New Epoxy Thermosets Organic-Inorganic Hybrid Nanomaterials Derived from Imidazolium Ionic Liquid Monomers and POSS(®Ph)

New epoxy-amine networks issue from epoxydized imidazolium ionic liquid monomers (ILMs) and isophorone diamine (IPD) were modified for the first time by incorporating unmodified trisilanol phenyl POSS(®) (POSS(®Ph)-triol) and two ionic liquid-modified POSS(®Ph) (IL-g-POSS(®Ph)) having chloride (Cl(−)) and bis-trifluoromethanesulfonimidate (NTf(2)(−)) counter anions. Then, 5 wt.% of unmodified and IL-modified POSS(®Ph) were introduced in order to develop new solid electrolytes. First, a homogeneous dispersion of the POSS(®Ph) aggregates (diameters from 80 to 400 nm) into epoxy networks was observed. As a consequence, ILM/IPD networks with glass transition temperatures between 45 and 71 °C combined with an enhancement of the thermal stability (>380 °C) were prepared. Moreover, a significant increase of the hydrophobic character and high oil repellency of the network surfaces were obtained by using IL-g-POSS(®Ph) (19–20 mJ.m(−2)), opening up promising prospects for surface coating applications. Finally, these new epoxy networks exhibited outstanding high ionic conductivities (from 3.4 × 10(−8) to 6.8 × 10(−2) S.m(−1)) combined with an increase in permitivity.