Sulfonated Binaphthyl-Containing Poly(arylene ether ketone)s with Rigid Backbone and Excellent Film-Forming Capability for Proton Exchange Membranes

Sterically hindered (S)-1,1'-binaphthyl-2,2'-diol had been successfully copolymerized with 4,4'-sulfonyldiphenol and 4,4'-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO₃H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with ion exchange capacities (IECs) ranging from 1.40 to 1.89 mmol·g^-1. The chemical structures of the polymers were confirmed by 2D ¹H⁻¹H COSY NMR and FT-IR. The thermal properties, water uptake, swelling ratio, proton conductivity, oxidative stability and mechanical properties of SPAEKs were investigated in detail. It was found that the conjugated but non-coplanar structure of binaphthyl unit endorsed excellent solubility and film-forming capability to SPAEKs. The SPAEK-50 with an IEC of 1.89 mmol·g^-1 exhibited a proton conductivity of 102 mS·cm^-1 at 30 °C, much higher than that of the state-of-the-art Nafion N212 membrane and those of many previously reported aromatic analogs, which may be attributed to the likely large intrinsic free volume of SPAEKs created by the highly twisted chain structures and the desirable microscopic morphology. Along with the remarkable water affinity, thermal stabilities and mechanical properties, the SPAEKs were demonstrated to be promising proton exchange membrane (PEM) candidates for potential membrane separations.