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博碩士論文 etd-0623118-142201 詳細資訊
Title page for etd-0623118-142201
論文名稱
Title
調控氫鍵作用力於嵌段共聚物混摻系統之自組裝結構
Utilizing Hydrogen-Bonding Interactions to Manipulate Self-assembly Structures of Block Copolymer Blends
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
82
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2018-07-06
繳交日期
Date of Submission
2018-07-23
關鍵字
Keywords
嵌段共聚物、混摻、多層次結構、自組裝、氫鍵
hierarchical structure, hydrogen bonding, self-assembly, blend, block copolymers
統計
Statistics
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中文摘要
本研究分為兩個部分,第一部分將利用poly(styrene-b-vinyl phenol)嵌段共聚物(PS-b-PVPh)個別與poly(ethylene oxide) (PEO)均聚物及poly(ethylene oxide-b-4-vinyl pyridine) (PEO-b-P4VP)嵌段共聚物進行混摻,來探討不同氫鍵強度對兩個混摻系統帶來之影響。我們使用了傅立葉紅外線光譜儀(FT-IR)、微差掃描熱卡儀(DSC)、穿透式電子顯微鏡(TEM)及小角度X光散射(SAXS)來分析PS-b-PVPh/PEO與PS-b-PVPh /PEO-b-P4VP混摻系統,探討系統於固態下各鏈段間相容性及藉由調控氫鍵作用力對系統自組裝之行為。在PS-b-PVPh/PEO混摻系統中,當開始混入均聚物時,由於氫鍵作用密度增加使得系統相容性提升,並可將自組裝結構從層板結構轉換為不規則的柱狀結構,且當混摻高比例的均聚物時,可以觀察到均聚物的結晶產生;在PS-b-PVPh/PEO-b-P4VP混摻系統中,PVPh與P4VP因產生較強的氫鍵作用力而形成一相,且PEO與PS又不相容而各自成相,我們可藉由調控氫鍵作用力得到特殊之多層次結構。本研究之第二部分,將利用polystyrene-block-poly(4-vinylpyridine)嵌段共聚物(PS-b-P4VP)與poly-(vinyl phenol-block-methyl methacrylate)嵌段共聚物(PVPh-b-PMMA)進行混摻,來探討不同合成比例之PVPh-b-PMMA在與PS-b-P4VP形成氫鍵後是如何誘導其自組裝結構發生轉變,我們藉由調控不同氫鍵作用比例來增加極性鏈段間的體積分率,並將結構從雙連續螺旋結構相轉換為層板及圓柱最後轉變成蟲狀結構,本研究首度利用氫鍵作用力將不互溶的嵌段共聚物A-b-B混摻互溶的嵌段共聚物C-b-D,並且透過高分子之自組裝成功獲得三相的多層次結構。
Abstract
In this study we investigated the hydrogen bonding strength and self-assembly supramolecular nanostructures of the poly(styrene-b-vinyl phenol) (PS-b-PVPh) diblock copolymer when blending with homopolymer poly(ethylene oxide) (PEO) and diblock copolymer poly(ethylene oxide-b-4-vinyl pyridine) (PEO-b-P4VP). In PS-b-PVPh/PEO blend, the system exhibited morphological transition from lamellae to cylindrical structures at the lower homopolymer concentrations and we also observed the crystallization of PEO when increasing concentrations of homopolymer, and in PS-b-PVPh/PEO-b-P4VP blending system, PVPh/P4VP have more strongly hydrogen bonding than PVPh/PEO so that the mixture possessed three phases including P4VP/PVPh, PEO, and PS domains, finally we can obtain the three phase structure such as core-shell cylindrical structure. Furthermore, the PS-b-P4VP/PVPh-b-PMMA blend underwent an order-order morphological transition from bicontinuous gyroid structure to lamellar to cylindrical to worm-like structures. This is the first study by using the immiscible A-b-B diblock copolymer blending with miscible C-b-D diblock copolymer through competitive hydrogen bonding interactions to form the hierarchical self-assembly nanostructures such as three-phase lamellar or core-shell cylindrical nanostructures.
目次 Table of Contents
論文審定書 i
誌謝 ii
摘要 iv
Abstract v
主目錄 vii
圖目錄 x
第一章 緒論 1
1-1 前言 1
1-2 研究動機 2
1-3 文獻回顧 4
1-3-1 活性陰離子聚合 4
1-3-2 氫鍵混摻系統原理 7
1-3-3 嵌段共聚物之自組裝行為 8
1-3-4 多層次結構 10
第二章 實驗方法 12
2-1 實驗內容及流程 12
2-2 實驗藥品 14
2-3 實驗步驟 15
2-3-1.1 合成poly(styrene-b-tert butoxystyrene) 15
2-3-1.2 合成poly(styrene-b-vinyl phenol) 15
2-3-1.3 合成poly(ethylene oxide-b-4-vinyl pyridine) 15
2-3-1.4 混摻PS-b-PVPh/PEO and PEO-b-P4VP(Polymer blend) 16
2-3-2.1 合成poly(styrene-b-4-vinyl pyridine) 17
2-3-2.2 合成poly(4-tert-butoxystyrene-b-methyl methacrylate) 17
2-3-2.3 合成poly(vinyl phenol-b-methyl methacrylate) 18
2-3-2.4 混摻PS-b-P4VP/PVPh-b-PMMA (Polymer blend) 18
2-4 儀器介紹 19
2-4-1 傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號:Bruker Tensor-27 19
2-4-2 核磁共振分析儀 (Nuclear Magnetic Resonance, NMR)
型號:Varian Unity Inova-500 20
2-4-3 凝膠滲透層析儀(Gel Permeation Chromatography, GPC)
型號:Jasco PU-980 21
2-4-4微差掃描熱卡儀(Differential Scanning Calorimeter, DSC)
型號:TA Q-20 22
2-4-5 小角度X光散射儀(Small Angle X-ray Scattering, SAXS)
型號:Bruker AXS VANTEC-2000 23
2-4-6 穿透式電子顯微鏡(Transmission Electron Microscope, TEM)
型號:JEOL-2100 23
第三章 結果與討論 24
3-1 PS-b-PVPh/PEO及PS-b-PVPh/PEO-b-P4VP混摻系統之分析 24
3-1-1.1 PS-b-PtBuOS、PS-b-PVPh之合成鑑定 24
3-1-1.2 PEO-b-P4VP之合成鑑定 27
3-1-2 PS-b-PVPh混摻系統之熱性質分析 30
3-1-3 PS-b-PVPh混摻系統之紅外線光譜分析 33
3-1-4 PS-b-PVPh混摻系統之自組裝結構分析 36
3-2 PS-b-P4VP/PVPh-b-PMMA混摻系統之分析 43
3-2-1.1 PS-b-P4VP之合成鑑定 43
3-2-1.2 PtBuOS-b-PMMA、PVPh-b-PMMA之合成鑑定 45
3-2-2 PS-b-P4VP混摻系統之熱性質分析 48
3-2-3 PS-b-P4VP混摻系統之紅外線光譜分析 49
3-2-4 PS-b-P4VP混摻系統之自組裝結構分析 54
第四章 結論 63
第五章 參考文獻 64
第六章 附件 67
參考文獻 References
1. Kuo, S. W., Polym. Int., 2009, 58, 455.
2. Hameed, N.; Guo, Q., Polymer, 2008, 49, 5268.
3. Zhao, J. Q.; Pearce, E. M.; Kwei, T. K., Macromolecules, 1997, 30, 7119.
4. Chen, S. C.; Kuo, S. W.; Jeng, U. S.; Su, C. J.; Chang, F. C., Macromolecules, 2010, 43, 1083.
5. Tsai, S. C.; Lin, Y. C.; Lin, E. L.; Chiang, Y. W.; Kuo, S. W., Polym. Chem., 2016, 7, 2395.
6. Lin, C. L.; Chen, W. C.; Liao, C. S.; Su, Y. C.; Huang, C. F.; Kuo, S. W.; Chang, F. C., Macromolecules, 2005, 38, 6435.
7. Chen, W. C.; Kuo, S. W.; Jeng, U. S.; Chang, F. C., Macromolecules, 2008, 41, 1401.
8. Ziegler, K.; Jacov, L.; Wollthan, H.; Wenz, A., Ann. Chem., 1934, 511, 64.
9. Szwarc, M., Nature, 1956, 178, 1168.
10. Bauer, B. J.; Fetters, L. J., Rubber Chem. Technol., 1978, 51, 406.
11. Graessley, W. W., Acc. Chem. Res., 1977, 10, 332.
12. Grest, G. S.; Fetters, L. J.; Huang, J. S., Adv. Chem. Phys., 1996, 44, 67.
13. Milner, S. T., Macromolecules, 1994, 27, 2333.
14. Tseng, H. W.; Juan, H. F.; Huang, H. C.; Lin, J. Y., Proteomics, 2006, 22, 5915.
15. Kim, J. K.; Jang, J.; Lee, D. H.; Ryu, D. Y., Macromolecules, 2004, 37, 8599.
16. Robinson, C.; Ward, J. C., Nature, 1957, 180, 1183.
17. Coleman, M. M.; Painter, P. C., Prog. Polym. Sci., 1995, 20, 1.
18. He, Y.; Zhu, B.; Inoue, Y., Prog. Polym. Sci., 2004, 29, 1021.
19. Kuo, S. W., J. Polym. Res., 2008, 15, 459.
20. Kuo, S. W.; Huang, C. F.; Tung, P. H.; Huang, W. J.; Huang, J. M.; Chang, F. C., Polymer, 2005, 46, 9438.
21. Kuo, S. W.; Huang, W. J.; Huang, C. F.; Chan, S. C.; Chang, F. C., Macromolecules, 2004, 37, 4164.
22. Jeon, H. K.; Kim, J. K., Macromolecules, 2000, 33, 8200.
23. Kuo, S. W.; Chang, F. C., Macromolecules, 2001, 34, 5224.
24. Chen, D.; Jiang, M., Acc. Chem. Res., 2005, 38, 494.
25. Yi, J. Z.; Goh, S. H.; Wee, A. T. S., Macromolecules, 2001, 34, 4662.
26. Masten, M. W.; Bate, F. S., Macromolecules, 1996, 29, 1091.
27. Semenov, A. N., Sov. Phys. JETP, 1958, 61, 733.
28. Riess, G., Prog. Polym. Sci., 2003, 28, 1107.
29. Hadjichristidis, N.; Iatrou, H.; Pitsikalis, M.; Pispas, S.; Avgeropoulos, A., Prog. Polym. Sci., 2005, 30, 725.
30. Asari, T.; Matsuo, S.; Takano, A.; Matsushita, Y., Macromolecules, 2005, 38, 8811.
31. Asari, T.; Arai, S.; Takano, A.; Matsushita, Y., Macromolecules, 2006, 39, 2232.
32. Li, M.; Douki, K.; Goto, K.; Li, X.; Coenjarts, C.; Smilgies, D. M.; Ober, C. K., Chem. Matter., 2004, 16, 3800.
33. Isasi, J. R.; Cesteros, L. C.; Katime, I., Macromolecules, 1994, 27, 2200.
34. Kuo, S. W.; Liu, W. P.; Chang, F. C., Macromolecules, 2003, 36, 5165.
35. Chinthamanipeta, P. S.; Kobukata, S.; Nakata, H.; Shipp, D. A., Polymer, 2008, 49, 5636.
36. Wei, Z.; Hao, X.; Kambouris, P. A.; Gan, Z.; Hughes, T. C., Polymer, 2012, 53, 1429.
37. Zheng, G.; Pan, C., Macromolecules, 2006, 39, 95.
38. Topuzogullari, M.; Bulmus, V.; Dalgakiran, E.; Dincer, S., Polymer, 2014, 55, 525.
39. Kuo, S. W.; Tung, P. H.; Chang, F. C., Macromolecules, 2006, 39, 9388.
40. Kuo, S. W.; Liu, W. P.; Chang, F. C., Macromol. Chem. Phys., 2005, 206, 2307.
41. Salim, N. V.; Hanley, T.; Guo, Q., Macromolecules, 2010, 43, 7695.
42. Yeh, C. L.; Hou, T.; Chen, H. L.; Yeh, L. Y.; Chiu, F. C.; Müller, A. J.; Hadjichristidis, N., Macromolecules, 2011, 44, 440.
43. Chiang, Y. W.; Hu, Y. Y.; Li, J. N.; Huang, S. H.; Kuo, S. W., Macromolecules, 2015, 48, 8526.
44. Yu, C. Y.; Kuo, S. W., Ind. Eng. Chem. Res., 2018, 57, 2546.
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