分子光學性質上的影響。結果顯示出全對位鍵結高分子主鏈的全共軛構象,導致在UV-vis 吸收和PL放射波長相較於對位-間位連接共聚高分子有較大的紅移現象產生。全對位共聚高分子膜最大吸收波長456nm,最大放射波長為548nm。而對位-間位共聚高分子之最大吸收波長為404nm,最大放射波長為495nm。
DEA介電分析結果於低頻升溫操作下,全對位共聚高分子約在熔點和液晶變化溫度附近發現兩個明顯的介電鬆弛峰,而在對位-間位共聚高分子熔點以後之介電常數變化較為複雜,主要是由於對位-間位連結的共聚高分子相對於全對位共聚高分子有較高的分子柔軟性,使高分子鏈的熱運動形態更為多樣。
共聚高分子與Ru錯合體的混摻,其光譜分析結果顯示,全對位共聚高分子混摻膜的UV-Vis吸收和PL放射光譜並不因Ru金屬混摻而有所影響。但在對位-間位共聚高分子之PL量測結果,發現其螢光強度隨著Ru錯合體的濃度增加而減少,原因為對位-間位共聚高分子之PL放射光譜區域與Ru錯合體吸收光譜區域產生重疊,導致混摻高分子受光激發產生能量轉移現象。由AFM表面形態分析結果,發現混摻膜表面形態不因Ru錯合體的加入產生相分離,其原因為側鏈改質所具有的相容性。
In this study, two types of all trans phenylenevinylene alternative copolymers with high polar oligo(ethylene oxide) side chains are synthesized by using Wittig reaction. The conjugated copolymer with polar side chain can increase the solubility of rigid polymer in common organic solvent. The polar side chain can act as ionic conducting components to facilitate the electrochemical doping process. It is found that all para-phenylenevinylene copolymer had more thermal stability than para-meta alternative phenylenevinylene copolymer by DSC and TGA analyses. It can be attributed to the higher ordered structure and conjugated degree of the copolymer with all para alternative backbone. It is also noted that all-trans poly(para-phenylenevinylene) containing fusible oligo(ethylene oxide) side chains exhibits liquid crystalline properties revealed by DSC and POM analyses. The maximum peaks of UV-vis absorption and PL emission in all para-phenylenevinylene copolymer solid film have larger red-shifted than para-meta alternative phenylenevinylene copolymer. It is likely due to the highly ordered structure existed in the all-para copolymer. This ordered structure in the solid state may arise from either intra- or intermolecular π-π interactions of the chromophores. The dielectric constant of these copolymers increases with increasing temperature at low frequency. The all-para PPVcopolymer has two relaxation peaks of dielectric constant around the melting and liquid crystalline transition temperature. There no apparent changes in UV-vis absorption appears for copolymers blending with Ru metal complex. The PL emissive intensity of the para-meta copolymer decreases with increasing Ru complex concentration. It results from the overlaps of copolymer PL emission and Ru complex UV-vis absorption that causes the energy transfer from copolymer to Ru complex. There is no phase separation on the blending morphology observed by AFM.
目錄…………………………………………………………………….. I
圖目錄………………………………………………………………….. III
名詞縮寫 V
第一章 緒 論………………………………………………………….. 1
1-1 前言………………………………………………………….. 1
1-2 本文目的…………………………………………………….. 1
第二章 文獻回顧……………………………………………………… 2
2-1 高分子發光材料的演進…………………………………….. 2
2-2 高分子發光二極體發光效率提升………………………….. 4
2-3 側鏈分子基團的作用……………………………………….. 10
2-4 混摻效應…………………………………………………….. 15
2-5 配位有基金屬錯合物應用………………………………….. 22
第三章 實驗內容……………………………………………………… 29
3-1 實驗藥品清單……………………………………………….. 29
實驗架構圖………………………………………………….. 32
3-2 實驗步驟…………………………………………………….. 33
Wittig reaction 反應機制介紹 35
3-3 實驗儀器原理……………………………………………….. 47
第四章 結果討論……………………………………………………… 54
4-1 高分子BTEOPPV-alt-PPV 合成與結構性質討論………… 54
4-2 高分子BTEOPPV-alt-MPV 合成與結構性質討論……… 62
全反式BTEOPPV-alt-PPV與BTEOPPV-alt-MPV copolymer 性質比較 68
4-3 Ru 金屬錯合物鑑定與分析………………………………… 73
4-4 BTEOPPV-alt-PPV/MPV 混摻效應探討………………… 78
第五章 結論………………………………………………………….. 81
參考文獻…………………………………………………….. 101
1. A.Bernanose,M.Comte,P.Vouaux, J.Chim.Phys. 50, 64(1953)
2. A.Bernanose,P.Vouaux J.Chim.Phys. 50,261(1953)
3. A.Bernanose. J.Chim.Phys.52,396(1955)
4. Bernanose,P.Vouaux. J.Chim.Phys. 52,509(1955)
5. R.Partridge, US Patent 3 995 299(1976)
6. R.Wessling,R.Zimmerman. U.S. patent 3 401 152(1968)
7. R.Wessling,R.Zimmerman. U.S. patent 3 706 677(1972)
8. R.Wessling, J.Polym.Sci.Polym.Symp. 72,55(1985)
9. D.Braun,A.Hegger. Appl.Phys.Lett. 58,1982(1991)
10. A.Holmes,D.Bradley,A.B.Brown,R.Marks et al. Nature. 347,539(1990)
11. Maki Hamguchi,Katsumi Yoshino, Appl.Phys.Lett. 69,143(1996)
12. M.berggren,O.Inganas, Nature. 372,444(1994)
13. Y.Z.Wang,R.G.Sun, Appl.Phys.Lett. 74,3613(1999)
14. F.zu,C.H.A.Huan, Thin Solid Films. 359,244(1999)
15. K.Zhang,F.Zhu, J.Appl.Phys. 86,974(1999)
16. T.Ishida,H.Kobayashi, J.Appl.Phys. 73,4344(1993)
17. J.Hu,R.G.Gordon, J.Appl.Phys. 72,581(1992)
18. J.S.Kim,F.Cacialli,A.Cola, Appl.Phys.Lett. 75,19(1999)
19. A.J.Heeger,Y.Cao, Synth. Met. 87,171-174(1997)
20. Yi He,Jerzy Kanicki, Appl.Phys.Lett. 76,661(2000)
21. M.G.Mason, Appl.Phys.Lett. 70,152(1997)
22. Jean Roncali, Chem.Rev. 97,173(1997)
23. M.Grell, D.D.C.Bradley,M.Inbasekaran. Adv. Mater. 9,798(1997)
24. Pei, Science. 269,1086(1995)
25. Qibing Pei,Yang Yang,Gang Yu. J.Am.Chem.Soc. 118, 3922(1996)
26. A.B.Holmes,J.Morgado,R.H.Friend et al.J.Appl.Phys. 86,6392(1999)
27. A.B.Holmes,Sung Tae Kim et al. Synth. Met. 91,279(1997)
28. A.B.Holmes,J.Morgado,R.H.Friend et al. J.Appl.Phys. 86,6392(1999)
29. A.B.Holmes,F.Cacialli,B.S.Chuah et al. Synth. Met. 102,1022(1999)
30. A.B.Hegger, J.Electrochem.Soc. 144,L317(1997)
31. A.B.Holmes,Franco Cacialli,Beng Sim Chuah. Synth. Met. 111-112,449(2000)
32. Blom, P.W.M.; Martens, H.C.F.; Schoo, H.E.M.; Vissenberg, M.C.J.M.; Huiberts. Synth. Met. 122,95(2001)
33. H.C.F.Martens, P.W.M.Blom, Phys. Rev. B. 61,7489(2000)
34. M.Yan,L.J.Rothberg,T.M.Miller. Phys.Rev.Lett. 73,744(1994)
35. S.A.Jenekhe, J.A.Osaheni. Chem.Mater. 6,1906(1994)
36. K.L.Brandon, P.G.Bentley,D.D.C.Bradley,D.A.Dunmur. Synth. Met. 91,305(1997)
37. K.E.Aasmundtveit, E.J.Samuelsen, Macro. 33,5481(2000)
38. Vicki Cleave, Goghan Yahioglu, Adv.Mater. 11,285(1999)
39. T. Virgili,D.G.Lidzey, Synth. Met. 111-112,203(2000)
40. T. Virgili,D.G.Lidzey, Adv.Mater. 12,58(2000)
41. Yu-Hua Niu,Wei Yang, Appl.Phys.Lett. 81,2884(2002)
42. Jeong-Ik Lee,In-Nam Kang, Chem.Mater. 8,1925(1996)
43. Fermi, Notes on Quantum Mechanics. p99-100(1961)published by the University of Chicago
44. T.Forster. Discuss.Faraday Soc. 27,7(1959)
45. D.L.Dexter. J.Chem.Phys. 21,836(1953)
46. Michael Gratzel,Jacques Moser, J.Am.Chem.Soc. 107,2988(1985)
47. Pau Liska,Michael Gratzel, J.Am.Chem.Soc. 110,1216(1988)
48. R.Amadelli,R.Argazzi,C.A.Bignozzi,F.Scandola J.Am.Chem.Soc. 112,7099(1990)
49. Sumi, J.Polym.Sci, Polym.Lett.Ed. 20,291(1982)
50. J.K.Lee,D.S.Yoo, Appl.Phys.Lett. 69,1686(1996)
51. J.K.Lee,M.F.Rubner, Chem.Mater. 9,1710(1997)
52. A.P.Wu,J.K.Lee. Thin Solid Films. 329,663(1998)
53. Lyons.C.H,Abbas.E.D,Lee J.K,Rubner M.F. J.Am.Chem.Soc. 120,12100(1998)
54. A.P.Wu,D.S.Yoo, J.Am.Chem.Soc. 121,4883(1999)
55. Ulrich S.Schubert, Bas G.G.Lohmeijer.Macromol.Chem.Phys. 204,1072(2003)
56. Jean-Franceois,Bas G.G.Lohmeijer,Ulrich S.Schubert, Macromolecules. 35,4560(2002)
57. Jean-François Gohy,Bas G.G.Lohmeijer,Ulrich S.Schubert, Macromol.Rapid Commun. 23,555(2002)
58. Ulrich S.Schubert, Chem.Eur.J. 9,3472(2003)
59. Charles J.Pedersen. J.Am.Chem.Soc. 87,7017(1967)
60. Choong Eui Song,Jung Woon Yang,Eun Joo Roh,Sang-gi Lee,Jou Hyeon Ahn,Hogyu Han. Angew.Chem.Int.Ed. 41,3852(2002)
61. Rainer Dobrawa,Frank Wiirthner, Chem Coommun. 17,1878-1879(2002)
62. Ulrich S.Schubert,Harald Hofmeier. Macromol.Rapid Commun. 23,561(2002)
63. Mauro Maestri,Ja Nicola Armaroli, Inorg.Chem. 34,2759(1995)
64. Creutz,C,Chou,M,J.F.Espinosa et al. J.Am.Chem.Soc. 102,1309(1980)
65. Jay R. Winkler, Thomas L. Netzel, Carol Creutz, Norman Sutin. J.Am.Chem.Soc. 109,2381(1987)
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