High Thermal Resistance of Epoxy/Cyanate Ester Hybrids Incorporating an Inorganic Double-Decker-Shaped Polyhedral Silsesquioxane Nanomaterial.

In this study, we prepared a difunctionalized cyanate ester double-decker silsesquioxane (DDSQ-OCN) cage with a char yield and thermal decomposition temperature () which were both much higher than those of a typical bisphenol A dicyanate ester (BADCy, without the DDSQ cage) after thermal polymerization. Here, the inorganic DDSQ nanomaterial improved the thermal behavior through a nano-reinforcement effect. Blending the inorganic DDSQ-OCN cage into the epoxy resin improved its thermal and mechanical stabilities after the ring-opening polymerization of the epoxy units during thermal polymerization. The enhancement in the physical properties arose from the copolymerization of the epoxy and OCN units to form the organic/inorganic covalently bonded network structure, as well as the hydrogen bonding of the OH groups of the epoxy with the SiOSi moieties of the DDSQ units. For example, the epoxy/DDSQ-OCN = 1/1 hybrid, prepared without Cu(II)-acac as a catalyst, exhibited a glass transition temperature, thermal decomposition temperature (), and char yield (166 °C, 427 °C, and 51.0 wt%, respectively) that were significantly higher than those obtained when applying typical organic curing agents in the epoxy resin. The addition of Cu(II)-acac into the epoxy/BADCy and epoxy/DDSQ-OCN hybrids decreased the thermal stability (as characterized by the values of and the char yields) because the crosslinking density and post-hardening also decreased during thermal polymerization; nevertheless, it accelerated the thermal polymerization to a lower curing peak temperature, which is potentially useful for real applications as epoxy molding compounds.