本研究利用2,5-dibromonitrobenzene (1)作為起始物，經過Ullmann coupling反應、關環、氰化反應及水解反應得到二酸單體3,8-benzo[c]cinnoline dicarboxylic acid (4)。以此二酸、對苯二酸(terephthalic acid)與聯苯四胺(3,3’-diaminobenzidine)以聚磷酸製程(PPA process)合成聚苯并咪唑PBI100N、PBI80N、PBI60N、PBI40N、PBI20N及PPBI等一系列高分子。其固有黏度(Inherent viscosity)分別為4.38、4.58、3.88、4.29、3.75及3.26 dL/g。研究中成功使用溶膠凝膠法(Sol-gel transition fabrication)製備聚苯并咪唑薄膜。PBI100N/80N/60N/40N/20N/PPBI薄膜之熱裂解溫度Td5%介於646至683 ℃，展現出良好的熱穩定性。PBI100N/80N/60N/40N/20N/PPBI薄膜的acid doping level(ADL)為65~31 PA/RU，對應之薄膜拉伸強度為1.0~5.2 MPa。由於PBI100N/80N/60N在高溫下會發生溶解之現象，我們將薄膜浸泡於10~70 %磷酸溶液後，調控薄膜之ADL進行後續的測試。我們將PBI100N-30%/80N-40%/60N-50%/40N/20N/PPBI在160 ℃進行質子傳導率的測試，當ADL為27、30、30、41、31及34 PA/RU時，質子傳導率分別為0.15、0.16、0.17、0.25、0.19及0.17 S/cm。最後在160 ℃下進行全電池測試，PBI100N-30%、PBI80N-40%、PBI60N-50%、PBI40N、PBI20N及PPBI薄膜可分別達691、1014、1253、800、676、556 mW/cm2之電池功率，導入benzo[c]cinnoline (BZC)結構能夠增加傳導率及電池效能，證實含有benzo[c]cinnoline之聚苯并咪唑薄膜可應用於質子交換膜燃料電池。

The dicarboxylic acid, 3,8-benzo[c]cinnoline dicarboxylic acid (4), was prepared via several synthetic steps from 2,5-dibromonitrobenzene (1). Polybenzimidazoles PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI were polymerized from 3,3’-diaminobenzidine and monomer (4) and terephthalic acid by using PPA process. The inherent viscosity of PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI, measured in methanesulfonic acid at 35 ℃ and 0.2 g/dL, was 4.38, 4.58, 3.88, 4.29, 3.75 and 3.26 dL/g, respectively. PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI could be prepared as flexible and tough membranes by sol-gel method. The thermal decomposition temperature at 5 % weight loss (T d5 %) of PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI were in a range of 646~683 ℃. The phosphoric acid doping level (ADL, PA/RU) of PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI membranes was 65~31 PA/RU. The tensile strength of PBI100N, PBI80N, PBI60N, PBI40N, PBI20N and PPBI membranes was 1.0~5.2 MPa with doping phosphoric acid. PBI100N, PBI80N, PBI60N membrane dissolve at high temperatures, we adjust ADL by immersing the film in 10 ~ 70% phosphoric acid solutions for subsequent test. The proton conductivities of PBI100N-30%, PBI80N-40%, PBI60N-50%, PBI40N, PBI20N and PPBI were 0.15, 0.16, 0.17, 0.25, 0.19 and 0.17 S/cm at 160 ℃ when acid doping level were 27, 30, 30, 41, 31 and 34 PA/RU, respectively. For single fuel cell test at 160 ℃, peak power density of PBI100N-30%, PBI80N-40%, PBI60N-50%, PBI40N, PBI20N and PPBI could reach 691, 1014, 1253, 800, 676 and 556 mW/cm2, respectively. It shows that polybenzimidazoles containing benzo[c]cinnoline are promising proton exchange membranes for HT-PEMFC applications.

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