Epoxy resin (EP) composites with improved thermal resistance were fabricated. To solve the problem of low thermal resistance derived from phosphazene flame-retardant additives, we designed a system based on flame-retardant microcapsules P(H), with hexaphenoxycyclotriphosphazene as the core and polymethyl methacrylate as the shell. The core-shell structure was characterized and confirmed. The thermal resistance of the cured EP composites containing 1 wt% P(H) microcapsules was improved because of the increased glass transition temperatures. The P(2.75H)/EP composites can reach a limited oxygen index of 30.5% and V-1 rating in UL-94 tests. Heat and gas release rates were reduced during combustion tests. Residual images implied that the P(H) microcapsules may promote the formation of a flame-retardant char layer. Pyrolysis analysis demonstrated that the P(H) microcapsules can decompose in two procedures to produce flame-retardant gas components. Therefore, the flame-retardant mechanism involved the flame inhibition effect in the gas phase, and the charring effect in the condensed phase.
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