研究生: |
簡嘉威 CHIA-WEI CHIEN |
---|---|
論文名稱: |
合成含苯並咪唑基與六氟丙基之聚醯亞胺質子傳導膜及其性質研究 Synthesis and Characterization of Polyimides Containing Benzimidazolyl and Hexafluoropropyl Groups for Proton Exchange Membrane |
指導教授: |
陳燿騰
Yaw-Terng Chern |
口試委員: |
王健珍
Jane-Jen Wang 葉旻鑫 Min-Hsin Yeh |
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: | 2018 |
畢業學年度: | 107 |
語文別: | 中文 |
論文頁數: | 119 |
中文關鍵詞: | 中溫型質子傳導膜 、聚醯亞胺 、六氟丙基 、苯並咪唑基 |
外文關鍵詞: | High-Temperature PEM, Polyimide, Hexafluoropropyl, Benzimidazolyl |
相關次數: | 點閱:236 下載:0 |
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由2,2-Bis(4-carboxyphenyl) hexafluoropropane與4-Nitro-o-phenylenediamine合成2,2-Bis(4-(2-(5-nitrobenzimidazolyl))phenyl)hexafluoropropane (6F/IM/NO2)二硝基化合物,再將6F/IM/NO2 還原成二胺單體2,2-Bis(4-(2-(5-aminobenzimidazolyl))phenyl)
hexafluoropropane (6F/IM/NH2)。
將6F/IM/NH2、2,2 ’-bis(2-benzimidazole)-4,4’- diaminobiphenyl (BP/IM/NH2)及其他芳香族二胺單體與六環酸酐NTDA合成在主鏈與側鏈含benzimidazole的聚醯亞胺(PI)共聚物,其固有黏度範圍在 0.56~1.44 dL/g 之間,均可塗佈成具韌性之薄膜,這些共聚物有好的熱安定性,於氮氣下10 %裂解溫度皆有450℃以上、以及有高的玻璃轉換溫度Tg (約在256~289℃),聚合物尚未摻雜磷酸的抗張強度91.9~140.9 MPa,但是當摻雜磷酸後,薄膜受到磷酸的膨潤,機械強度會大幅下降。藉由甲基側基進行交聯反應,形成交聯 PI 共聚物,交聯後 PI 共聚物因受交聯鍵結,形成緊密堆積高分子鏈,導致磷酸摻雜量下降,但仍能有足夠高的質子傳導度,並能維持好的機械性質,例如交聯後C10-6F4BPBI4F1DMB1 的抗張強度是6F4BPBI4F1DMB1的 1.6 倍。
本研究所合成PI共聚物雖然有較低磷酸摻雜量,但它們的質子傳導度在較低的磷酸摻雜量下幾乎都比m-PBI高,例如6F4BPBI4F1.7DMB0.3在160℃有高的質子傳導度(235% H3PO4 uptake, 58.0 mS/cm),6F4BPBI4PF1.7DMB0.3在160℃有高的質子傳導度(249% H3PO4 uptake, 66.1 mS/cm) , 6F4BPBI4O1.7DMB0.3在160℃有高的質子傳導度(241% H3PO4 uptake, 55.1 mS/cm)皆高於m-PBI(280% H3PO4 uptake, 54.1 mS/cm),這結果顯示導入六氟丙基在主鏈與benzimidazole環在主鏈與側基有利於形成離子通道與提高質子傳導度,很有潛力應用於中溫型燃料電池的質子傳導膜。
Reaction of 2,2-Bis(4-carboxyphenyl) hexafluoropropane with 4-nitro-o-phenylenediamine in polyphosphoric acid gave 2,2-bis(4-(2-(5-nitrobenzimidazolyl))phenyl)hexafluoropropane (6F/IM/NO2), which was hydrogenated to get novel monomer of 2,2-bis(4-(2-(5-aminobenzimidazolyl))phenyl)hexafluoropropane (6F/IM/NH2).
A series of polyimides (PIs) containing main –chain and pendant benzimidazole groups were synthesized from 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA), diamines which had benimidazole such as 6F/IM/NH2, 2,2 ’-bis(2-benzimidazole)-4,4’- diaminobiphenyl (BP/IM/NH2) and other aromatic diamines. The inherent viscosities in the range of 0.56~1.44 dL/g, and each of them could form tough and flexible films. The PIs exhibited high thermal stability with 10% decomposition temperature more than 450oC in nitrogen, and their glass transition temperature is at 256~289oC. These films exhibited good mechanical properties with tensile stress is 91.9~140.9 MPa. However, the mechanical properties of PI significantly decreased when phosphoric acid doping level increased. The mechanical properties of phosphoric acid doped PIs could be improved via crosslinking reaction of methyl group, cross-linked PI would form close packing, and it led to decrease of phosphoric acid doping level, but it could still maintain high proton conductivity and high mechanical properties. The tensile strength of C10-6F4BPBI4F1DMB1 in wet state was enhanced 1.6 times more than 6F4BPBI4F1DMB1. When PIs and m-BPI were in the similar phosphoric acid doping level PIs exhibited higher on proton conductivities at 160℃. For example, the proton conductivities of 6F4BPBI4F1.7DMB0.3 had relatively high proton conductivity at 160℃ (235% H3PO4 uptake, 58.0 mS/cm). 6F4BPBI4PF1.7DMB0.3 had relatively high proton conductivity at 160℃ (249% H3PO4 uptake, 66.1 mS/cm). 6F4BPBI4O1.7DMB0.3 also had high proton conductivity at 160℃ (241% H3PO4 uptake, 55.1 mS/cm). Thus, these polyimides (PIs) containing hexafluoropropyl on main chain and benzimidazole on main-chain and pendant could be the promising materials alternative to m-PBI membrane for medium-temperature fuel cells application because of they can easily form the ion channels and enhanced the proton conductivity.
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