Molecular dynamics simulation of nanoscale distribution and mobility of water and dimethylmethylphosphonate in...

The interest in a better understanding of the specific interactions of phosphor-organic compounds and water with sulfonated polystyrene (sPS) is motivated by the use of block copolymers as protective membranes against chemical warfare agents. Using classical molecular dynamics simulations, we explored the nanoscale segregation and diffusion of water and nerve gas simulant dimethylmethylphosphonate (DMMP) in sPS neutralized with calcium counterions at different sulfonation and hydration levels. The water content was varied from 15 to 54% of dry polymer weight, and the DMMP content was varied from 0 to 100 wt %. We found that, in the 40% sulfonated polystyrene, water forms well defined aggregates, which grow in size as the hydration increases, reaching approximately 20 A at the maximum water content. In the 100% sulfonated polystyrene, the overall structure of hydrated polymer is more uniform with smaller water aggregates. Diffusion of water at the same number of water molecules per sulfonate group is faster at a lower sulfonation level. The solvation of sPS in water-DMMP binary mixtures was found to differ substantially from Nafion, where DMMP forms a layer between the hydropholic and hydrophobic subphases. In sPS with divalent Ca(2+) counterions, DMMP and water compete for the solvation of the sulfonate group. At high water and DMMP contents, the diffusion of DMMP turned out to be rather fast with a diffusion coefficient of ca. 30% of that of water. At the same time, water diffusion slows down as the DMMP concentration increases. This observation suggests that although sPS is permeable for both solvents, water and DMMP are partially segregated on the scale of 1-2 nm and have different pathways through the system. The nonuniform nanoscale distribution of water and DMMP in sPS is confirmed by analyses of different pair correlation functions. This feature may significantly affect the perm-selective properties of sPS-contained block copolymer membranes.