燃料電池之質子交換膜應具備有三大優點：1.微相分離、2.機械性質、3.熱穩定性。參考近年來的文獻結構並結合本實驗室長期發展聚芳香醚高分子多苯環核心結構，本論文合成出一系列局部密集型磺酸化聚芳香醚高分子(Locally and Densely sulfonated polymer)。其中，單體部分，本研究係利用多苯環核心作為二醇單體，稱之為K1、K2和K3；另設計一種含CF3官能基的氟單體K4，經親核性聚縮合反應即可得到聚芳香醚高分子，稱之為KP1、KP2、KP3，最後再藉由不同濃度的磺酸化反應，製作出磺酸化高分子，命名為SKP1、SKP2、SKP3。在此，K1、K2和K3部分由於多苯環提供磺酸化位置因此作為親水端，K4部分則做為疏水端。
在分析方面，NMR結果可得知本論文所合成的高分子結構正確無誤，KP1、KP2、KP3的分子量藉由GPC量測都在兩萬左右；TGA結果顯示，高分子的熱裂解溫度皆在530OC以上，證明此系列的高分子熱穩定性極佳，經磺酸化後SKP1、SKP2、SKP3的熱裂解溫度則隨著磺酸化程度增加而下降，約在200OC~250OC不等。由DSC分析可得知，K1、K2和K3單體隨著苯環數上升而Tg跟著上升，但高分子並沒有測到明顯的吸放熱峰。
質子導電度部分，以SKP2C，IEC為2.23 mequiv / g 、 吸水率為94%時質子導電度68.2 mS / cm為最佳，已與Nafion 117的70 mS / cm相近。

The proton exchange membrane fuel cells should have three major advantages: 1. micro-phase separation, 2. mechanical properties and 3. thermal stability. According to the recent literature and the material of core benzene ring poly (arylene ether)s studied by our group, this paper synthesize a series of the locally and densely sulfonated polymer. We use core benzene ring as the diol monomer and the containing CF3 groups as the fluorine monomer to synthesis poly (arylene ether)s via nucleophilic displacement reactions, and then use the different concentrations synthesized sulfonated polymer by sulfonic acid reaction.
According to NMR’s result we confirmed that the structure of synthetic materials is correct. By using GPC we get that the KP1, KP2, and KP3’s molecular weight about 20000 (g/mol) ; The thermal stability up to 530OC for 5% loss in TGA under nithtrogen, to prove thisseries of polymer excellent thermal stability. After sulfonation, SKP1, SKP2 and SKP3’s decomposition temperature decreased about 200OC ~ 250OC ranging with increasing degree of sulfonation. By DSC analysis, K1, K2 and K3 monomer's Tg followed up with the increase of the benzene ring number, however, the polymer does not have any apparent peak.
About the Proton conductive, SKP2C IEC 2.23mequiv / g, water uptake 94%, the highest proton conductivity can be as high as 68.2 mS / cm, has been similar to Nafion 117 of 70 mS / cm.

摘要 i
目錄 iii
圖目錄 vi
表目錄 vii
第一章 序論 1
1-1前言 1
1-2燃料電池種類 1
1-3質子交換膜燃料電池 3
1-3-2質子傳遞機制 4
1-4質子交換膜種類 6
1-4-1 離子聚合物薄膜(Ionomer membrane) 6
1-4-2 有機/無機混成薄膜 10
1-4-3 酸鹼高分子薄膜 11
1-5 質子交換膜結構的設計 (Polymer Architectures of Proton Exchange Membrane ) 13
1-6 局部密集磺酸化聚芳香醚高分子文獻回顧 17
1-7 研究動機 19
第二章 實驗儀器介紹與原理 20
2-1鑑定分析儀器 20
2-1-1高磁場液態磁核共振儀器(Nuclear Magnetic Resonance，NMR) 20
2-1-2基質輔助雷射脫附游離飛行質譜儀(MALDI TOF/TOF) 20
2-1-3凝膠滲透層析儀(GPC) 21
2-2熱分析儀器 21
2-2-1 熱重量分析儀(Thermogravimetric Analyzer，TGA) 21
2-2-2 熱示差掃描卡量計(Differential Scanning Calorimetr，DSC) 21
2-2-3 熱機械分析儀(Thermal Mechanical Analyzer，TMA) 22
2-3 物理分析 22
2-3-1 尺寸安定性(Dimensional change) 22
2-3-2 吸水率(Water uptake，WU) 22
2-4 化學分析 22
2-4-1 離子交換容量(Ionic-exchange capacity，IEC) 22
2-4-2 λ(每個磺酸根含有多少水分子數量) 23
2-5 微觀分析 23
2-5-1 Transmission Electron Microscope(TEM) 23
2-6 電化學分析 23
2-6-1 AC Impedance 23
第三章 實驗 25
3-1實驗材料 25
3-2實驗流程 27
3-3雙酚單體製備與鑑定 30
3-4氟單體製備與鑑定 36
3-5高分子製備 37
3-6磺酸化高分子製備 39
3-7薄膜製備 40
第四章 結果與討論 41
4-1 鑑定分析 41
4-1-1 GPC 41
4-2 材料熱分析 42
4-2-1 TGA 42
4-2-2 DSC 45
4-3 物理、化學性質分析 47
第五章 結論 50
第六章 參考文獻 51
附錄 56

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