使用兩種不同的兩性嵌段共聚物Poly(ethylene oxide)-b-(ε-caprolactone) (PEO-b-PCL)和Polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP)作為範本，與帶有羥基Benzoxazine單體(Bzm-OH)做混摻，並升溫固化後移除範本，研究不同重量分率所造成微相分離的相轉換。
利用傅立葉轉換紅外光譜儀(FT-IR)探討混摻不同重量分率下結晶及氫鍵作用力對吸收峰值之影響，分析之後得知PEO上醚基和Benzoxazine單體上羥基間的氫鍵作用力大於PCL上羰基和Benzoxazine單體上羥基間的氫鍵作用力。透過微差掃瞄熱卡儀熱(DSC)分析混摻和交聯後之結晶放熱峰(Tf)及玻璃轉移溫度(Tg)，我們可得知PCL會被排除在PEO / Polybenzoxazine相之外並且受到侷限，這點也可從(FT-IR)上氫鍵的影響得到驗證。
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，原本升溫固化的結構和鍛燒以後的結構不同，故升溫固化的條件，和鍛燒的條件，可得知對Benzoxazine中孔洞結構具有相當程度之影響。根據反應導致微觀相分離(Reaction-Induced Microphase Separation, RIMPS)此法，可成功合成出Benzoxazine中孔洞，且利用PS-b-P4VP此範本，可合成出有序的Benzoxazine中孔洞材料。

A series of immiscible crystalline-crystalline diblock copolymers, poly(ethylene oxide)-b-(ε-caprolactone) (PEO-b-PCL), were blended with (3-phenyl-3,4-dihydro-2H-1,3-benzoxazin-6-yl) methanol (Pa-OH). 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 Pa-OH. Pa-OH after curing results in the excluded and confined PCL phase based on differential scanning calorimeter (DSC) analyses. In addition, the mesoporous structure was proved with the increasing the ratio of PCL to PEO in block copolymers by small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) analyses and N2 adsorption-desorption isotherms (BET)
The poly(styrene-b-4-vinyl pyridine) diblock copolymer was blended with Pa-OH monomer. FT-IR analyses demonstrate the intermolecular hydrogen bonding interaction between the pyridine group of P4VP and the hydroxyl group of Pa-OH. After curing, the block copolymers were incorporated into polybenzoxazine resin to access the nanostructure through the reaction induced microphase separation mechanism by TEM and SAXS analyses.

論文審定書 i
摘要 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 2
第二章 理論與文獻回顧 6
2-1 嵌段共聚物(Block copolymer) 6
2-3 氫鍵作用力(Hydrogen bond interaction) 7
2-3 反應導致微觀相分離(Reaction-Induced Microphase Separation, RIMPS) 7
2-5 Benzoxazine介紹 9
第三章 實驗方法及步驟 11
3-1 實驗內容 11
3-1-1 Poly(ethylene glycol)-block-Poly(ε-caprolactone) 混摻 Benzoxazine單體 (Pa-OH) 11
3-1-1 Polystyrene-block-poly(4-vinylpyridine) 混摻 Benzoxazine單體 (Pa-OH) 12
3-2 使用藥品 13
3-3 樣品製備 14
3-3-1 合成嵌段共聚物Poly(ε-caprolactone)-b-Poly(ethylene glycol) 14
3-3-2 合成嵌段共聚物Poly(styrene)-b-Poly(4-vinyl pyridine) 15
3-3-3 合成Benzoxazine單體( Pa-OH ) 15
3-3-4 利用PEO-b-PCL合成中孔洞Polybenzoxazine並鑑定 16
3-3-5 利用PS-b-P4VP合成中孔洞Polybenzoxazine材料並鑑定 17
3.4 儀器使用 18
3-4-1 氫核磁共振分析儀(Nuclear Magnetic Resonance, NMR)型號：UNITY INOVA-200 18
3-4-2 傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號：Bruker Tensor-27 18
3-4-3 微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 19
3-4-4熱重分析儀(Thermal Gravimetric Analyzer, TGA)型號：TA Q-50 19
3-4-5 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS) 型號：Bruker AXS VANTEC-2000 20
3-4-6穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 型號：JEOL-2100 20
3-4-7 比表面積分析儀(Specific Surface Area & Pore Size Distribution Analyzer,BET) 型號：ASAP 2020 21
第四章 結果與討論 22
4-1利用 PEO-b-PCL製備中孔洞Polybenzoxazine之分析 22
4-1-1 Benzoxazine/PEO-b-PCL微差掃瞄熱卡儀(DSC)之Tg分析 22
4-1-2 Benzoxazine / PEO-b-PCL微差掃瞄熱卡儀(DSC)之Tf分析 25
4-1-3傅立葉轉換紅外線光譜儀(FTIR)之分析 27
4-1-4中孔洞Polybenzoxazine小角度X光散射(SAXS)之分析 29
4-1-5中孔洞Polybenzoxazine穿透式電子顯微鏡(TEM)之分析 32
4-1-5中孔洞Polybenzoxazine比表面積分析儀(BET)之分析 36
4-1-6 Polybenzoxazine/PEO-b-PCL可撓程度分析 39
4-2利用 PS-b-P4VP製備中孔洞Polybenzoxazine之分析 40
4-2-1 Pa-OH/PS-b-P4VP混摻微差掃瞄熱卡儀(DSC)分析 40
4-2-2 Pa-OH/PS-b-P4VP混摻傅立葉轉換紅外光譜FTIR分析 42
4-2-3 Polybenzoxazine /PS-b-P4VP微差掃瞄熱卡儀DSC分析 44
4-2-3 Polybenzoxazine/PS-b-P4VP混摻FTIR分析 45
4-2-4 Polybenzoxazine熱重分析儀 (TGA)之分析 46
4-2-2中孔洞Polybenzoxazine小角度X光散射 (SAXS)之分析 47
4-2-3中孔洞Polybenzoxazine穿透式電子顯微鏡(TEM)之分析 49
4-2-3中孔洞Polybenzoxazine比表面積分析儀之分析 52
4-2-3中孔洞Polybenzoxazine傅立葉轉換紅外光譜儀之分析 53
第五章 結論 55
第六章 參考文獻 57
附錄 61
作者簡介 63

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