本論文主要合成一系列磺酸化無規共聚碳氫離子性高分子並研究結構、型態與質子導電度的關係。以自製多苯環芳香族單體4,4'-difluoro-2',3',5',6' -tetraphenyl-[1,1',4',1']-quinquephenyl與2',3',5'-triphenyl- [1,1';4',1';4',1';4',1' -quinquephenyl]-4,4'-diol以及市售Bisphenol AF單體經親核性聚縮合反應而得，並調控不同單體之進料比，隨後進行磺酸化並澆鑄成膜，得到離子交換能力(ion exchange capacity，IEC)介於2.8~3.4 mmol/g的磺酸化高分子薄膜。熱穩定性方面，高分子的熱裂解溫度547OC~569OC，磺酸化高分子的熱裂解溫度則隨著IEC增加而下降，介於203OC~254OC之間。在30OC下，薄膜的吸水率介於79%~237%，隨著溫度的升高，在80OC時，吸水率隨之上升到122%~314%之間，部分高IEC的薄膜因吸水率過高而溶解於水中。在80 °C、40% 相對濕度的環境下質子導電度約為5~21 mS/cm之間，而在80 °C、95% 相對濕度的環境下，質子導電度高則達199~354 mS/cm，表現出相當優異的質子傳遞能力。經由穿透式電子顯微鏡(TEM)亦可觀察到磺酸化高分子薄膜的微結構呈現良好的微相分離型態，離子團簇大小約為5nm~25nm之間。由於部分磺酸化高分子薄膜因過度膨潤在高溫高濕環境下會溶於水中，未來將製備低磺酸化程度的高分子，使這系列材料可以應用於燃料電池質子交換膜。

In this thesis, a series of sulfonated random hydrocarbon copolymers were synthesized, and their proton conductivities, molecular conformation also were examined. The polymers were prepared by polymerization of commercialized Bisphenol AF with two novel monomers, 4,4'-difluoro-2',3',5',6'-tetraphenyl-[1,1',4',1']-quinque phenyl, with different ratio of 2',3',5'-triphenyl-[1,1';4',1';4',1';4',1'-quinque phenyl]-4,4'-diol. Subsequent sulfonation and solution casting provided membranes possessing ion exchange capacities ranging from 2.8 to 3.4 mmol/g. The sulfonated polymers exhibited excellent proton conductivities ranged between 5 to 21 mS/cm at 80 oC/40% RH, and 199 to 354 mS/cm at 80 oC/95% RH. Moreover, the decomposition temperature (Td5%) of unsulfonated copolymers ranged between 547 oC to 569 oC and sulfonated copolymers ranged between 203 oC ~254 oC. TEM analysis of the polymers, in the dehydrated state, revealed isolated spherical aggregates of ions, which presumably coalesce when hydrated to provide highly conductive pathways. Especially, some of sulfonated membranes dissolves when immersed into the water at high temperature. It is because those membranes have too much sulfonate group in the structure. We will prepare sulfonated membrane with lower IEC value, making this series of copolymer could be application for proton exchange membrane fuel cell.

摘要 i
Abstract ii
目錄 iii
圖目錄 vi
表目錄 viii
第一章 序論 1
1-1 前言 1
1-2 燃料電池之種類 2
1-2-1 低溫型燃料電池 2
1-2-2 中、高溫型燃料電池 2
1-3 質子交換膜燃料電池 5
1-3-1 質子交換膜燃料電池之基本構造 5
1-3-2 質子交換膜燃料電池之工作原理 6
1-4 質子傳導機制 7
1-4-1 Grotthus Mechanism (Hopping mechanism) 7
1-4-2 Vehicular Mechanism 8
1-4-3 Surface Mechanism 8
1-5 質子交換膜燃料電池種類 9
1-5-1 全氟離子性高分子薄膜(Perfluorinated polymer membrane) 10
1-5-2 非氟離子性高分子薄膜(Non-Perfluorinated polymer membrane) 10
1-5-3部分含氟離子性高分子薄膜(Partially fluorinated polymer membrane) 11
1-5-4酸鹼混摻高分子薄膜(Acid-base blends polymer membrane) 11
1-5-5有機/無機混成薄膜(organic/inorganic blend membrane) 12
1-6 高分子結構設計 13
1-6-1 交替式共聚高分子(Alternating copolymer) 14
1-6-2 無規共聚型高分子(Random copolymer) 14
1-6-3 接枝式共聚高分子(Graft copolymer) 14
1-6-4 嵌段式共聚高分子(Block copolymer) 15
1-7 文獻回顧 16
1-7-1 交替式共聚高分子文獻回顧 16
1-7-2 無規共聚高分子文獻回顧 18
1-7-3 接枝式共聚高分子文獻回顧 20
1-7-4 嵌段式共聚高分子文獻回顧 21
1-8 研究動機 24
第二章 儀器介紹 26
2-1 鑑定分析儀器 26
2-1-1 高磁場液態核磁共振儀(Nuclear Magnetic Resonance，NMR) 26
2-1-2 基質輔助雷射脫附游離飛行質譜儀(MALDI TOF/TOF) 26
2-1-3凝膠滲透層析儀(Gel Permeation Chromatography，GPC) 27
2-1-4 傅立葉紅外線光譜儀(Fourier Transform infrared spectroscopy，FT-IR) 27
2-2 熱分析儀器 27
2-2-1 熱重量分析儀(Thermogravimetric Analyzer，TGA) 27
2-2-2 熱示差掃描卡量計(Differential Scanning Calorimetr，DSC) 28
2-2-3 熱機械分析儀(Thermal Mechanical Analyzer，TMA) 28
2-3 微觀結構分析 29
2-3-1 穿透式電子顯微鏡(Transmission Electron Microscope，TEM) 29
2-4 磺酸化薄膜之電性量測 29
2-4-1 交流阻抗分析儀(AC Impedance) 29
第三章 實驗 30
3-1 實驗藥品 30
3-2 實驗流程 32
3-2-1 單體製備 32
3-2-2 高分子聚合及磺酸化 33
3-3 二氟單體合成 34
3-3-1 (step1) 1,3-bis(4-bromophenyl)propan-2-one 34
3-3-2 (step2) 2,5-bis(4-bromophenyl)-3,4-diphenylcyclopenta-2,4-dienone 35
3-3-3 (step3-1) 4,4'-Dibromo-2',3',5',6'-tetraphenyl-[1,1;4,1]-terphenyl 36
3-3-4 (step4-1) 4,4'-Dihydroxy-2',3',5',6'-tetraphenyl-[1,1',4',1']-quinquephenyl 37
3-4 二醇單體合成 39
3-4-1 (step3-2) 4,4'-Dibromo-2',3',5'-triphenyl-[1,1;4,1]-terphenyl 39
3-4-2 (step4-2)4,4'-Dimethoxy-2',3',5'-triphenyl-1,1';4',1';4',1';4',1'- quinquephenyl 40
3-4-3 (step5-2) 2',3',5'-triphenyl-[1,1';4',1';4',1';4',1'-quinquephenyl]-4,4' '-diol 42
3-5 高分子聚合 43
3-5-1 X1聚合 43
3-5-2 高分子成膜 45
3-6 高分子磺酸化[42] 46
3-7 磺酸化後之材料處理 47
3-7-1 磺酸化高分子成膜 47
3-7-2 離子交換能力(IEC)滴定 47
3-7-3吸水率、尺寸安定性及λ值(Water Uptake, Dimensional Stability, and Hydration number) 48
第四章 結果與討論 49
4-1 材料結構鑑定 49
4-1-1 GPC分析 49
4-1-2 IEC數值滴定 49
4-1-3 1H NMR圖譜分析 50
4-1-4 傅立葉紅外線光譜(FT-IR)分析 52
4-2 熱分析及機械性質分析 56
4-2-1 TGA熱穩定性分析 56
4-3磺酸化薄膜之物理、化學性質分析 58
4-3-1 薄膜吸水率、尺寸安定性及λ值 58
4-3-2 薄膜氧化及水解穩定性 59
4-4磺酸化薄膜之電性及微相分離型態分析 60
4-4-1 薄膜質子導電度分析 60
4-4-2 TEM分析 62
4-4-3 薄膜密度量測 64
第五章 結論 65
第七章 附錄 70

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