A series of novel silicon-containing epoxy/PEPA phosphate flame retardants (EPPSi) were synthesized by polyphosphoric acid (PPA), caged bicyclic phosphate 1-oxo-4-hydroxymethy1-2,6,7trioxa-L-phosphabicyclo [2.2.2] octane (PEPA), and different ratios of silicon-containing epoxy 1,1,3,3-tetramethy1-1,3-bis(3-(oxiran-2-ylmethoxy)propyl)disiloxane (TMSEP) to 1,4-butanediol diglycidyl ether (BDE). The chemical structure of EPPSi was confirmed by Fourier transform infrared spectroscopy (FTIR) and H-1 nuclear magnetic resonance spectroscopy (H-1 NMR). Afterwards, the transparent intumescent fire resistant coatings were prepared by mixing EPPSi and melamine formaldehyde resin. The influence of silicon on the fire protection of coatings was intensively investigated by fire protection test, intumescence ratio, scanning electron microscope (SEM), compressive strength test, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and real-time FTIR. It was found that the fire resistant coatings obtained the best fire protection when the ratio of TMESP/BDE was 20/100, while excessive TMSEP made the fire protection of coatings deceased sharply. The intumescence ratio, compressive strength test and SEM result showed that a synergistic effect existed between phosphorus and silicon, which improved the foam structure and compressive strength of the char layer significantly. XPS result proved the out -migration effect of silicon. The high concentration silicon on surface played an important protecting role for the inner char residue and improved the fire protection of the coatings. TGA result demonstrated that silicon enhanced the thermo-oxidation resistance of coatings efficiently. Furthermore, real-time FTIR revealed the intumescent process of the fire resistant coatings according to the chemical structure changes of char residue. (C) 2016 Elsevier B.V. All rights reserved.