Highly-effective non-halogenated flame retardants have received widespread attention because they are environmentally friendly, with low toxicity and low smoke density. In this work, interlayer-functionalized graphene (fRGO) containing silicon and phosphorus elements was synthesized via hydrolytic condensation with 3-(methacryloyloxy)propyltrimethoxysilane and addition reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Interlayer spacing and oxygen-containing groups of reduced graphene oxide (RGO) were regulated by controlling the hydrazine hydrate dosage. Then, phosphorus–silicon-containing organic molecules were inserted into RGO interlayers; this was verified by FTIR, XPS, TEM, etc. The fRGO was added to a polyacrylonitrile (PAN) matrix using a solution blending method to prepare polyacrylonitrile (PAN) composites. The fRGO addition caused the significant decrease in cyclization heat and the considerable increase in char residues, indicating improved thermal stability. Importantly, PAN composites exhibited outstanding flame-retardant properties, with the peak heat release rate reduced by 45%, which is ascribed to the dense graphitic carbon layers induced by phosphorus–silicon-containing organics and the 2D barrier effect of RGO layers to prevent the heat and mass transfer.
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