本研究利用開環聚合的方式，將市售三嵌段共聚物Pluronic F127 (EO106-b-PO70-b-EO106)兩端接上PCL [poly(ε-caprolactone)]，合成多嵌段共聚物poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(propyleneoxide)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) (PCL-b-PEO-b-PPO-b-PEO-b-PCL)，並以此為模板，結合揮發誘導自組方法(Evaporation Induced Self-assembly, EISA)製備出中孔洞二氧化矽。由於PCL和F127鏈段上的PPO性質相近，因此在自組裝時PCL鏈段會將高分子鏈段尾端拉回至靠近同為疏水端的PPO鏈段 (m形摺疊) ，但由於PPO不夠疏水，在高矽源量下，部份PPO鏈段會被二氧化矽(silica)包住。在以F127為模板製備中孔洞二氧化矽方面，隨著矽源量愈多，結構從六角柱狀轉變為體心立方堆積 (body-centered cubic, bcc) 再轉變為球狀微胞，孔洞也明顯的變小許多；將F127兩端接上較短的PCL鏈段後，孔洞因為PCL鏈段將高分子鏈段尾端拉回而變小，隨著矽源量愈多，部份PPO鏈段會被二氧化矽包住，結構規則度變差；將F127兩端接上較長的PCL鏈段後，較長的PCL鏈段佔據的體積太大，一開始就將孔洞撐大並阻礙silica包住親水端的能力，導致孔洞變大且變化幅度更小，結構規則度也變差。

　　另外，本研究將F127與Novolac型酚醛樹脂混掺，經過交聯固化來製備中孔洞酚醛樹脂，由FT-IR可知，PEO和PPO的C-O-C基皆會和酚醛樹脂的O-H基產生氫鍵，且PEO形成氫鍵能力較PPO強。不同的酚醛樹脂/F127組成會因為反應導致微觀相分離機制而產生無序蟲狀、體心立方堆積、無序微胞等結構，當酚醛樹脂/F127在比例為50/50時有規則的體心立方堆積結構。

ABCBA type amphiphilic multiblock copolymers, poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(propyleneoxide)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) (PCL-b-PEO-b-PPO-b-PEO-b-PCL), were synthesized through ring-opening polymerization. Mesoporous silicas have been successfully fabricated via evaporation-induced self-assembly (EISA) strategy. Structures of mesoporous silicas templated by Pluronic F127 would transform from cylinder to body-centered cubic (bcc) and finally to disordered sphere and the pore size becomes smaller obviously with increasing of TEOS-to-F127 weight ratios. The assembled structures of the molecular were like “m” shape. The PEO segments of PCL-F127-PCL folded outside, and the PCL segments and PPO segment aggregated inside. Because PPO segment is not hydrophobic enough, it has a weak interaction with silica area. Mesoporous silica samples templated from CL12EO106PO70EO106CL12 (CFC1) or CL45EO106PO70EO106CL45 (CFC2) behaved with less regular arrangement.

　　When blending F127 triblock copolymer with Novolac-type phenolic resin, FT-IR spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen-bond acceptors for the OH group of phenolic resin than the ether groups of the PPO block. Thermal curing resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-center cubic spherical, disorder micelle. The mesoporous phenolic resins as long range order bcc structure were formed only when the phenolic content was 50 wt%.

論文審定書 i
誌謝 ii
摘要 iv
Abstract v
目錄 vi
表目錄 ix
圖目錄 x
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 氫鍵作用力(Hydrogen bond interaction) 6
2-3 反應導致微觀相分離(Reaction-Induced Microphase Separation, RIMPS) 6
2-4 揮發誘導自組裝(Evaporation Induced Self-assembly, EISA) 7
2-5 水熱處理(hydrothermal treatment) 10
2-6 Novolac型酚醛樹酯及交聯劑六甲烯基四胺 10
第三章 實驗方法及步驟 12
3-1 實驗內容 12
3-1-1　F127, PCL-b-F127-b-PCL 混摻 TEOS 12
3-1-2 F127 混摻 Novolac型酚醛樹酯 13
3-2 使用藥品 14
3-3 樣品製備 15
3-3-1 合成多嵌段共聚物poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-b-poly(ε-capro lactone) 15
3-3-2 合成Novolac型酚醛樹酯 16
3-3-3 合成中孔洞二氧化矽及TEM試片之製作 16
3-3-4 合成中孔洞酚醛樹脂及TEM試片製作 17
3.4 儀器使用 18
3-4-1 膠體滲透層析儀(Gel Permeation Chromatography, GPC) 型號：Jasco PU-980 18
3-4-2 氫核磁共振分析儀(Nuclear Magnetic Resonance, NMR)型號：UNITY INOVA-200 19
3-4-3熱重分析儀(Thermal Gravimetric Analyzer, TGA)型號：TA Q-50 20
3-4-4 微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 20
3-4-5 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS) 型號：NSRRC BL23A 21
3-4-6 廣角度Ｘ光繞射儀(Wide Angle X-ray Diffraction, WAXD) 型號：NSRRC BL17A 21
3-4-7 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 型號：JEOL-3010 22
3-4-8 比表面積分析儀(Specific Surface Area & Pore Size Distribution Analyzer, BET) 型號：ASAP2020 22
3-4-9 傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號：Bruker Tensor-27 23
第四章 結果與討論 24
4-1 嵌段共聚物PCL-b-F127-b-PCL之鑑定 24
4-2 以F127為模板製備體心立方堆積之中孔洞二氧化矽之分析 26
4-3 不同模板及矽源比例製備之中孔洞二氧化矽之分析 28
4-3-1 以F127為模板製備中孔洞二氧化矽之分析 29
4-3-2 以CFC1為模板製備中孔洞二氧化矽之分析 33
4-3-3 以CFC2為模板製備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 43
4-5 以F127為模板製備體心立方堆積之中孔洞酚醛樹脂之分析 50
4-6 以F127為模板製備之中孔洞酚醛樹脂之分析 52
4-6-1 酚醛樹脂混掺F127之微差掃瞄熱卡儀 (DSC) 分析 52
4-6-2 酚醛樹脂混掺F127之傅立葉紅外線光譜儀 (FT-IR) 分析 54
4-6-3 中孔洞酚醛樹脂之微差掃瞄熱卡儀 (DSC) 分析 55
4-6-4 中孔洞酚醛樹脂之熱重分析儀 (TGA) 分析 57
4-6-5 中孔洞酚醛樹脂之小角度X光散射 (SAXS) 分析 58
4-6-3中孔洞酚醛樹脂之穿透式電子顯微鏡 (TEM) 分析 59
4-6-4中孔洞酚醛樹脂之比表面積分析儀 (BET) 分析 62
第五章 結論 64
第七章 參考文獻 65

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