合成含十二氟結構二酸與聯苯四胺的新型聚并咪唑和其性質探討

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研究生：	陳俊融 Chun-jung Chen
論文名稱：	合成含十二氟結構二酸與聯苯四胺的新型聚并咪唑和其性質探討 Synthesis and Characterization of Novel Polybenzimidazole Derived from 2,2’-Bis[3,5-bis(trifluoromethyl)phenyl]-4,4’-oxybis(benzoic acid) with 3,3’-Diaminobenzidine
指導教授：	陳志堅 Jyh-Chien Chen
口試委員:	游進陽 Chin-Yang Yu 王英靖 none
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	59
中文關鍵詞：	聚并咪唑、燃料電池
外文關鍵詞：	Polybenzimidazole, fuel cell
相關次數：	點閱：276 下載：4
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上一筆

本研究利用4,4'-Oxybis(benzoic acid)作為起始物，經過溴化、酯化、鈴木偶合與水解反應得到含有bis(trifluoromethyl)phenyl 的新型二酸2,2’-bis[3,5-bis(trifluoromethyl)phenyl]-4,4’-oxybis(benzoic acid)。以此新型二酸與聯苯四胺(3,3'-diaminobenzidine)以Eaton’s reagent為溶劑聚合出一新型polybenzimidazole (PBI)，12F-PBI。其數目平均分子量為57000 g/mol，固有黏度(inherent viscosity，0.5 g/dL，NMP，30℃)為0.76 dL/g。熱裂解溫度T5%與T10%分別為445℃和470℃。並展現出極佳的氧化穩定性，在Fenton test 80小時後，僅有2.8%重量損失。12F-PBI的薄膜是以N-methyl-2-pyrrolidone為溶劑製備。在室溫摻雜磷酸後得到其ADL (acid doping level)為5.9，含磷酸重量百分比為170%。而80℃下摻雜磷酸後得到其ADL為8.8，含磷酸重量百分比為204%。12F-PBI薄膜未摻雜磷酸下，拉伸應力為97 MPa，而12F-PBI薄膜ADL為8.8時，拉伸應力為12 MPa。12F-PBI薄膜在160℃下進行質子傳導率的測試，當ADL為5.9時，質子傳導率為9 × 10-3 S/cm，當ADL為8.8時，質子傳導率為1.8 × 10-2 S/cm。而最後進行全電池測試，可得到最大電功率為200 mW/cm2，證實此新型高分子(12F-PBI)可應用於質子交換膜燃料電池。

A novel diacid (12F-acid) containing bis(trifluoromethyl)phenyl as side group was prepared via four steps from 4,4'-oxybis(benzoic acid). 12F-PBI was synthesized from 3,3’-diaminobenzidine and novel diacid (12F-acid). The Mn of 12F-PBI was 57000 g/mol and the inherent viscosity was 0.76 dL/g. The decomposition temperature at 5% and 10% weight loss under nitrogen was 445℃ and 470℃. The proton exchange memebrane of 12F-PBI was prepared in 5% (by weight) NMP solution. The phosphoric acid doping level was 5.9 and phosphoric acid doped weight percent was 170% at room temperature. The phosphoric acid doping level was 8.8 and phosphoric acid doped weight percent was 204% at 80℃. The tensile strength of 12F-PBI was 97MPa without doping phosphoric acid but the tensile strength was 18MPa with acid doping level was 5.9. The proton conductivity of 12F-PBI was 9 × 10-3 S/cm at 160℃ when acid doping level was 5.9. The proton conductivity of 12F-PBI was 1.8 × 10-2 S/cm at 160℃ when acid doping level was 8.8. The max power density was 200 mW/cm2 at 160℃ when acid doping level was 8.8.

目錄

中文摘要……………………………………………………………………………....I
Abstract……………………………………………………………………………….II
致謝…………………………………………………………………………...……...III
目錄…………………………………………………………………………...……...IV
Figure 索引…………...……………………………………………………….….....VI
Scheme 索引……..……………………………………………………………..…VIII
Table索引…………………………….…………………………………....………...IX

第一章	緒論…………………………………………………………………………..1
1.1	燃料電池簡介……………………………………………………………..……..1
1.2	Nafion的簡介…………………………………………………………………....4
1.3	PBI的合成與性質.........…………………………………………………………7
1.4	PBI的改質方法………………………………………………………………...11
1.5	研究動機………………………………………………………………………..15

第二章	實驗部分……………………………………………………..……………..16
2.1	實驗藥品……………………………………………………………..…………..16
2.2	實驗儀器……………………………………………………………………..…..18
2.3	單體合成………………………………………………………………..………..19
2.4	高分子合成………………………………………………………………..……..22
2.5	高分子薄膜製備…………………………………………………………………24

第三章	結果與討論…………………………………………………………………25
3.1	單體合成與表徵……………………………………………………..…………..25
3.2	高分子合成………………………………………………………..……………..32
3.3	高分子分子量與溶解度…………………………………………………………36
3.4	高分子熱學性質…………………………………………………………………38
3.5	高分子結晶性……………………………………………………………………41
3.6	高分子的磷酸摻雜能力…………………………………………………………42
3.7	高分子的機械強度和氧化穩定性………………………………..……………..45
3.8	高分子的質子傳導率……………………………………………………………48
3.9	高分子的電池性質………………………………………………………………52

第四章	結論…………………………………………………………………………56

參考文獻……………………………………………………………………………..57

                                

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