本論文主要係以本實驗室自行合成的多苯環單體搭配市售bis(4-fluorophenyl) Sulfone、4,4'-(hexafluoroisopropylidene)diphenol製備一系列具有高立體障礙性的磺酸化無規共聚聚芳香醚高分子。使用GPC, TGA, TMA等儀器量測並探討其特性，以及磺化之後應用於燃料電池質子交換膜之評估。
根據本實驗室之研究，磺化聚芳香醚高分子，由於多苯環的剛性結構可以提供良好的機械性質以及化學穩定性，而經由磺化之後，在高溫高濕下可以擁有良好的導電度，並維持優秀的機械性質與熱穩定性。具有取代商業化主流材料Nafion的潛力。
而本系列高分子分子量均在七萬以上，磺化後的IEC值介於1.36至2.02mmol./g之間；楊氏模數則在0.5GPa以上，機械性質比Nafion更加優異；熱裂解溫度(Td5%)則高於269℃；導電度的部分在80℃，RH 95%條件下ha-60s與ha-70s的導電度分別來到了178.4mS/cm及173.7mS/cm，皆大於Nafion 211，展現出本系列薄膜優異的質子傳導能力，並且極具發展潛力。

The master's thesis research is about synthesis fluorine-containing random poly(arylene ether)s copolymer by the multi-benzene monomer synthesized by ourselves going with commercially available bis(4-fluorophenyl) Sulfone and 4,4'-(hexafluoroisopropylidene)diphenol monomer. We use GPC, TGA, TMA and other instruments to measure and explore its properties, as well as the assessment of fuel cell proton exchange membrane.
According to the research, the sulfonated poly(arylene ether)s polymers can provide good mechanical properties and chemical stability due to the multi-benzene structure and have a good conductivity at high temperature and humidity.
This series of polymer molecular weighs more than 70,000, IEC values range from 1.36 to 2.02mmol/g； Young's modulus are all above 0.5GPa, which lead to better mechanical properties than Nafion. Moreover, pyrolysis temperature (Td5%) is higher than 269 oC; proton conductivity of ha-60s and ha-70s comes to 178.4mS / cm and 173.7mS / cm at 80 oC, RH 95%, which are greater than Nafion 211. This series of films shows excellent proton conductivity and great potential for development.

論文審定書 i
誌謝 ii
中文摘要 iii
英文摘要 iv
第一章 緒論 1
1.1前言 1
1.2燃料電池種類與介紹 1
1.3質子交換膜工作原理 4
1.4質子交換膜種類 8
1.5質子交換膜結構的設計 11
1.6文獻回顧 13
1.7研究動機 18
第二章 實驗儀器及原理 20
2.1鑑定分析儀器 20
2-1-1高磁場液態磁殼共振儀器(Nuclear Magnetic Resonance，NMR) 20
2-1-2凝膠滲透層分儀(Gel Permeation Chromatography，GPC) 20
2.2熱分析儀器 22
2-2-1熱重量分析儀(Thermogravimetric Analyzer，TGA) 22
2-2-2熱機械分析儀(Thermal Mechanical Analyzer，TMA) 23
2.3物理分析 24
2-3-1尺寸安定性(Dimensional change) 24
2-3-2吸水率(Water Uptake，WU) 24
2.4化學分析 24
2-4-1離子交換容量(Ionic-exchange capacity，IEC) 24
2-4-2 λ(每個磺酸根含有多少水分子量) 25
2.5微觀分析 25
2-5-1穿透式電子顯微鏡(TEM) 25
2.6電化學分析 26
2-6-1 AC Impedance 26
第三章 實驗 28
3.1實驗材料 28
3.2實驗流程圖 30
3.3雙氟單體製備與鑑定 31
3.4高分子聚合 33
3.5高分子磺酸化 34
3.6磺化高分子成膜、後處理 35
第四章 結果與討論 36
4.1未磺酸化高分子分析 36
4-1-1 GPC分析 36
4-1-2 1H NMR分析 37
4-1-3 4-1-3 FTIR分析 41
4-1-4 TGA分析 46
4-1-5 TMA分析 47
4.2磺酸化高分子分析 49
4-2-1 IEC 49
4-2-2 TGA分析 50
4-2-3 TMA分析 51
4-2-4吸水率、λ值、尺寸安定性 53
4-2-5氧化、水解穩定性 57
4-2-6質子導電度 58
4-2-7微相分離型態(TEM) 59
4-2-8 燃料電池元件分析 59
第五章 結論 62
第六章 參考文獻 64
附錄 66

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