我們成功的利用開環聚合的方式合成三嵌段共聚物Polyethylene-b-Poly(ethylene oxide)-b-Poly(ε-caprolactone)(PE-b-PEO-b-PCL)，並以此為模板結合揮發誘導自組裝(Evaporation Induced Self-assembly, EISA)製備多層次中孔洞二氧化矽。而在鍛燒後我們使用小角度X光散射(SAXS)、穿透式電子顯微鏡(TEM)及比表面積分析儀(BET)進行結構及孔洞分布的解析，並鑑定出在嵌段共聚物中屬於疏水段的PE的結構屬於面心立方(f.c.c.)鑲嵌於同樣是疏水段的PCL所形成的四角管柱(tetragonal cylinder)。另外我們也以改變酸量及PCL分子量的方式來觀察其對於結構規則度和孔洞大小的影響。
另外，我們同樣使用開環聚合的方式合成另一種三嵌段共聚物Poly(ethylene oxide)-b-Poly(ε-caprolactone)-b-Poly(L-lactide)(PEO-b-PCL-b-PLLA)為模板經過交聯固化來製備中孔洞酚醛樹脂，並利用SAXS, TEM進行結構的鑑定及BET分析孔洞的分布，但是因為親疏水段的排列方式的差異，其所形成的結構中只能觀察到六角管柱(hexagonal cylinder)和單一的孔洞尺寸。

ABC type amphiphilic triblock copolymers, polyethylene-b-poly(ethylene oxide)-b-poly (ε-caprolactone) (PE-b-PEO-b-PCL), were synthesized through ring-opening polymerization. We have successfully synthesized hierarchical mesoporous silicas using a simple evaporation-induced self-assembly (EISA) strategy. Two blocks of hydrophobic segment (PE and PCL) in the triblock copolymer (PE-b-PEO-b-PCL) involved in two-type mesepores after calcinations. We recognized the PE segment attributed to face centered cubic (f. c. c.) morphology (spherical pore) and the PCL segment attributed to tetragonal cylinder structure (cylinder pore) by small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and specific surface area & pore size distribution analyzer (BET), respectively. We also investigated the effect on pore size and morphology with changing the molecular weight of PCL and the ratios of TEOS/template/HCl.
We also synthesized the mesoporous phenolic resin by triblock copolymer poly(ethylene oxide)-b-poly(ε-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA). After curing and calcinations, we also explored the morphology and pore size distribution of mesoporous phenolic by SAXS, TEM, BET. Because of the sequence of hydrophobic segment PCL and PLLA lay in the same side, so we could only observe hexagonal cylinder structure and one pore size.

摘要 i
Abstract ii
目錄 iii
表目錄 v
圖目錄 vi
第一章 前言 1
1-1 簡介 1
1-2 研究動機 2
第二章 理論與文獻回顧 4
2-1嵌段共聚物(Block copolymer) 4
2-2 多層次中孔洞材料(Hierarchical Mesoporous Material) 9
2-3 揮發誘導自組裝(Evaporation Induced Self-assembly, EISA) 14
第三章 實驗方法及步驟 17
3-1 實驗內容： 17
3-2 使用藥品： 19
3-3 樣品製備 20
3-4 儀器使用 25
第四章 結果與討論 30
4-1 嵌段共聚物PE-b-PEO-b-PCL之鑑定 30
4-2 多層次中孔洞二氧化矽之結構分析 34
4-3 不同模板及矽源比例製備之中孔洞二氧化矽之分析 38
4-4 各模板固定矽源比例之中孔洞二氧化矽之比較分析 44
4-5 酸量變化對於中孔洞二氧化矽結構影響之分析 48
4-6 中孔洞二氧化矽以穿透式電子顯微鏡(TEM)做角度變換之討論 52
4-7 嵌段共聚物PEO-b-PCL-b-PLLA之鑑定 61
4-8 中孔洞酚醛樹脂微差掃描熱卡儀(DSC)之Tm之分析 63
4-9 中孔洞酚醛樹脂之傅立葉紅外線光譜儀(FT-IR)之分析 65
4-10中孔洞酚醛樹脂之結構分析 66
第五章 結論 73
第六章 參考文獻 74
附錄 77

1. Ciesla, U.; Schuth, F. Micropor. Mesopor. Mater. 1999, 27, 131.
2. Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.; Chu, C. T. W.; Olson, D. H.; Sheppard, E. W.; Higgins, S. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834.
3. Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D. Science 1998, 279, 548.
4. Brinker, C. J.; Lu, Y.; Sellinger, A.; Fan, H Adv. Mater. 1999, 11, 579.
5. Soler-Illia, G. J. A. A.; Crepaldi, E. L.; Grosso, D.; Sanchez, C. Current Opinion in Colloid and Interface Science 2003, 8, 109.
6. Wang, Z. J.; Qu, S. C.; Zeng, X. B.; Zhang, C. S.; Shi, M. J.; Tan, F. R.; Wang, Z. G.; Liu, J. P.; Hou, Y. B.; Teng, F.; Feng, Z. H. Polymer 2007, 48, 2925.
7. 廖美儀 國立成功大學化學研究所碩士論文 2006年
8. Deng, Y. H.; Yu, T.; Wan, Y.; Shi, Y. F.; Meng, Y.; Gu, D.; Zhang, L. J.; Huang, Y.; Liu, C.; Wu, X. J.; Zhao, D. Y. J. Am. Chem. Soc. 2007, 129, 1690.
9. Valvama, S.; Nykanen, A.; Kosonen, H.; Ramani, R.; Tuomisuto, F.; Engelhardt, P.; Brinke, G.; Ikkala, O.; Ruokolainen, J. Adv. Funct. Mater. 2007, 17, 183.
10. Kabanov, A. V.; Batrakova, E. V.; Alakhov, V. Y. J. Controlled Release 2002, 82, 189.
11. Wang, Y. G.; Cheng, L.; Li, F.; Xiong, H. M.; Xia, Y. Y. Chem. Mater. 2007, 19, 2095.
12. Chi, Y. S.; Lin, H. P.; Mou, C. Y. Appl. Catal. A: General 2005, 284, 119.
13. Lee, D.; Lee, J.; Kim, J.; Kim, J.; Na, H. B.; Kim, B.; Shin, C. H.; Kwak, J. H.; Dohnalkova, A.; Grate, J. W.; Hyeon, T.; Kim, H. S. Adv. Mater. 2005, 17, 2828.
14. Zhou, H. S.; Zhu, S. M.; Hibino, M.; Honma, I.; Ichihara, M. Adv. Mater. 2003, 15, 2107.
15. Masten, M. W.; Bate, F. S. Macromolecules 1996, 29,1091.
16. Semenov, A. N. Sov. Phys. JETP 1958, 61, 733.
17. Zheng, Wei; Wang, Z. Macromolecules 1995, 28, 7215.
18. Riess, G.; Schlienger, M.; Marti, S. J.Macromol. Sci.-Phys. Part B 1980, 17, 355.
19. Mogi, Y.; Kotsuji, H.; Kaneko, Y.; Mori, K.; Matsushita, Y.; Noda, I Macromolecules 1992, 25, 5408.
20. Gido, S. P.; Schwark, D. W.; Thomas, E. L. Macromolecules 1993, 26, 2636.
21. Hadjichristidis, N.; Iatrou, H.; Pitsikalis, M.; Pispas, S.; Avgeropoulos, A. Prog. Polym. Sci. 2005, 30, 725.
22. Innocenzi, P.; Malfati, L.; Soler-Illia G. J. A. A. Chem. Mater. 2011, 23, 2501.
23. Sel, O.; Sallard, S.; Brezesinski, T.; Rathousky, J.; Dunphy, D. R.; Collord, A.; Smarsly, B. M. Adv. Funct. Mater. 2007, 17, 3241.
24. Oh, C. G.; Baek, Y.; Ihm, S. K. Adv. Mater. 2005, 17, 270.
25. Fuertes, M. C.; Soler-Illia, G. J. A. A. Chem. Mater. 2006, 18, 2109.
26. Zhang, J.; Deng, Y.; Wei, J.; Sun, Z.; Gu, D.; Bongard, H.; Liu, C.; Wu, H.; Tu, B.; Schuth, F.; Zhao, D. Chem. Mater. 2009, 21, 3996.
27. Raman, N.; Anderson, M.; Brinker, C. Chem. Mater. 1996, 8, 1682.
28. Li, J. G.; Kuo, S. W. RSC Adv. 2011, 1, 1822.
29. Kimura, Y.; Lee, C. W. Bull.Chem. Soc. Jpn. 1996, 69, 1787
30. Huang, Y. Y.; Chen, H. L.; Hashimoto, T. Macromolecules 2003, 36, 764.
31. Chen, H. L.; Lu, J. S.; Yu, C. H.; Yeh, C. L.; Jeng, U. S.; Chen, W. C. Macromolecules 2007, 40, 3271.
32. Chiang, W. S.; Lin, C. H.; Yeh, C. L.; Nandan, B.; Hsu, P. N.; Lin, C. W.; Chen, H. L.; Chen, W. C. Macromolecules 2009, 42, 2304.
33. Sugiyama, M.; Shefelbine, T. A.; Vigild, M. E.; Bates, F. S. J. Phys. Chem. B 2001, 105, 12448.
34. Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Pierotti, R. A.; Rouquerol, J. Siemieniewska, T. Pure Appl. Chem. 1985, 57, 603.
35. Zhang, H.; Bhawagar, D. E.; Graf, J. F.; Painter, P. C.; Coleman, M. M. Polymer 1994, 35, 5379.