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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 趙基揚 | |
dc.contributor.author | I-Chun Hsieh | en |
dc.contributor.author | 謝依純 | zh_TW |
dc.date.accessioned | 2021-05-20T20:36:44Z | - |
dc.date.available | 2010-08-05 | |
dc.date.available | 2021-05-20T20:36:44Z | - |
dc.date.copyright | 2008-08-05 | |
dc.date.issued | 2008 | |
dc.date.submitted | 2008-07-29 | |
dc.identifier.citation | 參考文獻
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Journal of Physical Chemistry, 1987. 91(22): p. 5813-5818. 8. Macdiarmid, A.G., et al., Polyaniline - Protonic Acid Doping to the Metallic Regime. Molecular Crystals and Liquid Crystals, 1985. 125(1-4): p. 309-318. 9. Huang, J.X. and R.B. Kaner, The intrinsic nanofibrillar morphology of polyaniline. Chemical Communications, 2006(4): p. 367-376. 10. Huang, J.X. and R.B. Kaner, A general chemical route to polyaniline nanofibers. Journal of the American Chemical Society, 2004. 126(3): p. 851-855. 11. Konyushenko, E.N., et al., Polyaniline nanotubes: conditions of formation. Polymer International, 2006. 55(1): p. 31-39. 12. Stejskal, J., et al., Oxidation of aniline: Polyaniline granules, nanotubes, and oligoaniline microspheres. Macromolecules, 2008. 41(10): p. 3530-3536. 13. Osterholm, J.E., et al., Emulsion Polymerization of Aniline. Synthetic Metals, 1993. 55(2-3): p. 1034-1039. 14. Jing, L., et al., Micromorphology and electrical property of the HCl-doped and DBSA-doped polyanilines. Synthetic Metals, 2004. 142(1-3): p. 107-111. 15. Barra, G.M.O., et al., X-ray photoelectron spectroscopy and electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid as a function of the synthetic method. Journal of Applied Polymer Science, 2001. 80(4): p. 556-565. 16. Shreepathi, S. and R. Holze, Spectroelectrochemical investigations of soluble polyaniline synthesized via new inverse emulsion pathway. Chemistry of Materials, 2005. 17(16): p. 4078-4085. 17. Han, M.G., et al., Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution. Synthetic Metals, 2002. 126(1): p. 53-60. 18. Han, D.X., et al., Reversed micelle polymerization: a new route for the synthesis of DBSA-polyaniline nanoparticles. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2005. 259(1-3): p. 179-187. 19. Jang, W.H., et al., Synthesis and electrorheology of camphorsulfonic acid doped polyaniline suspensions. Colloid and Polymer Science, 2001. 279(8): p. 823-827. 20. Huang, J.X., et al., Polyaniline nanofibers: Facile synthesis and chemical sensors. Journal of the American Chemical Society, 2003. 125(2): p. 314-315. 21. Gangopadhyay, R., A. De, and G. Ghosh, Polyaniline-poly (vinyl alcohol) conducting composite: material with easy processability and novel application potential. Synthetic Metals, 2001. 123(1): p. 21-31. 22. Chen, S.A. and W.G. Fang, Electrically Conductive Polyaniline Poly(Vinyl Alcohol) Composite Films - Physical-Properties and Morphological Structures. Macromolecules, 1991. 24(6): p. 1242-1248. 23. Mirmohseni, A. and G.G. Wallace, Preparation and characterization of processable electroactive polyaniline-polyvinyl alcohol composite. Polymer, 2003. 44(12): p. 3523-3528. 24. Liu, J.M. and S.C. Yang, Novel Colloidal Polyaniline Fibrils Made by Template Guided Chemical Polymerization. Journal of the Chemical Society-Chemical Communications, 1991(21): p. 1529-1531. 25. Li, W.G., et al., Toward understanding and optimizing the template-guided synthesis of chiral polyaniline nanocomposites. Macromolecules, 2002. 35(27): p. 9975-9982. 26. Dorey, S., et al., Ultrafine nano-colloid of polyaniline. Polymer, 2005. 46(4): p. 1309-1315. 27. Jayanty, S., et al., Polyelectrolyte templated polyaniline-film morphology and conductivity. Polymer, 2003. 44(24): p. 7265-7270. 28. Karakisla, M., M. Sacak, and U. Akbulut, Conductive polyaniline poly(methyl methacrylate) films obtained by electropolymerization. Journal of Applied Polymer Science, 1996. 59(9): p. 1347-1354. 29. Park, S.Y., et al., Polyaniline microsphere encapsulated by poly(methyl methacrylate) and investigation of its electrorheological properties. Colloid and Polymer Science, 2003. 282(2): p. 198-202. 30. Cho, M.S., et al., Synthesis and electrorheological characteristics of polyaniline-coated poly(methyl methacrylate) microsphere: Size effect. Langmuir, 2003. 19(14): p. 5875-5881. 31. Kim, B.J., et al., Preparation of PANI-coated poly(styrene-co-styrene sulfonate) nanoparticles. Polymer, 2002. 43(1): p. 111-116. 32. Barra, G.M.O., et al., Processing, characterization and properties of conducting polyaniline-sulfonated SEBS block copolymers. European Polymer Journal, 2004. 40(9): p. 2017-2023. 33. Stejskal, J., et al., Polyaniline dispersions 2. UV--Vis absorption spectra. Synthetic Metals, 1993. 61(3): p. 225-231. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/9707 | - |
dc.description.abstract | 在這個研究中,我們利用陰離子聚合及後續的化學合成反應得到具高度磺酸化且分子量分布集中的團鍊共聚高分子電解質。此團鍊共聚高分子電解質在水溶液中會隨著濃度變化而形成不同自組裝的微結構,在苯胺進行聚合時可以當作模組(template)來導引聚苯胺複合物的微結構;同時高分子電解質鍊段的磺酸根也扮演摻雜(dopant)的角色,以使合成出的聚苯胺複合物有良好的導電度。聚苯胺複合物的製備是將苯胺單體在0℃下在團鍊共聚高分子電解質水溶液中進行乳化共聚合反應(in situ emulsion polymerization)。我們以團鍊共聚高分子電解質水溶液的濃度與反應時間為可變參數來研究影響聚苯胺與團鍊共聚高分子電解質的共聚物的微結構及導電度的因素,並探討這些複合物的成長機制。 | zh_TW |
dc.description.abstract | In this study, we used anionic polymerization and sequential analogous chemistry to synthesize sulfonic acid containing block polyelectrolytes with high degree of sulfonation and narrow molecular weight distribution. When these block polyelectrolytes were dispersed in water, various self-assembled morphologies were observed as a function of the concentration of the aqueous solution and of the molecular weight of the block polyelectrolyte. The block polyelectrolytes played the role as the templates to direct the morphology of PAni/block polyelectrolyte composites and they were also served as dopants simultaneously to enhance the electric conductivity of the PAni/block polyelectrolyte composites. The PAni composites were prepared by adding the aniline monomers to the block polyelectrolyte aqueous solution to proceed in situ emulsion polymerization at 0℃. Parameters affecting the morphologies and the conductivity were found to be the concentrations of the block polyelectrolyte aqueous solution and the reaction time. The growth mechanism of the PAni/polyelectrolyte composites were also investigated. | en |
dc.description.provenance | Made available in DSpace on 2021-05-20T20:36:44Z (GMT). No. of bitstreams: 1 ntu-97-R95527044-1.pdf: 11891269 bytes, checksum: 8f1d06edabc7f63aef1ac7e2df5c2b89 (MD5) Previous issue date: 2008 | en |
dc.description.tableofcontents | 目錄
口試委員審定書………………………………………………………………………..i 誌謝……………………………………………………………………………………i i 中文摘要……………………………………………………………………………..i i i 英文摘要………………………………………………………………………………iv 第一章 文獻回顧及原理……………………………………………………………...1 1.1 導電高分子之研究背景…………………………………………………1 1.2 導電高分子的導電機制[2]………………………………………………3 1.3 摻雜原理及方法…………………………………………………………6 1.4 聚苯胺……………………………………………………………………7 1.4.1 聚苯胺的結構…………………………………………………….7 1.4.2 聚苯胺的合成…………………………………………………….9 1.4.3 質子酸摻雜...................................................................................11 1.4.3.1 苯胺與無機酸或小分子有機酸共聚合……………....12 1.4.3.2 苯胺與有機質子酸共聚合……………………………15 1.4.3.3 以高分子為template的苯胺共聚合反應………….....18 1.4.3.4 聚苯胺與團鍊共聚高分子的共聚物............................20 1.5 聚苯胺與團鍊共聚高分子電解質之複合材料研究(directing the morphology of the PAni composites assisted by block polyelectrolytes)………………………………………………………21 第二章 實驗部份……………………………………………………………….........23 2.1 實驗藥品..……………………………………………………………..23 2.2 實驗儀器………………………………………………………………25 2.3 實驗步驟……………………………………………………………....26 2.3.1 Poly(styrene-block-sulfonated hydroxystyrene)(PS-b-sPHS)團鍊共聚高分子電解質的合成………………………………….......26 2.3.2 PAni/PS-b-sPHS複合物的製備………………………………..29 2.3.3 PAni/PS-b-sPHS複合物的結構與特性鑑定…………………..29 2.3.4 二次摻雜(Secondary doping)………………………………30 2.3.5 PAni/PS-b-sPHS2 composites UV-Vis吸收光譜………………30 第三章 結果與討論………………………………………………………………….31 3.1 Block polyelectrolyte的合成……………………………………………31 3.2 PAni/PS-b-sPHS複合物的製備與特性研究…………………………...36 3.2.1 PAni/PS-b-sPHS1複合物的微結構與導電特性…………………37 3.2.2 PAni/PS-b-sPHS2複合物的微結構與導電特性…………………53 第四章 結論………………………………………………………………………….74 第五章 未來展望…………………………………………………………………….75 文獻回顧 ……………………………………………………………………………...76 圖目錄 Figure.1-1 常見的導電高分子結構圖…………………………………………….....2 Figure.1-2 聚乙炔的電子結構與能隙圖[2]…………………………………………..4 Figure.1-3 (a)材料的能階圖;(b)摻雜前後導電高分子的能階圖………………….5 Figure.1-4 PA摻雜後形成未定域π電子…………………………………………….6 Figure.1-5 四種不同氧化態聚苯胺的結構…………………………………………..8 Figure.1-6 聚苯胺的聚合反應機構[7]………………………………………………10 Figure.1-7 聚苯胺經質子酸摻雜後的導電機制……………………………………11 Figure.1-8 苯胺與1.0M HCl 共聚合所產生的聚苯胺顆粒和少許纖維(箭頭處)的 SEM圖[10]…………………………………………………………….....12 Figure.1-9 苯胺與0.1M 硫酸共聚合產生的聚苯胺:(a) SEM、(b) TEM影像[11] …………………………………………………………………………...13 Figure.1-10 苯胺與0.4M acetic acid 共聚合產生的聚苯胺圖像:(a) SEM、(b) TEM [11]………………………………………………………………...13 Figure.1-11 苯胺與0.5M acetic acid 共聚合產生的聚苯胺圖像:(a) SEM、(b) TEM[12]………………………………………………………………...14 Figure.1-12 PANi-DBSA 的SEM圖像:(a)fibrils結構[16];(b)granular particles[17]……………………………………………………………....16 Figure.1-13 PANi-CSA的SEM 圖像:(a) granular particles[19];(b) fibrils結構[20] …………………………………………………………………………..17 Figure.1-14 (a)[21]與(b)[23] PAni-HCl/PVA 複合物的TEM 圖像………………….18 Figure.1-15 PANI-CSA/PAA共聚物的TEM圖像[25]……………………………...19 Figure.1-16 PANI-HCl/PSSNa共聚物的TEM影像:(a)在較低PSSNa濃度下反應 所得的球狀(spheres)結構[26];(b)在較高PSSNa濃度下所得的纖 (fibrils)結構[26]…………………………………………………………..19 Figure.1-17 PANI-HCl/PMMA共聚物的SEM影像:球狀結構[30]…………………...20 Figure.1-18 (a) PS-co-PSS 乳膠(latex)與;(b) PANi-HCl/PS-co-PSS core-shell 共聚物的TEM影像[31]…………………………………………………………………...20 Figure.2-1團鍊共聚高分子電解質合成途徑示意圖………………………………26 Figure.3-1 PS1與PS-b-PtBS1的GPC圖………………………………………….32 Figure.3-2 PS-b-PtBS1之分子結構與1H NMR圖譜……………………………...33 Figure.3-3 PS-b-PHS1之分子結構與1H NMR圖譜………………………………34 Figure.3-4 PS-b-sPHS1的FTIR圖譜……………………………………………....35 Figure.3-5 不同濃度的PS-b-sPHS1水溶液在TEM下所觀察到的micelle結構: (a) 3.42*10-4M;(b) 6.84*10-4M;(c) 1.368*10-3M;(d) 2.05*10-3M; (e) 2.74*10-3M;(f) 3.4210-3M................................................................43 Figure.3-6 PAni/PS-b-sPHS1複合物在[PS-b-PHS1]=3.42*10-4M水溶液中經過不同 反應時間所形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時…………………………………….44 Figure.3-7 PAni/PS-b-sPHS1複合物在[PS-b-PHS1]=6.84*10-4M水溶液中經過不 同反應時間所形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時………………………………….45 Figure.3-8 PAni/PS-b-sPHS1複合物在[PS-b-PHS1]= 1.368*10-3M水溶液中經過不 同反應時間形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時…………………………………46 Figure.3-9 PAni/PS-b-sPHS1複合物在[PS-b-PHS1]= 2.05*10-3M水溶液中經過不 同反應時間形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時…………………………………….47 Figure.3-10 PAni/PS-b-sPHS1複合物在[PS-b-PHS]= 2.74*10-3M水溶液中經過不 同反應時間形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時…………………………………...48 Figure.3-11 PAni/PS-b-sPHS1複合物在[PS-b-PHS1]= 3.42*10-3M水溶液中經過不 同反應時間形成的TEM影像:(a)尚未聚合(aniline仍未加入); (b)5小時;(c)10小時;(d)20小時…………………………………...49 Figure.3-12 (a)PAni分子量隨反應時間對導電度的影響;(b) Degree of doping 隨時間對導電度的影響;(c) Domain continuity 隨時間對導電度 的影響;(d) PAni分子量、Degree of doping 和 Domain continuity 隨時間對導電度的綜合影響;(e) PAni分子量和domain continuity 隨時間對導電度的綜合影響…………………………………………50 Figure.3-13不同PS-b-sPHS2濃度的水溶液與表面張力的關係圖……………...59 Figure.3-14 從TEM下所觀察到PS-b-sPHS2在8.7*10-5M的水溶液中所形成 的micelle結構的影像:(a)全影像;(b)放大後的串珠狀結構; (c)短柱狀結構…………………………………………………………60 Figure.3-15 Figure.3-14中不同結構的micelle的形成機制:(a)串珠狀結構; (b)短柱狀結構……………………………………………………….61 Figure.3-16從TEM下所觀察到PS-b-sPHS2在1.76*10-4M的水溶液中所形成 的micelle結構的影像:(a)球狀聚集;(b)長條狀的結構…………..62 Figure.3-17從TEM下所觀察到PS-b-sPHS2在2.63*10-4M的水溶液中所形成 的micelle結構的影像:(a)不規則的micelle聚集;(b)micelle聚集 而成的長條狀結構…………………………………………………...63 Figure.3-18利用Dynamic light scattering測得不同PS-b-sPHS2水溶液濃度中 PS-b-sPHS2的粒徑分布:(a) 8.7*10-5M;(b) 1.76*10-4M; (c) 2.63*10-4M…………………………………………………………64 Figure.3-19從TEM下所觀察到[PS-b-sPHS2]= 8.7*10-5M水溶液所形成的micelle 結構:(a)由≦50nm的micelle連接形成串珠狀;在與0.1M aniline 反應(b)5小時;(c)10小時;(d)20小時後的PAni/PS-b-sPHS2微結構 …………………………………………………………………………65 Figure.3-20 aniline吸附在串珠狀PS-b-sPHS 表面的磺酸根,並進行共聚合的示意 圖………………………………………………………………………..66 Figure.3-21從TEM下所觀察到[PS-b-sPHS2]= 1.76*10-4M 水溶液所形成的micelle結構:(a1)由≦50nm的micelle聚集成的更大micelle和(a2)此濃度下另一種micelle結構及不規則的micelle聚集;在與0.1M aniline反應(b)5小時;(c)10小時;(d)20小時後的PAni/PS-b-sPHS2微結構。 ………………………………………………………………………….67 Figure.3-22 TEM影像:(a1、a2) PS-b-sPHS2在2.63*10-4M的的水溶液中形成 的micelle;在與0.1M aniline反應 (b) 5小時;(c) 10小時; (d) 20小時所得的複合物結構…………………………………………68 Figure.3-23 [PS-b-sPHS2]= 2.63*10-4M的水溶液與0.1M aniline共聚合得到的 PAni/PS-b-sPHS2的導電度與共聚合時間的關係圖…………...........69 Figure.3-24 PS-b-sPHS2與sPHS的吸收光譜圖…………………………………..70 Figure.3-25 [PS-b-sPHS2]= 2.63*10-4M的水溶液與0.1M aniline在不同聚合時間 得到的PAni/PS-b-sPHS2的UV-Vis吸收光譜……………………......71 Figure.3-26 Aniline在不同濃度的PS-b-sPHS2的水溶液中反應20小時後所得 PAni/PS-b-sPHS2的導電度與PS-b-sPHS2的水溶液濃度的關係圖 …………………………………………………………………………...72 Figure.3-27 Aniline在不同濃度的PS-b-sPHS2的水溶液反應20小時後所得 PAni/PS-b-sPHS2的UV-Vis吸收光譜…………………………………73 表目錄 Table.3- 1六種不同PS-b-sPHS1濃度的水溶液與0.1M aniline反應在不同時間所 得的PAni/PS-b-sPHS1複合物在二次摻雜(Secondary doping)前後的導 電度比較表………………………………………………….....................51 Table.3-2 [PS-b-sPHS2]= 2.63*10-4M的水溶液與0.1M aniline在不同聚合時間得 到的PAni/PS-b-sPHS2的S/N比………………………………………....69 Table.3-3 0.1M aniline在不同濃度的 PS-b-sPHS2水溶液中反應20小時後所得的PAni/PS-b-sPHS2的S/N比……………………………………………… 72 | |
dc.language.iso | zh-TW | |
dc.title | 聚苯胺與團鍊共聚高分子電解質之複合材料研究 | zh_TW |
dc.title | Directing the morphology of polyaniline via in situ polymerization assisted by block polyelectrolytes | en |
dc.type | Thesis | |
dc.date.schoolyear | 96-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 廖文彬,薛景中,戴子安 | |
dc.subject.keyword | 團鍊共聚高分子電解質,聚苯胺,導電高分子,自組裝微結構,模組導引聚合反應,陰離子聚合, | zh_TW |
dc.subject.keyword | block polyelectrolyte,polyaniline(PAni),Conducting polymer,self-assembly,template guided polymerization,anionic polymerization, | en |
dc.relation.page | 79 | |
dc.rights.note | 同意授權(全球公開) | |
dc.date.accepted | 2008-07-29 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 材料科學與工程學研究所 | zh_TW |
顯示於系所單位: | 材料科學與工程學系 |
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