The Nanostructure of HMT-PMBI, a Sterically Hindered Ionene

EM Schibli and JC Stewart and AA Wright and BY Chen and S Holdcroft and BJ Frisken, MACROMOLECULES, 53, 4908-4916 (2020).

DOI: 10.1021/acs.macromol.0c00978

We have studied the nanoscale structure of a novel benzimidazolium-based ionene, methylated poly(hexamethyl-p-terphenyl benzimidazolium) (HMT- PMBI), using a combination of X-ray scattering experiments and molecular dynamics simulations to explore samples with different levels of hydration and containing different anions. HMT-PMBI shows a remarkably simple morphology. At low levels of hydration, the bulky polymer backbones are unable to pack efficiently, leaving approximately 10% of the sample volume free of polymers, anions, or water. As the hydration levels are increased, water fills the free volume, forming a percolating network. This network forms at hydration levels as low as lambda = 4 in samples containing less hydrophilic anions, such as bromide or iodide. At higher degrees of hydration, water simply forces the polymer backbones apart.

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