Synthesis of 3,13‐diglycidyloxypropyloctaphenyl double‐decker polyhedral oligomeric silsesquioxane and the thermal reaction properties with thermosetting phenol‐formaldehyde resin

3,13‐Diglycidyloxypropyloctaphenyl double‐decker silsesquioxane (EP‐DDSQ) was synthesized by process of alkaline hydrolysis condensation of phenyltrimethoxysilane and corner capping reaction of methyldichlorosilane, followed by hydrosilylation with allyl glycidyl ether, and the resultant structure was confirmed by fourier transform infrared spectrometer (FTIR) and nuclear magnetic resonance (NMR), respectively. The thermosetting phenol‐formaldehyde (PF) resin was then modified by EP‐DDSQ, and the reactivity of PF resin with EP‐DDSQ and thermal pyrolysis of modified cured resin were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The surface morphologies of modified resins at high temperature were characterized with field emission scanning electron microscope (FESEM), and chemical structure of modified resins was analyzed through X‐ray photoelectron spectrometer (XPS). The results showed that the appropriate addition of EP‐DDSQ did not affect the curing temperature of the PF resin itself, but could improve the heat resistance of the system. When the amount of EP‐DDSQ added was 10%, the initial degradation temperature of PF resin was increased by 49.31°C, and when the amount of EP‐DDSQ added was 16%, the char yield of which was reached up to 61.39%, compared with that of pure PF resin (TGA1,000°C of 57.62%) at Ar atmosphere. More importantly, the modified resin formed a regular and dense layer of SiC and SiOx ceramic on the surface after ablation in the muffle furnace at 800°C air atmosphere, which is very important for ablative resistant materials.