Sulfonated poly (phenyl-alkane)s with all-carbon backbones exhibit excellent chemical stability; however, their applications in proton exchange membranes are limited. Herein, we report a facile synthesis of three sulfonated poly (phenyl-alkane)s SP1–SP3 via efficient acid-catalyzed Friedel−Crafts polycondensations of commercially available 2,3,4,5,6-pentafluorobenzaldehyde with three aromatic monomers, followed by mild and efficient nucleophilic substitution of para-aryl-F with sodium 4-oxybenzenesulfonate. In the characterization of the three polymers, the single-component adsorption–desorption isotherms of N₂ and CO₂ confirmed their intrinsic ultramicroporosity. For the SP3 membrane, small-angle X-ray scattering and atomic force microscopy measurements revealed that larger ionic clusters and smaller hydrophobic assembly domains led to better ionic channel connectivity. These features and the observed high ion exchange capacity and narrowly distributed ultramicropores synergistically determined its high conductivity. Moreover, the SP3 membrane exhibited excellent oxidative stability and good mechanical properties, enabling the successful application in H₂/air proton exchange membrane fuel cells.

具有全碳骨架的磺化聚（苯基烷烃）具有优异的化学稳定性；然而，它们在质子交换膜中的应用受到限制。在此，我们报告了通过市售 2,3,4,5,6-五氟苯甲醛与三种芳族单体的高效酸催化 Friedel-Crafts 缩聚，轻松合成三种磺化聚（苯基烷烃）SP1 - SP3 ，然后是用 4-羟基苯磺酸钠对对芳基-F 进行温和有效的亲核取代。_{在三种聚合物的表征中，N 2}和 CO ₂的单组分吸附-解吸等温线证实了它们固有的超微孔隙率。对于SP3膜、小角度 X 射线散射和原子力显微镜测量表明，较大的离子簇和较小的疏水组装域导致更好的离子通道连通性。这些特征和观察到的高离子交换容量和窄分布的超微孔协同决定了它的高电导率。此外，SP3膜表现出优异的氧化稳定性和良好的机械性能，使其能够成功应用于H ₂ /空气质子交换膜燃料电池。