TWI384024B - 質子交換膜與其形成方法 - Google Patents
質子交換膜與其形成方法 Download PDFInfo
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- exchange membrane
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- bismaleimide
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 24
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 21
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000557 Nafion® Polymers 0.000 abstract description 31
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 3
- 229940113088 dimethylacetamide Drugs 0.000 abstract 3
- 239000000203 mixture Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- -1 γ-butyl lactone Chemical class 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229920005787 opaque polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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Description
本發明係關於一種質子交換膜，更特別關於改良質子交換膜尺寸安定性的組成及方法。
Nafion(sulfonated tetrafluorethylene copolymer，磺酸化四氟乙基共聚物)係1960年代由Dupont公司發展之導電高分子。由於其離子性質，此類化合物又稱作離子聚合物(ionomer)。Nafion獨特的離子性質係來自於接枝於聚四氟乙基主幹末端之磺酸基，由於其優異的熱穩定性及機械性質，Nafion在質子交換膜燃料電池(PEMFC)的領域中占有一席之地。
Nafion之磺酸基上的質子可由某一磺酸基轉移至另一磺酸基以完成質子交換。相反的，電子和陰離子並無法進行上述的轉移。
雖然Nafion具有許多優點，但在加熱後的尺寸變化過大。為了進一步改善Nafion成膜後的機械性質，美國專利第4983690號揭露了一種Nafion與雙馬來醯亞胺的混掺物。不過經實驗証明，上述之混掺物並無法有效解決薄膜加熱後尺寸變化過大的問題。
綜上所述，目前仍需新的方法改善Nafion成膜後的物理性質。
本發明提供一種質子交換膜，包括85至90重量份之磺酸化四氟乙基共聚物；以及15至10重量份之超分歧高分子，係由雙馬來醯亞胺與巴比土酸聚合而成；其中磺酸化四氟乙基共聚物與超分歧高分子相互穿透。
本發明亦提供一種質子交換膜之形成方法，包括取雙馬來醯亞胺與巴比土酸共聚形成超分歧高分子；將磺酸化四氟乙基共聚物水溶液之溶劑由水置換成二甲基乙胺；將10至15重量份之超分歧高分子加入90至85重量份之磺酸化四氟乙基共聚物溶液後，靜置並加熱至50℃，使超分歧高分子與磺酸化四氟乙基共聚物互相穿透；將加熱後之溶液塗佈至基板上，烘烤後進行前處理步驟去除二甲基乙胺即形成質子交換膜。
本發明提供一種質子交換膜的形成方法。首先，取雙馬來醯亞胺與巴比土酸共聚形成超分歧高分子。雙馬來醯亞胺之結構如式1：
其中R1
包括：
巴比土酸之結構如式2所示，其中R2
與R3
各自獨立，係氫原子、甲基、苯基、異丙基、異丁基、或異戊基。
在本發明一實施例中，雙馬來醯亞胺與巴比土酸之莫耳比約介於10：1至1：1之間。取適當比例之雙馬來醯亞胺與巴比土酸加入γ－丁基內酯後，加熱至130℃並反應4小時以進行共聚反應形成超分歧高分子。
在本發明一實施例中，超分歧高分子的單體除了上述的雙馬來醯亞胺與巴比土酸外，亦可含有單馬來醯亞胺及/或多馬來醯亞胺。單馬來醯亞胺可為N－苯基馬來醯亞胺、N－環己烷基馬來醯亞胺、或其他合適之單馬來醯亞胺。多馬來醯亞胺可為三(4－苯基馬來醯亞胺基)胺、聚苯甲基馬來醯亞胺、或其他合適之多馬來醯亞胺。在本發明一實施例中，雙馬來醯亞胺：(多馬來醯亞胺及/或單馬來醯亞胺)之莫
耳比約介於99：1至1：1。
接著將市售之磺酸化四氟乙基共聚物(以下簡稱Nafion)水溶液之溶劑由水置換成二甲基乙胺。置換方式為使用高沸點溶劑再加熱過程取代揮發的水分子。在本發明一實施例中，Nafion係購自DuPont之NAF DE2020CS。
之後將超分歧高分子加入Nafion溶液後，靜置並加熱至50℃，使超分歧高分子與Nafion互相穿透，形成所謂的互穿型高分子(interpenetrating polymer)。超分歧高分子與Nafion之重量比介於10－15：90－85。超分歧高分子與Nafion之間的互穿程度可由透明度判別。當互穿程度越高，透明度越高。反之若互穿程度越低其透明度越低，甚至為肉眼可辨之不透明。值得注意的是，上述靜置加熱的步驟係完全的靜置，額外步驟如超音波震盪或攪拌等常見混合手段並不利於形成互穿型高分子。若互穿程度低，之後形成的質子交換膜將具有較差的尺寸安定性。
最後將加熱後之互穿型高分子溶液塗佈至基板上，以130℃烘烤後，進行前處理步驟。前處理係將質子交換膜取下，依序以H2
O、3%H2
O2
、H2
O、0.5M H2
SO4
及H2
O，於80℃下浸泡各一小時。以去除殘留的二甲基乙胺，即形成質子交換膜。由實驗可知，未進行前處理步驟之質子交換膜因殘留溶劑，其導電性及升溫後之尺寸安定性遠低於前處理後之質子交換膜。可以理解的是，上述之離子交換膜適用於所謂的質子交換膜燃料電池。
為讓本發明之上述和其他目的、特徵、和優點能更明
顯易懂，以實施例說明如下。
比較例1－1
取30g之Nafion水溶液(購自DuPont之DE2020CS)，添加18g之DMAc溶液，於60℃下隔水加熱，以DMAc置換Nafion水溶液中之水及醇類。
將上述Nafion之DMAc溶液直接塗佈於基板上，烘乾後進行前處理以去除殘餘溶劑，形成10cm*10cm*0.003cm之質子交換膜。上述質子交換膜升溫後之尺寸變化如第1圖之曲線1及第2圖之曲線1所示。上述質子交換膜之導電性約為9*10－2
S/cm。
比較例1－2
與比較例1－1類似，差別在於未進行前處理去除殘餘溶劑。此比較例之質子交換膜升溫後之尺寸變化如第2圖之曲線1’所示。由第2圖的比較可知，前處理會大幅降低Nafion薄膜的尺寸安定性。
比較例2
取30g之Nafion水溶液(購自DuPont之DE2020CS)，添加18g之DMAc溶液，於60℃下隔水加熱，以DMAc置換Nafion水溶液中之水及醇類。
接著取0.2439g之BMI(雙馬來醯亞胺)溶於0.9756之γ－丁基內酯，加熱至完全溶解後，加入8.7805g Nafion之二乙基甲胺溶液中，靜置。將上述混合物直接塗佈於基板上，烘乾形成10cm*10cm*0.003cm之質子交換膜。上述質
子交換膜升溫後之尺寸變化如第1圖之曲線2所示。
實施例1－1
取16.967g之BMI(式3之雙馬來醯亞胺)及3.3033g之巴比土酸加入100g之γ－丁基內酯後加熱至130℃並反應4.5小時，以形成超分歧高分子。
接著取30g之Nafion水溶液(購自DuPont之DE2020CS)，添加18g之DMAc溶液，於60℃下隔水加熱，以DMAc置換Nafion水溶液中之水及醇類。
將上述超分歧高分子溶液加入Nafion之二甲基乙胺溶液後，靜置加熱至50℃直到溶液由不透明變透明，形成互穿型高分子溶液。
將互穿型高分子溶液塗佈於基板後，烘烤至130℃以去除大部份的溶劑。接著將質子交換膜取下，依序以H2
O、3%H2
O2
、H2
O、0.5M H2
SO4
、H2
O，於80℃下各處理一小時。去除殘餘溶劑，即形成10cm*10cm*0.003cm之質子交換膜。上述質子交換膜升溫後之尺寸變化如第1圖之曲線3及第2圖之曲線3。上述質子交換膜之導電性約為8*10－2
S/cm，近似於純Nafion薄膜的導電性。
由第1圖之曲線1－3可知，實施例1－1的質子交換膜比比較例1－1與比較例2的質子交換膜具有更佳之尺寸安定性。此外，由雙馬醯亞胺與巴比土酸共聚形成的超分歧高
分子，比雙馬來醯亞胺更能改善Nafion的機械性質。
實施例1－2
與實施例1－1類似，差別在於沒有前處理去除殘餘溶劑。上述質子交換膜升溫後之尺寸變化如第2圖之曲線3’所示。上述未前處理之質子交換膜的導電性約為5*10－4
S/cm。由第2圖的曲線3及3’之比較可知，雖然前處理也會降低此實施例之尺寸安定度，但降低幅度遠小於前處理對純Nafion薄膜造成的影響(曲線1’至1)。此外，前處理雖然會降低尺寸安定性，但可有效提升質子交換膜的導電性。
實施例1－3
與實施例1－1類似，差別在於將上述超分歧高分子溶液加入Nafion之二甲基乙胺溶液後，便直接將不透明的混合物(非互穿型高分子)塗佈於基板上。經前處理的質子交換膜升溫後之尺寸變化如第2圖之曲線4所示，未經前處理的質子交換膜升溫後之尺寸變化如第2圖之曲線4’所示。與靜置加熱形成互穿型高分子的實施例1－1及1－2相較，不透明的高分子混合物在形成質子交換膜後具有較差的尺寸安定性。
雖然本發明已以數個實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
第1圖係本發明比較例與實施例中質子交換膜的尺寸安定性對溫度曲線；以及第2圖係本發明比較例與實施例中質子交換膜在前處理前後的尺寸安定性對溫度曲線。
Claims (15)
- 一種質子交換膜，包括：85至90重量份之磺酸化四氟乙基共聚物；以及15至10重量份之超分歧高分子，係由雙馬來醯亞胺與巴比土酸聚合而成；其中該磺酸化四氟乙基共聚物與該超分歧高分子相互穿透。
- 如申請專利範圍第1項所述之質子交換膜，其中該雙馬來醯亞胺之結構如下式：
- 如申請專利範圍第1項所述質子交換膜，其中該雙馬來醯亞胺與該巴比土酸之莫耳比約介於10：1至1：1之間。
- 如申請專利範圍第1項所述之質子交換膜，其中該 超分歧高分子之單體更包括單馬來醯亞胺及/或多馬來醯亞胺。
- 如申請專利範圍第4項所述之質子交換膜，其中該單馬來醯亞胺包括N－苯基馬來醯亞胺或N－環己烷基馬來醯亞胺。
- 如申請專利範圍第4項所述之質子交換膜，其中該多馬來醯亞胺包括三(4－苯基馬來醯亞胺基)胺或聚苯甲基馬來醯亞胺。
- 如申請專利範圍第4項所述之質子交換膜，其中該雙馬來醯亞胺：(該多馬來醯亞胺及/或該單馬來醯亞胺)之莫耳比約介於99：1至1：1。
- 一種質子交換膜燃料電池，包括如申請專利範圍第1項所述之質子交換膜。
- 一種質子交換膜之形成方法，包括：取雙馬來醯亞胺與巴比土酸共聚形成一超分歧高分子；將磺酸化四氟乙基共聚物水溶液之溶劑由水置換成二甲基乙胺；將10至15重量份之該超分歧高分子加入90至85重量份之該磺酸化四氟乙基共聚物溶液後，靜置並加熱至50℃，使該超分歧高分子與該磺酸化四氟乙基共聚物互相穿透；將加熱後之溶液塗佈至一基板上，烘烤後進行前處理步驟去除二甲基乙胺即形成一質子交換膜。
- 如申請專利範圍第9項所述之質子交換膜之形成方法，其中該雙馬來醯亞胺之結構如下式：
- 如申請專利範圍第9項所述之質子交換膜之形成方法，其中該雙馬來醯亞胺與該巴比土酸之莫耳比約介於10：1至1：1之間。
- 如申請專利範圍第9項所述之質子交換膜之形成方法，其中該超分歧高分子之單體更包括單馬來醯亞胺及/或多馬來醯亞胺。
- 如申請專利範圍第12項所述之質子交換膜之形成方法，其中該單馬來醯亞胺係包括N－苯基馬來醯亞胺或 N－環己烷基馬來醯亞胺。
- 如申請專利範圍第12項所述之質子交換膜之形成方法，其中該多馬來醯亞胺包括三(4－苯基馬來醯亞胺基)胺或聚苯甲基馬來醯亞胺。
- 如申請專利範圍第12項所述之質子交換膜之形成方法，其中該雙馬來醯亞胺：(該多馬來醯亞胺及/或該單馬來醯亞胺)之莫耳比約介於99：1至1：1。
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| TWI418580B (zh) * | 2008-12-31 | 2013-12-11 | Ind Tech Res Inst | 具高質子傳導率之質子交換膜組成物 |
| US8575235B2 (en) | 2009-06-12 | 2013-11-05 | Industrial Technology Research Institute | Removable hydrophobic composition, removable hydrophobic coating layer and fabrication method thereof |
| TWI437027B (zh) | 2011-12-29 | 2014-05-11 | Ind Tech Res Inst | 一種含有軟鏈段之馬來醯亞胺聚合物及其製備方法 |
| EP2796488A4 (en) | 2012-08-01 | 2014-11-26 | Nat Inst For Materials Science | IN HIGH TIMES PROTON-CONDUCTIVE POLYMERIC FILM, MANUFACTURING METHOD AND HUMIDITY SENSOR |
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| CN108752614B (zh) * | 2018-06-20 | 2020-08-04 | 四川大学 | 一种含有相容剂的共混质子交换膜及其制备方法 |
| CN114122470B (zh) * | 2021-11-24 | 2023-12-29 | 中汽创智科技有限公司 | 一种质子交换膜及其制备方法和应用 |
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