Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments

Abstract

Poly(arylene ether sulfone) (PSU) ionomers containing disulfonated aryl-SO₂-aryl and tetrasulfonated aryl-SO₂-aryl-aryl-SO₂-aryl segments, respectively, were synthesized and studied to establish their structure–property relationships as proton-exchange membranes. High molecular weight PSUs with different distributions of sulfone bridges in the backbone were prepared by nucleophilic aromatic substitution reactions involving 4,4′-dichlorodiphenyl sulfone (DCDPS), 4,4′-bis[(4-chlorophenyl)sulfonyl]-1,1′-biphenyl (BCPSB), 4,4′-isopropylidenediphenol (bisphenol A), and 4,4′-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P). The polymers were sulfonated viametallation and reaction with sulfur dioxide, followed by oxidation of the resulting sulfinates. This procedure allowed the introduction of two sulfonic acid units on electron-deficient aryl rings in ortho positions to each sulfone bridge of the PSUs. Analysis by small angle X-ray scattering of solvent cast membranes showed that ionic clustering was promoted in ionomers containing sulfonated BCPSB residues and flexible bisphenol P residues. The fully sulfonated PSUs had ion-exchange capacities (IECs) of 3.3–4.1 meq g⁻¹ and were water soluble. However, partly sulfonated polymers with IECs of approx. 1.7 meq g⁻¹ showed high proton conductivity at moderate water uptake and decomposed only above 240 °C during heating 1 °C min⁻¹ under air. This work demonstrated that BCPSB residues can be conveniently and fully tetrasulfonated, which opens possibilities to prepare various aromatic copolymers and membranes with locally very high densities of hydrolytically stable sulfonic acid groups.