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研究生: 邱茂興
Mao-Hsing Chiu
論文名稱: 合成新型含雜環結構之磺酸化聚醯亞胺於質子交換膜材料之性質研究
Synthesis and Characterization of New Sulfonated Polyimides Containing Heterocyclic Groups for Proton Exchange Membrane Materials
指導教授: 陳燿騰
Yaw-Terng Chern
口試委員: 賴森茂
Sen-Mao Lai
華沐怡
Mu-Yi Hua
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 111
中文關鍵詞: 磺酸化聚醯亞胺燃料電池質子交換膜
外文關鍵詞: sulfonated, polyimide, fuel cell, proton exchange membrane
相關次數: 點閱:221下載:3
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  • 本研究成功製備了含側鏈磺酸基的新型二胺單體2,2'-(4,4'- diaminobiphenyl -2,2'-diyl)dibenzothiazole-5-sulfonic acid (TWS) and 2,2'-(4,4'- diaminobiphenyl-2,2'-diyl) dibenzooxazole-5-sulfonic acid (TWO),在聚合物合成以六環酸酐(NTDA)、含磺酸基之二胺單體(TWS、TWO)以及與其他不含磺酸基的二胺單體(F/NH2、ODA、AP/CF3/NH2、2,3’NA/CF3/NH2)形成SPIs。所合成的聚合物的IEC值範圍在1.41~2.03 meq g-1之間,而磺酸基的裂解溫度都在340oC以上,擁有高的熱安定性。所形成的質子交換膜有好的機械性質並且也具有高的離子傳導度(σ),如聚合物TWSAP7的IEC值為1.7 meq g-1下,離子傳導度在30oC以及80oC分別為125、177 mS/cm,這些聚合物也有好的水解安定性,如TWSAP6、7都有4500小時以上的耐水解安定性時間,因此這些膜有潛力應用於燃料電池應用上。


    Two novel sulfonated diamines of 2,2'-(4,4'-diaminobiphenyl-2,2'-diyl) dibenzothiazole-5-sulfonic acid (TWS) and 2,2'-(4,4'-diaminobiphenyl -2,2'-diyl)dibenzooxazole-5-sulfonic acid (TWO) were systhesized. Sulfonated copolyimides(SPIs) derived from 1,4,5,8-naphthalene tetracarboxylic dianhydride(NTDA),TWS,TWO and other non-sulfonated diamines were successfully synthesized. The SPIs have ion exchange capacity (IEC) of 1.41-2.03 meq g-1 and high desulfonation temperature of 320oC, suggesting the high stability of sulfonic acid groups. The flexible and tough membranes with high mechanical strength were prepared. They showed fairly high proton conductivity(σ). For example, the TWSAP7 with an ion exchange capacity of 1.70 meq g-1 were 125 and 177 mS/cm at 30oC and 80oC in water. They maintained high mechanical strength after aging in water 100oC for 4500 h, showing the excellent water stability. This class of novel sulfonated polyimides containing heterocylic groups is very promising for proton exchange membrane fuel cell.

    摘要 Ⅰ Abstract Ⅱ 目錄 Ⅲ Table索引 Ⅵ Figure索引 Ⅷ 第一章 緒論 1 1.1前言 1 1.2 燃料電池 3 1.2.1燃料電池的種類介紹 3 1.2.2 燃料電池的特點以及應用 6 1.3直接甲醇燃料電池介紹(DMFC) 8 1.4 文獻回顧 12 1.5 研究動機 19 1.6 研究內容 20 第二章 實驗 21 2-1 實驗藥品 21 2.2 實驗程序 24 2.2.1含磺酸基單體製備 25 2.2.2含磺酸基之聚醯亞胺製備 27 2.3聚合物之物性與化性分析 29 第三章 結果與討論 37 3.1 固有黏度之測試 37 3.1.1 TWS系列之聚合物黏度測試 37 3.1.2 TWO系列之聚合物黏度測試 38 3.2溶解度測試 39 3.3 熱性質測試 41 3.4離子交換能力(IEC)測量 46 3.5 吸濕率的測試 48 3.5.1 TWS系列 48 3.5.2 TWO系列 51 3.6離子傳導度分析 55 3.6.1 室溫下離子傳導度分析 56 3.6.2離子傳導度對溫度的效應 62 3.7 甲醇滲透率測量 73 3.8 安定性與機械強度測試 77 3.8.1水解安定性與機械強度 77 3.8.2 氧化安定性量測 87 3.9 TWS與TWO系列之選擇率 89 第四章 結論 91 參考文獻 93

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