Linear Viscoelastic and Dielectric Properties of Phosphonium Siloxane Ionomers.

The linear viscoelastic (LVE) and dielectric relaxation spectroscopic (DRS) properties of polysiloxanes with phosphonium (fraction f) and oligo(ethylene oxide) (fraction 1 - f) side groups with a fraction of ionic monomers f = 0-0.26 have been studied. LVE master curves of those ionomers have been constructed. The ionic dissociation has been witnessed as a delayed polymer relaxation in LVE with increasing ion content, as well as an α2 ionic segmental relaxation process in DRS. LVE exhibits glassy and delayed rubbery relaxation at low ionic fraction f ≤ 11%, where the ionic dissociation time detected in DRS enables description of LVE with a sticky Rouse model. In contrast, the glassy and rubbery stress relaxation moduli merge into one broad process at high f ≥ 22%, where the whole LVE response from glassy to terminal relaxation can be described phenomenologically by a single Kohlrausch-Williams-Watts (KWW) equation with the lowest stretching exponent β = 0.10 ever seen for polymeric liquids, describing LVE over 15 decades of frequency.

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