A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR and non-isothermal differential scanning calorimetry (DSC), which showed that the composites had completely cured with multiple polymerization mechanisms according to the oxazine ring-opening and epoxy resin (EP) polymerization. The thermal properties of the organic–inorganic polybenzoxazine (PBZ) nanocomposites were analyzed by DSC and thermogravimetric analysis (TGA). Furthermore, the X-ray diffraction analysis and the scanning electron microscopy (SEM) micrographs of the SPOSS-PBZ-E nanocomposites indicated that SPOSS was chemically incorporated into the hybrid nanocomposites in the size range of 80–200 nm. The flame retardancy of the benzoxazine epoxy resin composites was investigated by limiting oxygen index (LOI), UL 94 vertical burn test, and cone calorimeter tests. When the amount of SPOSS reached 10% or more, the vertical burning rating of the curing system arrived at V-1, and when the SPOSS-BOZ content reached 20 wt %, the thermal stability and flame retardancy of the material were both improved. Moreover, in the cone calorimeter testing, the addition of SPOSS-BOZ hindered the decomposition of the composites and led to a reduction in the peak heat release rate (pHRR), the average heat release rate (aHRR), and the total heat release (THR) values by about 20%, 25%, and 25%, respectively. The morphologies of the chars were also studied by SEM and energy dispersive X-ray spectroscopy (EDX), and the flame-retardant mechanism of POSS was mainly a condensed-phase flame retardant. The ceramic layer was formed by the enrichment of silicon on the char surface. When there are enough POSS nanoparticles, it can effectively protect the combustion of internal polymers.

In this work, the effect of a modified metal organic framework material on the fire resistance and mechanical properties of epoxy resin (EP) has been explored. The cobalt based metal organic framework (ZIF-67) was synthesized from an organic ligand with a Schiff base structure. Then DOPO@ZIF-67 was synthesized by modifying ZIF-67 with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and its effect on EP modification was explored. Compared with the pure EP, 4% DOPO@ZIF-67/EP passed the UL94 V-0 level and the ultimate oxygen index (LOI) reached 32.1%. The SEM pictures of carbon residue indicated that DOPO@ZIF-67 formed a more continuous and dense microstructure, which can enhance the thermal barrier and the physical barrier effect. The addition of DOPO@ZIF-67 also can effectively improve the stiffness and damping coefficient of EP composite material. The porous skeleton structure of DOPO@ZIF-67 can endow EP with rigidity and flame-retardant properties. Furthermore, the existence of DOPO made the combination of ZIF-67 with EP better. The results of this study suggest that DOPO@ZIF-67 may be a good additive for modification of the properties of epoxy thermosetting materials.