Water diffusion within hydrated model grafted polymeric membranes with bimodal side chain length distributions

The effect of bimodal side chain length distributions on pore morphology and solvent diffusion within hydrated amphiphilic polymeric membranes is predicted. Seven polymeric architectures are constructed from hydrophobic backbones from which at regular intervals side chains branch off that are alternatingly short (composed of p hydrophobic A fragments or beads) and long (q A fragments, q > p). The side chains are end-linked with a hydrophilic C fragment. Pore morphologies at a water volume fraction of 0.16 are calculated by dissipative particle dynamics (DPD). Water diffusion through the water containing pores is calculated by tracer diffusion calculations through 140 selected snapshots and from the water bead motions. Diffusion constants decrease with difference in side chain lengths, q - p. Overall, the distance between pores also decreases with q - p. The results are explained by counting for every architecture the average number of bonds 〈N(bond)〉 between an A and the nearest C fragment. These results are in line with a database that contains more than 60 architectures. Diffusion constants tend to increase linearly with 〈N(bond)〉|C|(-1)|A|, where |C| and |A| are the C and A bead fractions within the architecture. 〈N(bond)〉 is therefore expected to be an interesting design parameter for obtaining low percolation thresholds for solvent and/or proton diffusion.