本論文以雙氟單體4,4””-Difluoro-3,3””-bsi-trifluoromethyl-2”,3”- bisphenyl-[1,1’;4’,1”;4”,1”’;4”’,1””]-quinquephenyl(G2)4,4””-Difluoro-3,3””-bsi-trifluoromethyl-2”,3”,5”-triphenyl-[1,1’;4’,1”;4”,1”’;4”’,1””]- quinquephenyl(G3)4,4””-Difluoro-3,3””-bsi-Trifluoromethyl-2”,3”,5”,6”-tetraphenyl-[1,1’;4’,1”;4”,1”’;4”’,1””]-quinquephenyl(G4)和雙酚單體4,4'-(9-Fluorenylidene)diphenol 經由親核性(nucleophilic)聚縮合反應，產生三種型式之聚芳香醚高分子P2、P3、P4。
物性方面，GPC結果顯示分子量大約為1.6×105，分子量分佈指數PDI (Mw/Mn)大約為1.5~2；本論文以NMR鑑定高分子結構無誤，在熱穩定性方面，以TGA及TMA量測聚芳香醚高分子，其裂解溫度(Td)在520℃~ 550℃，軟化溫度皆約在310℃，另外楊氏係數則為(1.25-2.5Gpa)，顯示此系列聚芳香醚高分子擁有良好的熱穩定性及機械特性。
且由於雙氟單體為多苯環結構(五苯環、六苯環、七苯環)，推估磺酸化後不僅擁有良好的機械性質還擁有高質子導電度。本論文將控制磺酸化程度，並以滴定法作定量的分析。
由於此類型聚芳香醚高分子特性良好，本論文將高分子進行磺酸化（sulfonation），而磺酸化後之P4 ，離子交換容積高達3.3(meq/g)，磺酸化後之P2在高溼度(95%)下，質子導電度為Nafion117之1.75倍，在80℃下高達0.28(S/cm) 。

Three aromatic poly(arylene ether)s P2、P3、P4 were synthesized from bis(fluoride)4,4””-Difluoro-3,3””-bsi-trifluoromethyl-n”-bisphenyl-[1,1’;4’,1”;4”,1”’;4”’,1””]-quinquephenyl(n”:2”,3”[G2];2”,3”,5”[G3];2”,3”,5”,6”[G4]) with 4,4'-(9-Fluorenylidene)diphenol. The molecular weight of the polymer (Mw: 105-1.6×105, PDI:1.5-2.2) was measured by gel permeation chromatography and the structure was confirmed by NMR spectra. Thermal stability was measured using Thermogravimetry and Thermomechanical Analysis. The polymer had a Td at 520℃ ~550℃, and soft point at 310℃. Young's modulus of polymer was (1.25-2.5Gpa). This polymer has high strength, modulus of elasticity, and thermal stability. The polymer consists of polyaromatic groups with bisfluoride monomer, (5, 6, 7 aromatic). We hypothesized that sulfonation of the polymer will exhibit high conductivity and great mechanical properties. Ion exchange capacities (IECs) were evaluated by acid–base titration. We sulfonated the polymer in order to apply to the proton exchange membrane fuel cell. The results showed after sulfonation of P4, IEC is 3.3(meq/g), and sulfonation of P2 showed that its proton conductivity is 75% more than Nafion117 at 80℃ with 0.28(S/cm).
Keywords: proton exchange membrane, proton conductivity, Nafion, sulfonated, ion exchange capacity

目錄

摘要………………………………………………………..…. i
Abstract ………………………………………………………….ii
目錄………………………………………………………………. iii
圖次............................................................................................ vi
表次……………………………………………………………. vii
第一章 緒論 1
1.1前言 1
1.2燃料電池 2
1.2.1燃料電池簡述及類別 2
1.2.2質子交換膜燃料電池運作機制 4
1.3質子交換膜目前發展 5
1.4 locally and densely sulfonated polymer 8
1.5 研究動機 12
第二章 儀器介紹 13
2.1 高磁場液態核磁共振儀(nuclear magnetic resonance，NMR) 13
2.2 熱重分析儀(Thermogravimetric analyzer，TGA) 14
2.3 熱機械分析儀(Thermomechanical Analysis ，TMA) 15
2.4 液滴形狀分析系統(Drop shape analysis system) 16
第三章 實驗 17
3.1 二氟單體及高分子製備流程 17
3.2 二氟單體合成 18
3.2.1 1,3-Bis(p- bromophenyl)-2-propanone 18
3.2.2 2,5-Bis(4-bromophenyl)-3,4-diphenylcyclopenta-2,4- dienon 19
3.2.3.1 4,4”-Dibromo-2’,3’-diphenyl-[1,1; 4,1]-terphenyl 20
3.2.3.2 4,4”-Dibromo-2’,3’,5’-diphenyl-[1,1; 4,1]-terphenyl 21
3.2.3.3 4,4”-Dibromo-2’,3’,5’,6’- diphenyl -[1,1; 4,1]-terphenyl 22
3.2.4 4-Fluoro-3trifluoromethylphenylboronic acid 23
3.2.5.1 4,4’’’’-Difluoro-3,3’’’’-bistrifluoromethyl-2’’,3’’- diphenyl-[1,1’;4’,1’’;4’’,1’’’;4’’’,1’’’’]-quinquephenyl………………………………………………………25
3.2.5.2 4,4’’’’-Difluoro-3,3’’’’-bistrifluoromethyl-2’’,3’’,5’’- triphenyl-[1,1’;4’,1’’;4’’,1’’’;4’’’,1’’’’]-quinquephenyl………………………………………………………27
3.2.5.3 4,4’’’’-Difluoro-3,3’’’’-bistrifluoromethyl -2’’,3’’,5’’,6’’-tetraphenyl-[1,1’;4’,1’’;4’’,1’’’;4’’’,1’’’’] - quinquephenyl……………………………………….. 29
3.3 高分子聚合和結構鑑定 31
3.4 高分子薄膜製備 31
3.5 P4高分子磺酸化 32
(a)chlorosulfonic acid(CSA) 32
(b)Trimethylsilyl chlorosulfonate(TMSCS) 32
3.6高分子磺酸化後處理 33
(a)薄膜製備 33
(b)IEC測定 33
(c)Water Uptake Measurements 33
第四章 結果與討論 34
4.1 溶解度(Solubility)測試 34
4.2高分子熱穩定性分析 35
4.2.1 熱裂解溫度(Td5%) 35
4.2.2 軟化溫度 36
4.3高分子機械強度 37
4.4疏水性分析 38
4.5 P4高分子磺酸化參數分析 39
(a)以CSA磺酸高分子之分析 39
(b) 以TMSCS磺酸化高分子之分析 40
4.6 質子導電度(proton conductivity) 41
第五章 結論 43
參考文獻…………………………………………………………44
附錄………………………………………………………………48

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