Double-Decker-Shaped Polyhedral Silsesquioxanes Reinforced Epoxy/Bismaleimide Hybrids Featuring High Thermal Stability

In this study, we synthesized bismaleimide into a functionalized double-decker silsesquioxane (DDSQ) cage. This was achieved by hydrosilylation of DDSQ with nadic anhydride (ND), reacting it with excess p-phenylenediamine to obtain DDSQ-ND-NH(2), and treating with maleic anhydride (MA), which finally created a DDSQ-BMI cage structure. We observed that the thermal decomposition temperature (T(d)) and char yield were both increased upon increasing the thermal polymerization temperature, and that these two values were both significantly higher than pure BMI without the DDSQ cage structure since the inorganic DDSQ nanoparticle could strongly enhance the thermal stability based on the nano-reinforcement effect. Based on FTIR, TGA, and DMA analyses, it was found that blending epoxy resin with the DDSQ-BMI cage to form epoxy/DDSQ-BMI hybrids could also enhance the thermal and mechanical properties of epoxy resin due to the organic/inorganic network formation created by the ring-opening polymerization of the epoxy group and the addition polymerization of the BMI group due to the combination of the inorganic DDSQ cage structure and hydrogen bonding effect. The epoxy/DDSQ-BMI = 1/1 hybrid system displayed high T(g) value (188 °C), T(d) value (397 °C), and char yield (40.4 wt%), which was much higher than that of the typical DGEBA type epoxy resin with various organic curing agents.