本論文以多苯環為核心，製備含氟的雙氟單體並分別與實驗室發展的三種雙酚單體 (9-phenyl type、8-phenyl type、7-phenyl type)材料，經親核性聚縮合反應得到三種交替型含氟碳氫性離子高分子(FA series)。調配高(H)、中(M)、低(L)不同濃度的磺酸化試劑，在溫和的條件下進行後磺酸化反應，得到九種不同微相分離型態的局部密集磺酸化高分子，IEC值介於1.28-2.47mmol/g之間，並以sFA series命名。藉由在雙氟單體的多苯環結構上導入具有強拉電子CF3官能基，因而不受到磺酸化反應的影響，使磺酸根集中在雙酚單體的多苯環結構上。
透過FT-IR鑑定材料的官能基及1H -NMR鑑定結構無誤，GPC量測三種未磺酸化高分子之重量平均分子量介於7.80×104-1.08×105 g/mol之間，高分子的熱裂解溫度(Td5%)則在584oC以上。九種磺酸化高分子的Td5%皆高於260oC以上，顯示主鏈具有不錯的熱穩定性。在高溫、高濕的狀態下，薄膜具有相當優異的尺寸安定性(0-13%)及機械性質(拉伸強度：41.7-105MPa)，使薄膜皆不易膨潤且水溶，而中、高磺酸化程度的薄膜吸水率在低溫高濕環境下皆高於Nafion的20%，說明此系列材料具有不錯的保水能力，並以sFA9-H及sFA9-M擁有與Nafion 117(0.074S/cm)相當的質子導電度，0.069S/cm及0.061S/cm。綜合上述，本論文認為在碳氫性離子高分子導入適量的含氟官能基，能改善磺酸化碳氫離子性高分子的特性，因此sFA series材料有做為質子交換膜燃料電池的潛力。

Three different bisphenol monomers (9-phenyls, 8-phenyls and 7-phenyls) containing multiple phenyl substituents on the middle triphenylene moiety have been synthesized in this thesis. Through reacting with the fluorine-containing bisfluoro monomer, three bisphenol monomers were converted into a series of alternating fluorine-containing hydrocarbon ionic polymers (FA series) by nucleophilic displacement of the fluorine atoms on the terminal benzene ring of bisfluoro monomers. The obtained polymers were sulfonated in different reagent concentrations under mild condition to control the degree of sulfonation (high, medium and low). Owing to locally and densely sulfonic acid substituent design, the 9 sulfonated polymers show well defined phase separations with IEC values between 1.28 and 2.47 mmole/g, named "sFA series". Introducing trifluoromethyl group on multi-core benzene of bisfluoride makes sulfonated groups graft on bisphenol monomer and preventing to be sulfonated due to trifluoromethyl group owing powerful electron-withdrawing effect.
The obtained polymers exhibit the average molecular weight ranging from 7.80×104 to 1.08×105g/mol in GPC. The chemical structures of polymers were characterized and confirmed by FT-IR and NMR measurements. The polymers show thermal degradation temperatures up to 260oC which indicates good thermal stability. At high temperature and high humidity environments, the sulfonated polymer membranes show excellent dimensional stabilities (0-13%) and mechanical properties (tensile strength:41.7-105 MPa), making the membranes not swollen or soluble in water. All the water uptakes of sulfonated polymers with high or middle degree of sulfonation are higher than 20%, which are comparable to Nafion’s. This confirms that these sulfonated polymers well preserve water in the films and subsequently good proton conductivities with 0.069S/cm and 0.061S/cm for sFA9-H and sFA9-M, which are comparable to Nafion 117. On the basis of above results, we believe introducing trifluoromethyl group on phenyl substituents can improve ionic conductivity of hydrocarbon ionomers and this validates sFA series have a good potential in PEMFC application.

論文審定書 i
誌謝 ii
中文摘要 iii
英文摘要 iv
目錄 vi
圖目錄 x
表目錄 xiii
第一章 序論 1
1-1 前言 1
1-2 燃料電池簡介 2
1-3 質子交換膜燃料電池 4
1-3-1 元件組成及工作原理 4
1-3-2 質子交換膜 5
1-3-3 質子交換膜傳導機制 6
1-4 質子交換膜種類 8
1-4-1 全氟離子性高分子 8
1-4-2 部分含氟離子性高分子 9
1-4-3 非氟碳氫離子性高分子 9
1-4-4 其他 10
1-5 質子交換膜結構設計 11
1-6 文獻回顧 13
1-7 研究動機 19
第二章 實驗儀器及原理 21
2-1 鑑定分析儀器 21
2-1-1 超導核磁共振儀(NMR) 21
2-1-2 基質輔助雷射脫附游離飛行質譜儀(MALDI TOF/TOF) 22
2-1-3 凝膠滲透層析儀(GPC) 23
2-1-4 傅立葉紅外線光譜儀(FT-IR) 25
2-2 熱分析儀器 27
2-2-1 熱重量分析儀(TGA) 27
2-2-2 熱示差掃描卡量計(DSC) 28
2-2-3 熱機械分析儀(TMA) 29
2-3 微觀分析 30
2-3-1 穿透式電子顯微鏡(TEM) 30
2-4 電化學分析 31
2-4-1 交流阻抗分析儀(AC Impedance) 31
2-4-2 燃料電池元件測試儀 32
第三章 實驗 34
3-1 藥品 34
3-2 實驗流程 36
3-2-1 雙酚單體流程 36
3-2-2 雙氟單體流程 37
3-2-3 高分子與磺酸化高分子流程 38
3-3 雙酚單體製備 39
3-4 雙氟單體製備 53
3-5 高分子聚合 59
3-6 高分子磺酸化 66
3-7 磺酸化後處理 68
3-7-1 薄膜製備與酸的置換 68
3-7-2 IEC測定 68
3-7-3 吸水率及尺寸安定性測試 69
3-7-4 Hydration number(λ) 70
3-7-5 氧化、水解穩定性 70
第四章 結果與討論 71
4-1 材料結構鑑定 71
4-1-1 GPC分析 71
4-1-2 FT-IR 72
4-2 熱分析及機械特性 74
4-2-1 TGA分析 74
4-2-2 機械特性 77
4-3 磺酸化薄膜可靠度分析 81
4-3-1 吸水率、λ值及尺寸安定性 81
4-3-2 氧化及水解穩定性 86
4-4 電性及微觀分析 87
4-4-1 電性分析 87
4-4-2 微觀分析 89
4-5 元件分析 91
第五章 結論 92
參考文獻 93
附錄 98
附錄3-1 MALDI-TOF 98
附錄3-2 NMR 102
附錄4-1 A series吸水率、λ值、尺寸安定性 118
附錄4-2 sA series質子導電度 119

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