質子交換膜燃料電池為目前推動綠能產業主要項目之一，其功率密度高、體積小、重量輕的優點為我們所看重。而現今主要的質子交換膜材料（Nafion）其缺點為無法在高溫環境下操作，而且受限於成本過高。因此本研究以低價位的雙氟單體Decafluorobiphenyl經由親核性(Nucleophilic)取代反應與高立體結構性二苯酚(Bisphenol)單體產生聚合反應產生高功能聚芳香醚高分子從聚芳香醚高分子的熱穩定性測量中可知，其劣解溫度(Td> 500°C），而玻璃轉移溫度(Tg)為225∼250°C，顯示聚芳香醚高分子擁有很好的熱穩定性。因此我們對於這些高性能聚芳香醚高分子以Chlorosulfonic acid進行磺酸化形成高分子電解質作為燃料電池的質子交換膜。
經過各項分析，FTIR光譜顯示我們成功地以Chlorosulfonic acid將高性能聚芳香醚高分子磺酸化，並由熱重分析儀（TGA）測得良好的熱穩定性(Td≈ 500°C)，而且以0.15M磺酸化的s(DFB+M3)高分子其低溫(25℃)高濕(77%)下質子導電度（約10-6∼10-7S cm-1）於商業化的Nafion117（約3.0x10-3S cm-1）相差甚遠，由於我們在磺酸化條件尚未達到最佳化，而量測環境濕度的條件也可再改進，未來提昇質子導電度的可能性還是存在。

PEM (Proton Exchange Membrane) fuel cell is one of the most important green energy, because it has high energy density, lifetime, small and light.etc advantages. Nafion , the major material for PEM now, However, has some disadvantages such as high cost ($600–1000/m2) and limited choices for operation temperature about 25℃~80℃. Consequently, there is an increasing interest in the development of alternative ionomer membranes with lower cost, and higher proton conductivity, and that are more easily processed. Here we present polymeric membranes made of sulfonic Poly(arylene ether)s (PAEs) which is achieved by nucleophilic displacement reactions of dihalo or dinitro compounds with alkali metal bisphenolates and direct polymer sulfonation was carried out in heterogeneous media using chlorosulfonic acid as both solvent and sulfonating agent. In our PAEs which has high Tg values about 225∼250°C depends on the barriers to rotation along the main polymer chain. And weight losses above 500 °C by thermogravimetric (TGA) analysis, indicative of their high thermal stability.
After FTIR analysis we preparation sulfonated polymer successfully by using chlorosulfonic acid as sulfonating agent. Thermogravimetric analysis (TGA) studies were carried out to investigate the thermal stability of sulfonated PAEs (Td≈ 500°C). The proton conductivity of polymer s(DFB+M3) sulfonated with chlorosulfonic acid about 10-6∼10-7S cm-1 .Compared with Nafion membrane measured in the same condition, the conductivity of our membrane is smaller than 3~4 order. In the future, it is possible to improve the conductivity of our membrane with optimization.

致謝 I
中文摘要 IV
Abstract V
目錄 VI
圖目錄 VIII
表目錄 X
第一章 緒論1
1.1前言1
1.2燃料電池 2
1.2.1燃料電池種類 2
1.2.2質子交換膜燃料電池工作原理 4
1.3質子交換膜現況發展 5
1.4 研究動機 7
第二章 實驗 11
2.1 氟單體製備流程圖 11
2.2 氟單體合成與鑑定 12
2.2.1 1,3-Bis(p- bromophenyl)-2-propanone12
2.2.2 2,5-Bis(4-bromophenyl)-3,4-diphenylcyclopenta- 2,4-dienon 13
2.2.3 4,4-Dibromo-2,3-diphenyl-[1,1; 4,1]-terphenyl 14
2.2.4 4-Fluoro-3trifluoromethylphenylboronic acid 15
2.2.5 4,4’’’’-Difluoro-3,3’’’’-bistrifluoromethyl-2’’,3’’,5’’,6’’-tetraphenyl-[1,1’;4’,1’’;4’’,1’’’;4’’’,1’’’’]-pentaphenyl 17
2.2.6 氟單體各步驟產物、1H-NMR圖譜結構鑑定 19
2.3 高分子聚合和結構鑑定 28
2.4 高分子磺酸化 29
2.5薄膜的製備 30
第三章 結果與討論 32
3.1高分子物理性質分析 32
3.1.1 溶解度(Solubility)測試 32
3.1.2 傅立葉轉換紅外光譜儀(FTIR)結構鑑定 36
3.2高分子熱穩定性分析 39
3.2.1 熱重分析儀(TGA) 39
3.2.2 示差掃描熱量分析儀(DSC) 42
3.3磺酸化高分子質子導電度分析(AC Impedence) 43
第四章 結論 48
參考文獻 49

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