Hydration, Ion Distribution, and Ionic Network Formation in Sulfonated Poly(arylene ether sulfones)

B Vondrasek and CY Wen and SF Cheng and JS Riffle and JJ Lesko, MACROMOLECULES, 54, 302-315 (2021).

DOI: 10.1021/acs.macromol.0c01855

We use molecular dynamics simulations to probe hydration, ion spacing, and cation-anion interaction in two sulfonated polysulfones with different ion distributions along the polymer backbone. At room temperature, these polymers are below their experimental glass transition temperatures even with water contents more than 10%. At the equilibrium water uptake, the ions exhibit a similar level of hydration as they would in their saturated aqueous solution. The framework of Manning's limiting law for counterion condensation is used to examine ionic interactions in the simulated polysulfones. The dielectric constant (epsilon) that the ions experience can be well approximated by a volume-weighted average of the dielectric constants of the polymer backbone and water. Our results show that a reasonable estimate of the average interionic distance, b, is obtained by using the distance where the sulfonate-sulfonate coordination number reaches 1. The spacing of the sulfonate ions along the polysulfone backbone plays a role in determining their spatial distribution inside the hydrated polymer. As a result, the value of b is slightly larger for polymers where the sulfonate ions are more evenly spaced along the backbone, which is consistent with experimental evidence. The simulations reveal that the sulfonate ions and sodium counterions form fibrillar aggregates at water contents below the equilibrium water uptake. Such extensive ionic aggregates are expected to facilitate ion transport in sulfonated polysulfone membranes without the need for long-range chain motion as in the case of traditional rubbery ionic polymers. Our estimates for e and b are used in conjunction with Manning's theory to estimate the fraction of counterions condensed to the fixed ions. The prediction of Manning's theory agrees well with the result computed by directly counting the condensed sodium ions in the molecular dynamics simulations.

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