Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.