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研究生：	許常佑 Hsu, Chang-Yu
論文名稱：	含聚乙烯醚交聯型苯乙烯-馬來酸酐之醯亞胺質子傳導膜之製備與其特性分析 Preparation and Properties of Proton-Conducting Membranes of Crosslinked Polyimide based on Poly(styrene-co-maleic anhydride) and Polyoxyalkylene diamines
指導教授：	郭炳林 Kuo, Ping-Lin
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	68
中文關鍵詞：	高分子質子傳導膜、聚(苯乙烯-馬來酸酐) 、燃料電池
外文關鍵詞：	polyoxyalkyl diamine, proton- conducting membrane, poly(styrene-co-maleic anhydride)
相關次數：	點閱：92 下載：1
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本研究利用帶有磺酸基之monoamine混摻polyoxyalkylene diamine依等化學計量與帶有酸酐基之聚(苯乙烯-馬來酸酐)進行熱交聯反應，製備出含有不同磺酸基之一系列質子傳導薄膜，更進一步探討與分析其特性。結果顯示，自行製備出之高分子薄膜具透明及韌性；在DSC分析方面可發現此系列高分子薄膜均具有二個玻璃轉移溫度(Tg)：一個在-30 ~ -50°C(聚醚鏈段之Tg)，另一個在40 ~ 70°C(整個高分子主鏈移動之Tg)。在TGA結果方面，其Td0.1約在420°C，顯示本系列薄膜具有良好的熱穩定性。此外，本系列氫離子傳導高分子薄膜在完全水合狀態及100°C下，其質子傳導度可達8.4×10-2 S/cm(SMEO-SO3H-1.10)。在甲醇穿透度結果方面，本系列氫離子高分子薄膜對甲醇穿透速率約在3.0 ~ 6.2 × 10-6 cm2/s。

A new class of proton-conducting membranes were prepared based on poly(styrene-co-maleic anhydride) (SMA), polyoxylalkylene diamine (XTJ-502) and sodium 2-aminoethanesulfonate. The obtained proton- conducting membranes are transparent, tough and flexible. From DSC results, these polymers show two glass transition temperatures rang from -30 ~ -50°C(ethylene oxide) and 40 ~ 70°C(polymer matrix). Form TGA analysis, these membranes possess good thermal stability (Td0.1 = 420°C). In proton conductivity measurements, it is observed that the fully-hydrated membranes with the –SO3H content of 1.1 meq/g has the protonic conductivity of 8.4×10-2 S/cm at 100°C, and the methanol permeability of 6.2 × 10-6 cm2/s at 30°C.

壹、中文摘要..................................................................................................Ⅰ
貳、英文摘要..................................................................................................Ⅱ
參、總目錄.....................................................................................................Ⅲ
肆、表目錄.....................................................................................................Ⅶ
伍、圖目錄.....................................................................................................Ⅷ
柒、主文
第一章 緒論.....................................................................................................1
1-1 前言............................................................................................................1
1-2 燃料電池的歷史及其優點........................................................................2
1-3 燃料電池的種類........................................................................................4
1-4 質子交換膜燃料電池................................................................................6
1-5 直接甲醇燃料電池....................................................................................8
1-6 質子交換膜................................................................................................9
1-6.1 放質型氟素系質子交換膜...................................................................11
1-6.2 磺酸化之碳氫系質子交換膜...............................................................12
1-6.3有機-無機複合膜...................................................................................13
1-6.4含酸鹼對之質子交換膜........................................................................16
1-7本研究動機...............................................................................................16
第二章 實驗及儀器之原理...........................................................................18
2-1 固態核磁共振(Solid-State Nuclear Magnetic Resonance)........................18
2-1.1 魔術角旋轉(Magic Angle Spinning，MAS).........................................19
2-1.2 交叉極化(Cross-Polarization，CP).......................................................20
2-2 交流阻抗分析(Alternating Current Impedance Spectroscopy).................22
2-2.1 基礎電路學簡介...................................................................................22
2-2.2 交流阻抗分析.......................................................................................24
2-3 聚醯胺酸之合成與醯亞胺化(Imidization)..............................................28
2-3.1 熱閉環(Thermal Imidization).................................................................29
2-3.2 溶液環化法(Solution imidization).........................................................30
2-3.3 化學環化法(Chemical Imidization).......................................................30
第三章 實驗方法與步驟...............................................................................32
3-1 實驗藥品..................................................................................................32
3-2 儀器設備..................................................................................................32
3-3 含聚乙烯醚交聯型苯乙烯-馬來酸酐之醯亞胺質子傳導膜之製.........33
3-3.1 Sodium 2-Aminoethanesulfonate (SAES)之合成...................................33
3-3.2 鈉式-高分子電解質薄膜之製備..........................................................34
3-4 質子傳導膜之鑑定..................................................................................37
3-4.1 傅立葉轉換紅外線光譜儀(FT-IR).......................................................37
3-4.2 醯亞胺化程度(Degree Imidization)......................................................37
3-4.3 13C固態核磁共振光譜(13C Solid-State NMR)....................................37
3-4.4 離子交換當量(Ion Exchange Capacity, IEC)之測定...........................38
3-4.5 熱性質分析..........................................................................................38
3-4.5.1 微差式掃描卡計(Differential Scanning Calorimeter, DSC) ..............38
3-4.5.2 熱重分析(thermogravimetric analysis, TGA).....................................39
3-4.6 含水量測試(Water uptake)...................................................................39
3-4.7 結合水(bound water)............................................................................39
3-4.8 X光繞射分析(XRD).............................................................................40
3-4.9交流阻抗分析(AC Impedance Measurements)......................................40
3-4.10 甲醇穿透(Methanol permeability).......................................................41
第四章 結果與討論.......................................................................................43
4-1 質子傳導膜之製備與結構之鑑定..........................................................43
4-1.1 Sodium 2-Aminoethanesulfonate (SAES)結構之鑑定...........................43
4-1.1 傅立葉轉換紅外線光譜(FT-IR)...........................................................44
4-1.2 離子交換當量(Ion Exchange Capacity)及醯亞胺化程度(Degree of  
     Imidization).....................................................................................................44
4-1.3 13C 交叉極化/魔術轉角固態核磁共振光譜(13C CP/MAS NMR).....45
4-2 熱性質分析..............................................................................................46
4-3 X光繞射(XRD).........................................................................................47
4-4 水在質子傳導膜(SMEO-SO3H-x)中的狀態...........................................47
4-5 甲醇穿透度(Methanol Permeability)........................................................48
4-6 質子傳導度..............................................................................................49
4-7 氧化穩定..................................................................................................50
第五章 結論.................................................................... ..............................51
第六章 參考文獻...........................................................................................52
第七章 自述...................................................................................................68


                                    

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校內：2008-08-04公開
校外：2008-08-04公開

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