Highly phosphonated poly(N‐phenylacrylamide) for proton exchange membranes
Highly phosphonated poly(N‐phenylacrylamide) for proton exchange membranes
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DOI：
10.1002/pola.24422
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发表时间：
2011
期刊：
影响因子：
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通讯作者：
Fukuzaki Namiko;Kazuhiro Nakabayashi;S. Nakazawa;S. Murata;Tomoya Higashihara;M. Ueda
中科院分区：
文献类型：
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作者：
Fukuzaki Namiko;Kazuhiro Nakabayashi;S. Nakazawa;S. Murata;Tomoya Higashihara;M. Ueda
以N-[2，4-二（二乙氧基膦酰基）苯基]丙烯酰胺（DEPAA）为原料，通过自由基聚合，再用三甲基溴化硅水解，合成了一种新型的离子交换容量（IEC）为6.72 mequiv/g的高膦酸化聚N-苯基丙烯酰胺（PDPAA）。然后，以六甲氧基甲基三聚氰胺（CYMEL）为交联剂，在甲磺酸存在下，通过PDPAA的芳环与碳阳离子发生亲电取代反应，成功制备了交联PDPAA膜。交联后的PDPAA膜在室温下对芬顿试剂具有很高的氧化稳定性。交联PDPAA膜的质子传导率在95%相对湿度（RH）和80 °C下为8.8 X 10 - 2S/cm，其与Nafion 112相当。在低相对湿度下，交联PDPAA膜在50和30% RH时的质子电导率分别为1.9 × 10 - 3和4.7 × 10 - 5S/cm。交联的PDPAA膜的质子传导率在所报道的膦酸化聚合物中处于最高级别，因此，PDPAA的酸的非常高的局部浓度（IEC = 6.72 mequiv/g）在高RH下实现了高且有效的质子传导。
A novel highly phosphonated poly(N-phenylacrylamide) (PDPAA) with an ion-exchange capacity (IEC) of 6.72 mequiv/g was synthesized by the radical polymerization of N-[2,4-bis(diethoxyphosphinoyl)phenyl]acrylamide (DEPAA), followed by the hydrolysis with trimethylsilyl bromide. Then, the crosslinked PDPAA membrane was successfully prepared by the electrophilic substitution reaction between the aromatic rings of PDPAA and the carbocation formed from hexamethoxymethylmelamine (CYMEL) as a crosslinker in the presence of methanesulfonic acid. The crosslinked PDPAA membrane had high oxidative stability against Fenton's reagent at room temperature. The proton conductivity of the crosslinked PDPAA membrane was 8.8 x 10 -2 S/cm at 95% relative humidity (RH) and 80 °C, which was comparable to Nafion 112. Under low RH, the crosslinked PDPAA membrane showed the proton conductivity of 1.9 × 10 -3 and 4.7 × 10 -5 S/cm at 50 and 30% RH, respectively. The proton conductivity of the crosslinked PDPAA membrane lied in the highest class among the reported phosphonated polymers, and, consequently, the very high local concentration of the acids of PDPAA (IEC = 6.72 mequiv/g) achieved high and effective proton conduction under high RH.