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研究生：	劉家瑋 Liu, Chia-Wei
論文名稱：	高溫質子交換膜燃料電池用聚苯基喹惡啉之合成與性質研究 Synthesis and properties of polyphenylquinoxalines for high-temperature proton exchange membrane fuel cells
指導教授：	許聯崇 Hsu, Lien-chung
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	61
中文關鍵詞：	一步驟合成、聚苯基喹惡啉、摻雜磷酸
外文關鍵詞：	one-pot synthesis, polyphenlyquinoxaline, phosphoric acid doping
相關次數：	點閱：63 下載：4
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本論文研究成功以benzyl 4-hydroxyphenyl ketone和1,2-diamino-4-fluorobenzene為反應物並利用1,4-diazabicyclo[2.2.2]octane作為觸媒，以一步驟合成出自聚合聚苯基喹惡啉之單體3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline和2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline，並利用此單體聚合成出含醚基的聚苯基喹惡啉(polyphenylquinoxaline，PPQ)。而此PPQ可溶於一般有機溶劑中方便加工成膜，在摻雜磷酸之後於高溫下可以獲得良好的質子導電度，可以做為高溫質子交換膜燃料電池之材料。研究中發現，相較於聚苯咪唑(polybenzimidazole，PBI)的系統，PPQ可以在較短的時間達到比PBI更好的摻雜程度，而相同的摻雜程度下，PPQ也有較佳的導電度，推測其原因是PPQ結構中可以摻雜以及傳導磷酸的位置較多所致。但由於PPQ在摻雜過程中會發生溶解的情形，造成機械性質大幅下降，使得PPQ的摻雜程度產生上限，故若要改善此情形未來可以藉由混摻或交聯的方式來提升PPQ薄膜對磷酸的溶解阻抗。

關鍵字 : 一步驟合成 ; 聚苯基喹惡啉 ; 摻雜磷酸

In this study, the one-pot synthesis of self-polymerizable quinoxaline monomer was developed. 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline and 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxalinemixture was synthesized from benzyl 4-hydroxyphenyl ketone and 1,2-diamino-4-fluorobenzene, catalyzed by 1,4-diazabicyclo[2.2.2]octane. Then, an ether-containing polyphenylquinoxaline(PPQ) was synthesized successfully from the monomer. The ether-containing PPQ is organosoluble, and has good proton conductivity at high temperature after doping with phosphoric acid. It is suitable to use in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Compared to polybenzimidazole (PBI), PPQ has a higher acid doping level at the same doping time, because the sites which can be doped with phosphoric acid in the PPQ’s molecular structure are more than PBI. However, the PPQ can be dissolved in high concentration phosphoric acid during the doping, and cause the decrease of mechanical properties. In the future study, the resistance to phosphoric acid of PPQ might be improved by copolymerization or crosslinking reaction.

Key words : one-pot synthesis ; polyphenlyquinoxaline ; phosphoric acid doping

摘要..............................I
Extended Abstract................II
誌謝.............................XI 
總目錄..........................XII 
圖目錄..........................XVI
表目錄........................XVIII 
Scheme目錄......................XIX 
第一章    緒論.....................1
   1-1      前言..................1
   1-2      研究動機及目的.........3
第二章    文獻回顧及原理............5
   2-1      燃料電池之簡介.........5
     2-1-1    燃料電池之發展史......5
     2-1-2    燃料電池之工作原理....6
     2-1-3    燃料電池之分類........8
   2-2      質子交換膜燃料電池(PEMFC)之簡介....8
   2-3      質子交換膜之簡介........12
   2-4      Polyphenylquinoxaline(PPQ)之簡介.......13
     2-4-1    PPQ之簡介............13
     2-4-2    PPQ之合成............15
   2-5     摻雜磷酸(H3PO4)PPQ之質子傳導機制.......19
第三章    實驗方法與步驟............24
   3-1      實驗材料...............24
   3-2      實驗儀器...............25
   3-3      實驗步驟...............26
     3-3-1    自聚合PPQ之單體3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline和2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline合................26
     3-3-2    自聚合PPQ之高分子合成與薄膜製備.........27
     3-3-3    自聚合PPQ薄膜酸質子化之製備.............29
   3-4      結構鑑定................29
     3-4-1    傅利葉轉換紅外線光譜分析(FITR)..........29
     3-4-2    核磁共振光譜分析(NMR) .................30
     3-4-3    元素分析儀(Element analysis，EA).......30
   3-5      性質分析................32
     3-5-1    固有黏度(Inherent viscosity)測定.......32
     3-5-2    薄膜機械性質分析.......32
     3-5-3    機械分析儀(TMA)........33
     3-5-4    熱重損失分析儀(TGA)....34
     3-5-5    熱差掃描卡計(DSC) .....34
     3-5-6    薄膜之磷酸溶解度分析...35
     3-5-7    交流阻抗分析(AC impedance) .35
第四章    結果與討論.................38
   4-1      4-2 自聚合PPQ之單體3-(4-hydroxyphenyl)-2-phenyl-6-
fluoroquinoxaline和2-(4-hydroxyphenyl)-3-phenyl-6-
fluoroquinoxaline合成與結構鑑定分析..................38
     4-1-1    自聚合PPQ之單體3-(4-hydroxyphenyl)-2-phenyl-6-
              fluoroquinoxaline和2-(4-hydroxyphenyl)-3-phenyl-                        6-fluoroquinoxaline合成.................38
     4-1-2    傅利葉轉換紅外線光譜分析(FTIR)...........38
     4-1-3    核磁共振光譜分析(NMR)...................39
     4-1-4    元素分析(EA)...........................40
   4-2      自聚合PPQ之合成性質分析...................41
     4-2-1    固有黏度之測試.............41
     4-2-2    薄膜機械性質分析...........41
     4-2-3    PPQ熱性質分析(TGA、DSC、TMA)...........43
     4-2-4    薄膜之磷酸溶解度分析....................44
     4-2-5    自聚合PPQ薄膜酸質子化之分析.............44
     4-2-6    質子導電度分析.............45
第五章    結論...........................57
參考文獻.................................59
                                    

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校內：2020-08-18公開
校外：2020-08-18公開

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