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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 戴子安(Chi-An Dai) | |
| dc.contributor.author | Li-Ting Chen | en |
| dc.contributor.author | 陳莉婷 | zh_TW |
| dc.date.accessioned | 2021-06-15T01:50:19Z | - |
| dc.date.available | 2012-07-14 | |
| dc.date.copyright | 2009-07-14 | |
| dc.date.issued | 2009 | |
| dc.date.submitted | 2009-07-03 | |
| dc.identifier.citation | (1) Wong, W. Y.; Liu, L.; Cui, D. M.; Leung, L. M.; Kwong, C. F.; Lee, T. H.; Ng, H. F. Macromolecules 2005, 38, 4970-4976.
(2) Pei, Q. B.; Yang, Y. Journal of the American Chemical Society 1996, 118, 7416-7417. (3) Klaerner, G.; Miller, R. D. Macromolecules 1998, 31, 2007-2009. (4) Kreyenschmidt, M.; Klaerner, G.; Fuhrer, T.; Ashenhurst, J.; Karg, S.; Chen, W. D.; Lee, V. Y.; Scott, J. C.; Miller, R. D. Macromolecules 1998, 31, 1099-1103. (5) Yamamoto, T.; Maruyama, T.; Zhou, Z. H.; Ito, T.; Fukuda, T.; Yoneda, Y.; Begum, F.; Ikeda, T.; Sasaki, S.; Takezoe, H.; Fukuda, A.; Kubota, K. Journal of the American Chemical Society 1994, 116, 4832-4845. (6) Miyaura, N.; Suzuki, A. Chemical Reviews 1995, 95, 2457-2483. (7) Ranger, M.; Rondeau, D.; Leclerc, M. Macromolecules 1997, 30, 7686-7691. (8) Stambuli, J. P.; Incarvito, C. D.; Buhl, M.; Hartwig, J. F. Journal of the American Chemical Society 2004, 126, 1184-1194. (9) Yokoyama, A.; Suzuki, H.; Kubota, Y.; Ohuchi, K.; Higashimura, H.; Yokozawa, T. Journal of the American Chemical Society 2007, 129, 7236-+. (10) Huang, L.; Wu, S. P.; Qu, Y.; Geng, Y. H.; Wang, F. S. Macromolecules 2008, 41, 8944-8947. (11) Chen, S. H.; Chou, H. L.; Su, A. C.; Chen, S. A. Macromolecules 2004, 37, 6833-6838. (12) Chen, S. H.; Su, A. C.; Su, C. H.; Chen, S. A. Macromolecules 2005, 38, 379-385. (13) Teetsov, J.; Fox, M. A. Journal of Materials Chemistry 1999, 9, 2117-2122. (14) Dias, F. B.; Morgado, J.; Macanita, A. L.; da Costa, F. P.; Burrows, H. D.; Monkman, A. P. Macromolecules 2006, 39, 5854-5864. (15) Hadjichristidis, N.; Iatrou, H.; Pispas, S.; Pitsikalis, M. Journal of Polymer Science Part a-Polymer Chemistry 2000, 38, 3211-3234. (16) Rempp, P.; Franta, E.; Herz, J. E. Advances in Polymer Science 1988, 86, 145-173. (17) Peters, M. A.; Belu, A. M.; Linton, R. W.; Dupray, L.; Meyer, T. J.; Desimone, J. M. Journal of the American Chemical Society 1995, 117, 3380-3388. (18) Lazzari, M.; Lopez-Quintela, M. A. Advanced Materials 2003, 15, 1583-1594. (19) Park, C.; Yoon, J.; Thomas, E. L. Polymer 2003, 44, 7779-7779. (20) Lee, M.; Cho, B. K.; Zin, W. C. Chemical Reviews 2001, 101, 3869-3892. (21) Sandee, A. J.; Williams, C. K.; Evans, N. R.; Davies, J. E.; Boothby, C. E.; Kohler, A.; Friend, R. H.; Holmes, A. B. Journal of the American Chemical Society 2004, 126, 7041-7048. (22) Ndoni, S.; Papadakis, C. M.; Bates, F. S.; Almdal, K. Review of Scientific Instruments 1995, 66, 1090-1095. (23) Chunwaschirasiri, W.; Tanto, B.; Huber, D. L.; Winokur, M. J. Physical Review Letters 2005, 94. (24) Chen, S. H.; Su, A. C.; Chen, S. A. Journal of Physical Chemistry B 2005, 109, 10067-10072. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/43335 | - |
| dc.description.abstract | 本研究是利用Suzuki-Miyaura 偶合反應合成出一系列具均一分子量分布(monodisperse)的聚芴高分子 (poly(9,9-di-n-octyl-2,7-fluorene), PFO) ，並利用帶有醛基的金屬鈀錯合物為觸媒合成出尾端帶有醛基的聚芴高分子，再以陰離子聚合法合成兩組不同分子量大小且分子量分布(polydispersity index, PDI) 均在1.2以內的聚2乙烯吡啶 (poly(2-vinylpyridine) ，再將兩種高分子進行尾端偶合反應，得到兩組導電─絕緣團聯共聚高分子。
將四組聚芴高分子及兩組共聚高分子進行基本的性質測試。包含以膠體滲透層析儀 (Gel Permeation Chromatography, GPC) 測量其分子量與分子量分布情形、以質譜儀 (MALDI-TOF) 鑑定尾端官能基結構、以及用紫外光─可見光光譜儀 (UV-Vis Spectrophotometer) 和螢光光譜儀 (Photoluminescence) 量測其光學性質，還有利用熱重分析儀 (Thermogravimetric Analyzer, TGA) 及微差掃描卡計 (differential scanning calorimeter, DSC) 進行熱性質量測，了解團聯共聚高分子與原組成高分子的性質差異之處。也藉由小角度X光散射 (small angle X-ray scattering, SAXS)、廣角度X光散射 (wide angle X-ray scattering, WAXS) 及穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 來偵測聚芴高分子及共聚高分子的微結構排列情形、使用偏光顯微鏡 (polarized optical microscopy, POM) 來觀測相轉換的情形。總結以上的數據資訊，獲得不同分子量之聚芴高分子、以聚芴和聚2乙烯吡啶所組成的團聯共聚高分子之基本特性與其在微結構方面的認識。 | zh_TW |
| dc.description.abstract | In the thesis, a series of low polydispersity poly(9,9-di-n-octyl-2,7-fluorene) (PFO) was synthesized by Suzuki-Miyaura coupling reaction, and was tried to use arylpalladium(II) halide complexes with formyl group as catalysts to convert aldehyde-terminated PFO. In addition, a monodispersed homopolymer living anion of poly(2-vinyl pyridine) (P2VP) was synthesized via anionic polymerization using sec-butyllithium as an initiator. Block copolymers of PFO-b-P2VP were synthesized by a nucleophilic addition reaction between P2VP living anion and aldehyde-terminated PFO. Two PFO-b-P2VP block copolymers with different PFO/P2VP molar ratio were successfully synthesized with high yield.
The synthesized PFO and PFO-b-P2VP were characterized by using various techniques including Gel Permeation Chromatography (GPC), MALTI-TOF, UV-Vis, Photoluminescence (PL), Thermogravimetric Analyzer (TGA), Differential Scanning Calorimeter (DSC). Furthermore, we used the small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS) and Transmission Electron Microscope (TEM) techniques to study the crystalline structures of homo PFO and PFO in the PFO-b-P2VP nanostructures, and used Polarized Optical Microscopy (POM) to observe phase transition phenomenon. It was found that the different properties and microstructures of PFO and their block copolymers. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T01:50:19Z (GMT). No. of bitstreams: 1 ntu-98-R96524040-1.pdf: 5421778 bytes, checksum: e8512d110d0e0f2ba5abace914a1bdfc (MD5) Previous issue date: 2009 | en |
| dc.description.tableofcontents | 誌謝 ............................................................................................................................... I
摘要 .............................................................................................................................. II Abstract ...................................................................................................................... III 目錄 ............................................................................................................................. IV 圖目錄 ........................................................................................................................ VII 表目錄 .......................................................................................................................... X 附圖目錄 .............................................................................................................. X 第一章 緒論 ................................................................................................................. 1 第二章 文獻回顧 ........................................................................................................ 2 2.1 聚芴高分子 (Polyfluorene) ......................................................................... 2 2.1.1 合成方法 ............................................................................................. 2 2.1.1-1 Yamamoto coupling .......................................................................... 2 2.1.1-2 Suzuki coupling6 ............................................................................... 3 2.1.1-3 Grignard metathesis method ............................................................. 6 2.1.2 PFO的相行為及分子堆疊 ................................................................ 8 2.1.3 光學性質 ............................................................................................. 9 2.2 陰離子聚合15 .............................................................................................. 11 2.2.1 陰離子反應之起始劑 ...................................................................... 11 2.2.2 陰離子反應之單體與反應機制 ...................................................... 11 2.2.3 特殊尾端官能基之陰離子聚合17 .................................................. 13 2.3 團聯共聚高分子 (Block Copolymer)....................................................... 16 第三章 實驗 ............................................................................................................... 18 3.1 實驗藥品 ...................................................................................................... 18 3.2 儀器設備 ...................................................................................................... 20 3.3 實驗步驟 ...................................................................................................... 21 3.3.1 合成poly(9,9-dioctylfluorene) ....................................................... 21 3.3.1-1 合成2-(4',4',5',5'-tetramethyl-1',3',2'-dioxa-borolan-2'-yl)-7-bromo-9,9-dioctylfluorene 21 ..................................................................................................... 21 3.3.1-2 合成tBu3PPd(Ph)Br 9 .................................................................... 21 3.3.1-3 合成PFO 9 ..................................................................................... 22 3.3.1-4 尾端醛基化之PFO 合成 ............................................................. 22 3.3.2 陰離子聚合 ...................................................................................... 24 3.3.2-1 無水溶劑的製備22 ....................................................................... 24 3.3.2-2 聚合用單體之純化 ....................................................................... 24 3.3.2-3 陰離子聚合反應步驟 ................................................................... 26 3.3.3 合成團聯共聚高分子 PFO-b-P2VP ............................................. 28 3.3.3-1 反應前PFO的製備 ...................................................................... 28 3.3.3-2 尾端偶合反應 ............................................................................... 28 第四章 結果與討論 .................................................................................................. 30 4.1 Poly(9,9-dioctylfluorene)及單體合成之鑑定 ........................................... 30 4.1.1 2-(4',4',5',5'-tetramethyl-1',3',2'-dioxa-borolan-2'-yl)-7-bromo-9,9-dioctylfluorene合成鑑定 ................................................................................. 30 4.1.2 PFO合成鑑定 ................................................................................... 31 4.1.3尾端醛基化之PFO合成鑑定 ......................................................... 33 4.2 P2VP合成之鑑定 ........................................................................................ 35 4.3 團聯共聚高分子PFO-b-P2VP合成之鑑定 ............................................ 36 4.4 熱性質分析 .................................................................................................. 38 4.4.1 熱重分析儀 (thermal gravimetric analyzer, TGA) .................... 38 4.4.2微差掃描卡計 (differential scanning calorimeter, DSC) ............ 41 4.4.2-1 homo PFO ....................................................................................... 41 4.4.2-2 PFO-b-P2VP ................................................................................... 43 4.5 光學性質分析 ............................................................................................. 45 4.5.1 紫外線/可見光 (UV/Vis)光譜及螢光光譜儀 (luminescence spectrophotometer, PL) 分析 .................................................................. 45 4.5.1-1 Homo PFO ...................................................................................... 45 4.5.1-2 PFO-b-P2VP ................................................................................... 47 4.5.1-3 PFO-b-P2VP 在兩種不同溶劑比例混合下之光學性質 ............ 49 4.6 微結構分析 .................................................................................................. 54 4.6.1 小角度X光散射 (small angle X-ray scattering, SAXS) 圖譜分析 ................................................................................................................. 54 4.6.2 廣角度X光散射 (wide angle X-ray scattering, WAXS) 圖譜分析 ................................................................................................................. 56 4.6.2-1 PFO之WAXS分析 ...................................................................... 56 4.6.2-2 PFO-b-P2VP之WAXS分析 ........................................................ 59 4.6.3 偏光顯微鏡 (polarized optical microscopy, POM) ..................... 62 4.6.3-1 homo PFO ....................................................................................... 62 4.6.3-2 PFO-b-P2VP ................................................................................... 64 4.6.4 homo PFO之相圖 ............................................................................ 66 4.6.5 TEM影像分析 ................................................................................. 66 4.6.5-1 PFO-b-P2VP之塊材分析 .............................................................. 66 4.6.5-2 PFO-b-P2VP在溶劑─非溶劑系統下之分析 ............................. 68 第五章 結論 ............................................................................................................... 72 VI 參考文獻 ..................................................................................................................... 74 附圖 ............................................................................................................................. 76 | |
| dc.language.iso | zh-TW | |
| dc.subject | 聚芴 | zh_TW |
| dc.subject | 微結構 | zh_TW |
| dc.subject | 導電/絕緣共聚高分子 | zh_TW |
| dc.subject | 結晶結構 | zh_TW |
| dc.subject | 尾端偶合反應 | zh_TW |
| dc.subject | 陰離子聚合 | zh_TW |
| dc.subject | 啶 | zh_TW |
| dc.subject | 聚2乙烯吡 | zh_TW |
| dc.subject | poly(9 | en |
| dc.subject | rod-coil block copolymer | en |
| dc.subject | nanostructure | en |
| dc.subject | crystalline structure | en |
| dc.subject | end-coupling reaction | en |
| dc.subject | anionic polymerization | en |
| dc.subject | poly(2-vinyl pyridine) | en |
| dc.subject | 7-fluorene) | en |
| dc.subject | 9-di-n-octyl-2 | en |
| dc.title | 合成分子量均一之聚芴導電高分子及利用偶合反應合成導電/絕緣之團聯共聚高分子 | zh_TW |
| dc.title | Synthesis of Low Polydispersity Polyfluorene and Their Block Copolymer via Coupling Reaction | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 97-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 梁文傑(Man-kit Leung),王立義(Lee-Yih Wang) | |
| dc.subject.keyword | 導電/絕緣共聚高分子,聚芴,聚2乙烯吡,啶,陰離子聚合,尾端偶合反應,結晶結構,微結構, | zh_TW |
| dc.subject.keyword | rod-coil block copolymer,poly(9,9-di-n-octyl-2,7-fluorene),poly(2-vinyl pyridine),anionic polymerization,end-coupling reaction,crystalline structure,nanostructure, | en |
| dc.relation.page | 88 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2009-07-06 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 化學工程學研究所 | zh_TW |
| 顯示於系所單位： | 化學工程學系 | |
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