Proprietary polyurea-based thermosets were produced from polyisocyanate and water glass (WG) using a phosphate-type phase transfer catalyst. WG was dispersed in the polyisocyanate resulting in water-in-oil (W/O) type emulsion. The polyurea matrix, formed after crosslinking, contained the WG derived silicate in coarse particles showing a broad particle size distribution. The mean particle size of the silicate was markedly reduced and its distribution narrowed when the polyisocyanate was hybridized with a peroxide crosslinkable vinylester resin (VE) when the amount of the latter was < 75%. This resin hybridization strongly improved the mechanical (flexural) properties of the related thermosets, however, at cost of the fracture mechanical characteristics (fracture toughness and energy under mode I condition). This was mostly attributed to the formation of a co-network or interpenetrated network between the polyurea and VE. The static flexural and fracture mechanical properties were determined as function of the resin hybridization ratio. It was found that the mechanical properties change according to the additivity rule as a function of the resin hybridization in the first approximation. The silicate dispersion and the failure behavior in the polyurea/VE hybrids were studied by scanning electron microscopy (SEM) and discussed. (c) 2006 Wiley Periodicals, Inc.