Water Dissolved in a Variety of Polymers Studied by Molecular Dynamics Simulation and a Theory of Solutions

The performance of a polymer medium as a separation membrane is determined by the dissolution free energy ΔG and diffusion coefficient D of the permeant. In this work, ΔG and D of water are investigated with all-atom molecular dynamics simulation in a wide variety of polymer species in the amorphous state. The computed ΔG is shown to agree well with the experimental value for linear homopolymers, and the degrees of polymerization of the homopolymers do not affect ΔG when they are beyond ∼10. The copolymers of ethylene-vinylidene difluoride, ethylene-vinyl acetate, and ethylene-acrylamide are then examined by changing the repeating patterns of the constituent monomers in both the periodic and graft forms. It is found that ΔG is determined primarily by the overall compositions of the monomers and is not affected by the copolymerization topology (periodic or graft). The hydrophobicity of the copolymer is enhanced, furthermore, when the hydrophobicity and hydrophilicity of the ethylene and non-ethylene parts are well contrasted and those parts are fragmented along the polymer chain. According to the computed D, the diffusivity of water tends to be larger when the (co)polymer is more hydrophobic and ΔG is more positive. D is actually seen to vary by orders of magnitude with the polymer structures, while the effect of the polymer species on the water permeation is stronger for ΔG than for D.