本研究以m-PBI 及2,2'-dimethylpoly(oxyphenylene benzimidazole) (Me-OPBI)
為高分子主鏈，並於側鏈導入四級胺基團與末端炔官能基，以進料比、溫度與時
間調控陰離子交換膜之離子交換容量與交聯比例，接著利用疊氮-炔環加成反應，
將末端炔與1, 3-二疊氮丙烷進行交聯，並探討不同接枝率、交聯程度、交聯時間
對於薄膜性質之影響，以及硫醇-烯加成反應與疊氮-炔環加成反應進行交聯後性
質之比較。
以m-PBI 為主鏈之聚苯并咪唑起初在接枝過程遇溶解度不佳之問題，IEC 若
低於2.85 mmol/g 即無法溶於有機溶劑中，將乙基導入結構中可有效改善溶解度，
且可調IEC 範圍可擴大從0.76 至2.65 mmol/g。交聯後之薄膜吸水率介於10-45%，
溶脹率為0.3-17%，結果顯示交聯可使尺寸穩定性更佳且有效抑止吸水率，於乾
溼膜狀態亦有良好之機械性質。導入乙基後之氫氧根離子傳導率在80°C 下可提
升至106.7 mS/cm，並更進一步利用AFM、SAXS 分析薄膜之離子簇尺寸。高IEC
之薄膜在60°C 1 M KOH 鹼性環境中720 小時後，80°C 之傳導率還保有大於
80%。電池功率的部分，以操作溫度60 ℃、氫氣/氧氣量測下可得到576.9 mW
cm-2 之單電池功率密度。將本研究與硫醇-烯加成反應進行交聯後的薄膜比較性
質，顯示疊氮-炔環加成反應進行交聯之薄膜具有良好之熱性質與鹼性穩定性。
本研究同時以Me-OPBI 含有醚鏈的主鏈高分子進行薄膜性質之探討，交聯
後薄膜之長度與厚度溶脹率分別只有3.2%及5.3%，吸水率只有25%，80 °C 下
之陰離子傳導率可達140.2 mS/cm。薄膜在60°C 1 M KOH 鹼性環境中720 小時
後，80°C 之傳導率損失小於20%。以上結果顯示本研究所製備之陰離子交換膜
具備足夠性質應用於燃料電池。

In this work, we grafted the long alkyl quaternary ammonium side chain and
terminal alkyne onto the polybenzimidazole-based backbone, m-PBI and 2,2'-
dimethylpoly(oxyphenylene benzimidazole) (Me-OPBI). We successfully controlled
the IECs and crosslinking degree of the anion exchange membrane(AEM) by feeding
ratio, temperature, and time. Alkyne-azide cycloaddition was used to crosslink the
AEMs subsequently. The different properties of membrane, such as graft ratio,
crosslinking degree and crosslinking time were discussed. Various crosslinking
reactions were also compared, including thiol-ene reaction and alkyne-azide
cycloaddition.
Due to the poor solubility of m-PBI, the polymer cannot be dissolved in organic
solvent if the IEC is lower than 2.85 mmol/g, thus we introduce ethyl side chain onto
the polymer backbone and effectively improve the solubility. Futhermore, the
adjustable range of IEC value could be expanded from 0.76 to 2.65 mmol/g. The water
uptake of crosslinked membrane ranged from 10 to 45 % and the swelling ratio between
0.3 and 17 %. The results indicate that swelling ratio and water uptake can be inhibited by crosslinking, the crosslinked membrane showed excellent mechanical properties of dry and hydrated membranes as well. After introducing ethyl side chain onto m-PBI, hydroxide conductivity of AEMs at 80°C increased to 106.7 mS/cm which further investigate the size of ionic cluster by AFM and SAXS. Even if the membrane with high IEC value, the conductivity still retain more than 80% after immersing in 1 M KOH at 60°C for 720 h. H2/O2 single cell performance was tested at 60°C, the cell with membrane shows a peak power density of 576.9 mW/cm2. The properties of membrane
in this work was compared to the crosslinked membrane via thiol-ene reaction from literature. The data demonstrate that the crosslinked membrane via alkyne-azide
cycloaddition showed outstanding thermal properties and alkaline stability.
Additionaly, the membrane properties of Me-OPBI which had ether linkage on its
main chain was disscussed. The Me-OPBI based AEM also exhibited low swelling ratio
of 3.2%, 5.3% in length and thick respectively and water uptake of 25%, hydroxide
conductivity of AEMs at 80°C could achieve 140.2 mS/cm. Afterwards the membrane
immersing in 1 M KOH at 60°C for 720h, the conductivity loss less than 20%. The
above results suggest that the fabricated membrane in this work have enough properties for fuell cell application.

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