臺灣博碩士論文加值系統

成功合成主鏈含苯並咪唑之新型二胺單體3-(2-(5-amino-benzimidazolyl))aniline (m/IM/NH2)，並與六環酸酐Naphthalenetetra-carboxylic dianhydride (NTDA)進行高溫聚縮合形成一系列的PI共聚物；其固有黏度範圍在1.01~1.59 dL/g之間，均可塗佈成具有韌性之薄膜；這些共聚物有好的熱安定性，於氮氣下10 %重量損失溫度皆有530℃以上，而氮氣下的裂解溫度也在500℃以上；這些PI共聚物乾膜的抗張強度介於92~135 MPa，但是當摻雜磷酸後，薄膜受到磷酸的膨潤，機械強度會明顯下降。因此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，使高分子鏈緊密堆積，導致磷酸摻雜量減少，但仍能有足夠高的質子傳導度，並能維持好的機械性質。所合成PI共聚物的質子傳導度在磷酸摻雜率大於240%的時候，幾乎都比m-PBI高，例如交聯前後之m6BPBI2PF1.5DMB0.5在160℃時之質子傳導度都高於m-PBI (54.1 mS/cm)，分別為65.6 mS/cm與61.0 mS/cm，非常有潛力應用於高溫型燃料電池的質子傳導膜。

A Novel diamine 3-(2-(5-aminobenzimidazolyl))aniline(m/IM/NH2), containing benzimidazole backbone was synthesized. The polyimides (PIs) were prepared by polycondensation of the diamines and Naphtha-lenetetracarboxylic dianhydride(NTDA). They had inherent viscosities in the range of 1.01~1.59 dL/g, and they could form tough and flexible films. The PIs exhibited high thermal stability with 10% decomposition temper-ature more than 530℃ in nitrogen, and their onset temperature was more than 500℃ in nitrogen. These films exhibited good mechanical properties with tensile stress around 92~135 MPa. However, the mechanical proper-ties of PIs significantly decreased when phosphoric acid doping level in-creased. This situation could be improved via crosslinking reaction of methyl group, cross-linked PIs would form close packing, and it led to decrease of phosphoric acid doping level, but it could still maintain high proton conductivity. The PIs when phosphoric acid doping level exceeded 240%, exhibited higher proton conductivity than m-PBI. For example, the proton conductivities of m6BPBI2PF1.5DMB0.5 and C5-m6BPBI2PF1.5DMB0.5 were 65.6 and 61.0 mS/cm at 160℃, respec-tively. Thus, these PIs could be the promising materials alternative to m-PBI membrane for high-temperature fuel cells applications because of their high proton conductivity and good oxidative stability.

中文摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VIII
第一章 緒論 1
1.1 前言 1
1.2 燃料電池發展簡介 3
1.3 燃料電池的特色 5
1.4 燃料電池的種類與應用 7
1.5 質子傳導膜燃料電池工作原理 11
1.6 質子傳導膜之瓶頸與發展方向 13
1.7 高溫型質子傳導膜種類與介紹 16
1.7.1 全氟磺酸改質薄膜系列 16
1.7.2 替代磺化聚合物及其複合膜系列 16
1.7.3 酸鹼聚合物膜系列 17
1.8 研究動機與內容 19
第二章 文獻回顧 21
2.1 聚苯並咪唑(Polybenzimidazole，PBI) 21
2.2 PBI傳導機制 24
2.3 聚醯亞胺(Polyimide，PI) 27
2.4 交聯劑 30
第三章 實驗 33
3.1 實驗藥品 33
3.2 實驗程序 35
3.2.1 單體合成 36
3.2.2 聚醯亞胺共聚物(PIs)合成 38
3.3 聚合物之化性與物性分析 40
第四章 結果與討論 44
4.1 單體與PIs的合成 44
4.2 固有黏度 50
4.3 溶解度測試 52
4.4 確認交聯反應 53
4.5 熱性質分析 56
4.6 PBI共聚物組成對磷酸摻雜量的效應 60
4.7 膨潤度測試 63
4.8 質子傳導度分析 65
4.8.1 溫度對質子傳導度的效應 65
4.8.2 化學構造對質子傳導度的效應 72
4.9 機械性質量測 74
4.9.1 未摻雜磷酸薄膜機械性質量測 74
4.9.2 摻雜磷酸薄膜機械性質量測 76
4.10 甲基交聯對機械性質影響 78
4.11 氧化安定性測試 79
第五章 結論 80
第六章 參考文獻 82

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