Kang Na Rae, Pham Thanh Huong, Jannasch Patric
Polymer & Materials Chemistry, Department of Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden.
ACS Macro Lett. 2019 Oct 15;8(10):1247-1251. doi: 10.1021/acsmacrolett.9b00615. Epub 2019 Sep 16.
We report on the straightforward metal-free synthesis of poly(-terphenyl perfluorophenylsulfonic acid)s by efficient superacid-catalyzed Friedel-Crafts polycondensations of commercially available perfluoroacetophenone and -terphenyl, followed by sulfonation of the pendant pentafluorophenyl groups via a selective and quantitative thiolation-oxidation procedure. The stiff and well-defined polymer structure with precisely sequenced and highly acidic units induces efficient ionic clustering, restricted water uptake and swelling, excellent resistance against radical attack, and very high proton conductivity. At 120 °C, the conductivity reaches 40 and 232 mS cm at 50 and 90% relative humidity, respectively, which very closely matches the benchmark Nafion NR212 membrane. The properties are further tuned by copolymerizations. Overall, the results demonstrate that these materials possess a very attractive combination of characteristics for use as high-performance proton-exchange membranes for fuel cells and water electrolyzers.
我们报道了通过高效的超强酸催化的市售全氟苯乙酮和对三联苯的傅克缩聚反应，直接进行无金属合成聚（对三联苯全氟苯磺酸），随后通过选择性定量硫醇化-氧化程序对侧链五氟苯基进行磺化。具有精确序列和高酸性单元的刚性且明确的聚合物结构可诱导有效的离子簇聚、限制水分吸收和溶胀、优异的抗自由基攻击能力以及非常高的质子传导率。在120°C时，在相对湿度为50%和90%时，电导率分别达到40和232 mS/cm，这与基准Nafion NR212膜非常接近。通过共聚进一步调节性能。总体而言，结果表明这些材料具有作为燃料电池和水电解槽的高性能质子交换膜使用的极具吸引力的综合特性。
