我們選擇雙結晶性的嵌段共聚物poly(ethylene oxide)-b-(ε-caprolactone) (PEO-b-PCL)，並使用開環聚合的方式合成，然後和酚醛樹脂(Phenolic resin)做混摻並利用傅立葉紅外線光譜儀(FTIR)分析得知PEO上醚基和酚醛樹脂上羥基間的氫鍵作用力大於PCL上羰基和酚醛樹脂上羥基間的氫鍵作用力。透過微差掃瞄熱卡儀(DSC)熱分析得知PCL會被排除在PEO-酚醛樹脂相之外，且受到侷限。這種效應會形成各種不同的奈米結構，包括不規則、球狀、雙連續相、柱狀結構。這些自組裝的中孔洞結構必須將酚醛樹脂含量控制在40~60 wt%間，並且在酚醛樹脂和PEO及PCL間取得平衡點。另外從小角度Ｘ光散射儀(SAXS)和穿透式電子顯微鏡(TEM)分析得知，中孔洞結構會受到嵌段共聚物內PCL/PEO比例增加而被破壞。最後從高規則度雙連續相結構的中孔洞酚醛樹脂經過氮氣高溫碳化後可獲得高規則度雙連續相結構的碳材。

A series of immiscible crystalline-crystalline diblock copolymers, poly(ethylene oxide)-b-(ε-caprolactone) (PEO-b-PCL), were synthesized through ring-opening polymerization and then blended with phenolic resin. FT-IR analyses provide that the ether group of PEO is a stronger hydrogen bond acceptor than the carbonyl group of PCL with the hydroxyl group of phenolic. Phenolic after curing with hexamethylenetetramine (HMTA) results in the excluded and confined PCL phase based on differential scanning calorimeter (DSC) analyses. This effect leads to the formation of a variety of composition-dependent nanostructures, including disorder, gyroid and short cylinder. The self-organized mesoporous phenolic resin was only found at 40~60 wt% phenolic content by intriguing balance of the contents of phenolic, PEO, and PCL. In addition, the mesoporous structure was destroyed with the increasing the ratio of PCL to PEO in block copolymers by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) analyses. In addition, the large and long-range order of bicontinuous gyroid-type mesoporous carbon was obtained from mesoporous gyroid phenolic resin calcined at 800 °C under nitrogen.

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 ................................................................................................................ 3
第二章 理論與文獻回顧 ................................................................................................ 4
2-1 嵌段共聚物(Block copolymer) ............................................................................. 4
2-2揮發誘導自組裝(Evaporation induced self-assembly, EISA) .............................. 5
2-4 水熱處理(hydrothermal treatment) ....................................................................... 8
2-3 氫鍵作用力(hydrogen bond interaction) .............................................................. 9
2-4 Painter-Coleman Association Model .................................................................... 10
2-5 Novolac type酚醛樹酯及交聯劑六甲烯基四胺 ................................................ 11
第三章 實驗方法及步驟 .............................................................................................. 13
3-1 實驗內容 ............................................................................................................. 13
3-2 使用藥品 ............................................................................................................. 14
3-3 樣品製備 ............................................................................................................. 15
3-3-1 合成嵌段共聚物Poly(ε-caprolactone)-block-Poly(ethylene glycol)及poly(ε-caprolactone)-block-Poly(ethylene glycol) -block- Poly(ε-caprolactone) ... 15
3-3-2 合成Novolac type Phenolic resin ................................................................ 16
3-3-3 合成中孔洞酚醛樹脂及TEM試片製作 .................................................... 16
3-3-4 合成中孔洞二氧化矽 .................................................................................. 17
3.4 儀器使用 ............................................................................................................. 19
iv
3-4-1 氫核磁共振分析儀(Nuclear Magnetic Resonance, NMR)型號：UNITY INOVA-200 ............................................................................................................. 19
3-4-2 傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號：Bruker Tensor-27 ............................................................................................ 20
3-4-3 微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 ................................................................................................................................ 20
3-4-4 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS) 型號：Bruker AXS VANTEC-2000 .............................................................................................. 21
3-4-5穿透式電子顯微鏡(Transmission Electron Microscope,TEM) 型號：JEOL-3010 .............................................................................................................. 21
3-4-6 比表面積分析儀(Specific Surface Area & Pore Size Distribution Analyzer,BET) 型號：ASAP 2020 ....................................................................... 22
第四章 結果與討論 ...................................................................................................... 23
4-1 嵌段共聚物PEO-b-PCL及PCL-b-PEO-b-PCL鑑定 ...................................... 23
4-2 中孔洞酚醛樹脂分析 ......................................................................................... 28
4-2-1中孔洞酚醛樹脂微差掃瞄熱卡儀(DSC)之Tg分析 .................................. 28
4-2-2傅立葉紅外線光譜儀(FTIR)之分析 ............................................................ 32
4-2-3中孔洞酚醛樹脂微差掃瞄熱卡儀(DSC)之Tc分析 ................................... 36
4-2-4中孔洞酚醛樹脂小角度X光散射(SAXS)之分析 ..................................... 38
4-2-5中孔洞酚醛樹脂穿透試電子顯微鏡(TEM)之分析 .................................... 42
4-2-6中孔洞酚醛樹脂比表面積分析儀(BET)之分析 ......................................... 48
4-3中孔洞碳材和中孔洞酚醛樹脂之互相比對及分析 .......................................... 53
4-4 中孔洞二氧化矽分析 ......................................................................................... 57
4-4-1中孔洞二氧化矽小角度X光散射(SAXS)之分析 ..................................... 57
4-4-2中孔洞二氧化矽穿透試電子顯微鏡(TEM)之分析 .................................... 60
4-4-3中孔洞二氧化矽比表面積分析儀(BET)之分析 ......................................... 65
第五章 結論 .................................................................................................................. 67
參考文獻 ........................................................................................................................ 68

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