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In this paper, the ODOPM, a kind of 9, 10-dihydro-9-oxygen-heterooxy-10-phosphoro-10-oxygen (DOPO) derivative, was obtained by hydroxylation of DOPO. Further, a phosphorus nano-flame retardant (GO-ODOPM) was obtained by addition reaction with carboxylated Graphite Oxide (GO-COOH). And then Graphene Oxide/polystyrene (GO-ODOPM/PS) composite microspheres were obtained via suspension polymerization of styrene with GO-ODOPM. The decrease of the peak heat release rate (HRR) and total heat release rate (THR) for the GO-ODOPM/PS composite micro