研究生: |
王伯隆 Po-lung Wang |
---|---|
論文名稱: |
合成含苯並咪唑或苯並噻唑側基之聚苯咪唑及其性質研究 Synthesis and Characterization of New Polybenzimidazoles Containing Pendent Benzimidazole or Benzothiazole Groups |
指導教授: |
陳燿騰
Yaw-terng Chern |
口試委員: |
王健珍
Chien-chen Wang 曾文祺 Wen-chi Tseng |
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: | 2014 |
畢業學年度: | 102 |
語文別: | 中文 |
論文頁數: | 122 |
中文關鍵詞: | 聚苯咪唑 |
外文關鍵詞: | polybenzimidazole |
相關次數: | 點閱:153 下載:1 |
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Part I
本研究主要合成側鏈含benzimidazole之Polybenzimidazole(PBI),並引進甲基側基應用於質子交換膜的交聯上,合成交聯型之C-PBI聚合物,在未高溫交聯前,這些聚合物具有好的溶解度,其固有黏度範圍在0.9~1.21 dL/g之間,均可塗佈成具韌性之薄膜,在高溫交聯後,這些聚合物有好的熱安定性,高的玻璃轉移溫度( Tg 大約在 300 ℃左右)。未添加交聯劑之聚合物,其抗張強度大於92 MPa,添加交聯劑後,其抗張強度大於101 MPa。未添加交聯劑的聚合物,在摻雜磷酸後,由於膨潤導致機械強度大幅下降,為了提高吸磷酸後薄膜的機械強度,本研究合成了一系列交聯型的C-PBI聚合物。
PBI質子傳導度隨溫度與磷酸摻雜量增加而增加,由於本研究導入甲基側基,進行交聯形成網狀結構,降低了吸附磷酸的量,提升了機械強度,其中C5-CPBI-BIside-30飽和磷酸摻雜程度達342 wt%,具有高的抗張強度22 MPa,質子傳導度在180℃為65.8 mS/cm,C5-CPBI-BIside-30的濕膜抗張強度與質子傳導度高,有潛力應用於中溫型燃料電池的質子傳導膜。
這些側基含benzimidazole且有網狀交聯結構的C-PBI薄膜具有高的磷酸摻雜量、高質子傳導度、好的熱安定性且有良好的機械性質,很有潛力成為中溫型燃料電池的質子傳導膜。
Part II
本研究主要合成側鏈含benzothiazole之Polybenzimidazole(PBI),引進甲基側基應用於質子交換膜的交聯上,合成交聯型之C-PBI聚合物,在未高溫交聯前,這些聚合物具有好的溶解度,其固有黏度範圍在0.9~1.47 dL/g之間,均可塗佈成具韌性之薄膜,在高溫交聯後,這些聚合物有好的熱安定性,高的玻璃轉移溫度( Tg 大約在 300 ℃左右)。未添加交聯劑之聚合物,其抗張強度大於78 MPa,添加交聯劑後,其抗張強度大於90 MPa。未添加交聯劑的聚合物,在摻雜磷酸後,由於膨潤導致機械強度大幅下降,為了提高吸磷酸後薄膜的機械強度,本研究合成了一系列交聯型的C-PBI聚合物。
由於本研究導入甲基側基的交聯劑,直接改變原本PBI的結構,導致有些系列在低的交聯程度,磷酸摻雜量比未添加交聯劑的還高,因而有高的吸附磷酸量與機械強度的加強,以C5-CPBI-1-10為例,在160℃溫度下,有高的導電度57.6 mS/cm與好的抗張強度7.9 MPa。
因此這些含benzothiazole側基交聯型的C-PBI薄膜具有高的磷酸摻雜量、高質子傳導度、好的熱安定性且有良好的機械性質,是成為中溫型燃料電池的質子傳導膜很好的材料。
Part I
A series of new polybenzimidazoles (PBIs) with pendant benzimidazole ring had been synthesized. This is the first study that improved mechanical properties of proton exchange membranes via crosslinking reaction using methyl pendent. The uncrosslinked PBI showed good solubility in aprotic solvents. They had high inherent viscosities in the range of 0.9~1.21 dLg-1, and they could form tough and flexible films. After crosslinking, they exhibited high thermal stability and their glass transition temperature exceeded 300oC. The PBI had the high tensile stress exceeded 92 MPa. The mechanical properties of phosphoric acid doped PBI significantly decreased.
The conductivity of the PBIs was increased with increasing temperature and phosphoric acid doped. The tensile stress of C5-CPBI-BIside-30 containing 342 wt% of phosphoric acid doped was 22 MPa. The proton conductivity at 180oC was 65.8 mS/cm that is higher than the m-PBI (56.8 mS/cm).
Thus, these C-PBIs have high phosphoric acid doped, high proton conductivity, good thermal stability and good mechanical properties. They are great potential to become a medium temperature fuel cell proton conducting membrane material in the future.
Part II
A series of new polybenzimidazoles (PBIs) with pendant benzothiazole ring had been synthesized. This study improved mechanical properties of proton exchange membranes via crosslinking reaction using methyl pendent. The uncrosslinked PBI showed good solubility in aprotic solvents. They had high inherent viscosities in the range of 0.9~1.47 dLg-1, and they could form tough and flexible films. After crosslinking, the PBI exhibited high thermal stability and their glass transition temperature exceeded 300oC. The PBI had the high tensile stress exceeded 78 MPa. The mechanical properties of phosphoric acid doped PBI significantly decreased.
The conductivity of the PBIs was increased with increasing temperature and phosphoric acid doped. C5-CPBI-1-10 exhibited high proton conductivity (57.6 mS/cm at 160oC) and the tensile stress (7.9 MPa).
Thus, some of C-PBIs have high phosphoric acid doped, high proton conductivity, good thermal stability and good mechanical properties. They are great potential to become a medium temperature fuel cell proton conducting membrane material in the future.
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