Part 1
本研究成功合成具有benzimidazole側基之PI 共聚物，其固有黏度範圍在 0.96~1.20dL/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 %裂解溫度皆有500℃以上、以及高軟化溫度(Ts約在 300 ℃左右)，聚合物尚未摻雜磷酸的抗張強度大於132 MPa，但是當摻雜磷酸後，薄膜受到磷酸的膨潤，致使機械強度會大幅下降，經由甲基側基進行交聯反應，在高的質子傳導度能維持好的機械性質，本研究所開發PI很有潛力應用於中溫型燃料電池。
質子傳導度隨溫度與磷酸摻雜量增加而增加，本研究所合成PI共聚物的質子傳導度幾乎都比m-PBI高，這結果顯示導入benzimidazole環在側基比在主鏈更有利於提高質子傳導度，例如交聯前後之BPBI8mBI1F0.5DMB0.5在160℃時之質子傳導度都高於m-PBI (52.0 mS/cm)分別為75.4 mS/cm與78.4 mS/cm。
因此這些具有benzimidazole側基之 PI 薄膜皆具有高磷酸摻雜量、高質子傳導度和好的熱安定性，經由交聯結構的形成，使得PI薄膜在高的磷酸摻雜量下，仍保有良好的機械性質，與高的質子傳導
度，很有潛力成為中溫型燃料電池中質子交換膜材料。
Part 2
本研究成功合成具有benzoxazole側基之 PBI 共聚物，其固有黏度範圍在 0.85~2.4dL/g 之間，均可塗佈成具有韌性之薄膜，這些共聚物隨著側基比例的提升，共聚物的溶解度也增加，且有好的熱安定性，於氮氣下10% 裂解溫度皆為470℃以上、以及高玻璃轉換溫度與軟化溫度( Tg和Ts大約在 300 ℃左右)，它的抗張強度大於70 MPa，但是當摻雜磷酸後，薄膜受到磷酸的膨潤，致使機械強度會大幅下降，經由甲基側基交聯，形成交聯 PBI 共聚物，交聯後 PBI 共聚物因受交聯鍵結，產生高分子鏈堆積緊密，導致磷酸摻雜量下降，雖然質子傳導度有稍微降低，但機械性質比起原先未交聯之 PBI 共聚物，其抗張強度增加了 1~2倍。
質子傳導度隨溫度與磷酸摻雜量增加而增加，其中 PBI-3-3在160℃(低濕度的環境下)，磷酸摻雜量為322 wt%，質子傳導度為 60.2 mS/cm 高於m-PBI(52.0 mS/cm)，至於交聯後之 PBI 薄膜 C-PBI-3-3在160℃(低濕度的環境下)，磷酸摻雜程度達305 wt%，質子傳導度為51 mS/cm，但摻雜磷酸後膜的抗張強度增加1倍從5 Mpa提高至11 Mpa。
因此這些含benzoxazole側基之 PBI 薄膜具有高磷酸摻雜量、高質子傳導度和好的熱安定性，與氧化安定性，經由交聯結構的形成，使得PBI薄膜在高的磷酸摻雜量下，仍保有良好的機械性質，與高的質子傳導度，是很有潛力成為中溫型燃料電池中質子交換膜材料。

Part 1
A series of new polyimides (PIs) with pendant benzimidazole had been synthesized. They had inherent viscosities in the range of 0.96~1.20 dLg-1, and they could form tough and flexible films. The PIs exhibited high thermal stability with 10% decomposition temperature more than 500℃ in nitrogen, and their and soft temperature around 300℃. These films exhibited good mechanical properties with tensile stress exceeded 132 MPa.However,the mechanical properties of phosphoric acid doped PI significantly decreased. The mechanical properties of crosslinked polyimides (C-PI) were improved via crosslinking reaction of methyl group.
The proton conductivity of phosphoric acid doped PBI was dependent on doping PA level and temperatures. The proton conductivity of BPBI8mBI1F0.5DMB0.5 and C5-BPBI8mBI1F0.5DMB0.5 were 75.4 and 78.4 mS/cm at 160℃,respectively.The proton conductivity of PI and C-PI were significantly higher than m-PBI (52.0 mS/cm).Thus, these polyimides (PIs) with pendant benzimidazole membranes could be the promising materials alternative to m-PBI membrane for medium-temperature fuel cells applications because they had high proton conductivity,and good thermal stability.

Part 2
A series of new polybenzimidazoles (PBIs) with pendant benzoxazole had been synthesized. They had inherent viscosities in the range of 0.85~2.4 dLg-1, and they could form tough and flexible films. , The PBIs exhibited high thermal stability with 10% decomposition temperature more than 470 ℃ in nitrogen, and their glass transition temperature and soft temperature around 300℃. These films also exhibited good mechanical properties with tensile stress exceeded 70 MPa.
However, the mechanical properties of phosphoric acid doped PBI significantly decreased. This is the study that improved mechanical properties of proton exchange membranes via crosslinking reaction of methyl groups.The tensile strength of cross-linked PBI was a approximately twice as strong as uncross-linked PBI.
The proton conductivity of phosphoric acid doped PBI was dependent on doping PA level and temperatures. The proton conductivity of PBI-3-3 was 60.2 mS/cm at 160 ℃.The proton conductivity of PBI-3-3
was higher than m-PBI (52.0 S/cm). The proton conductivity of C-PBI-3-3 was 51.7 mS/cm at 160℃,the tensile strength of crosslinked C-PBI-3-3 was about double.Thus, these polybenzimidazoles (PBIs) with pendant benzoxazole membranes could be the promising materials alternative to m-PBI membrane for medium-temperature fuel cells applications because they had high proton conductivity,and good thermal stability.

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