Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle

Abstract

A phosphorous/nitrogen-containing reactive phenolic derivative (DOPO–HPM) was synthesized via the addition reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and N-(4-hydroxyphenyl) maleimide (HPM). The structure of DOPO–HPM was characterized by Fourier transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic resonance (NMR) and elemental analysis (EA). The studied flame-retardant epoxy resin systems were prepared by copolymerizing diglycidyl ether of bisphenol-A (DGEBA) with DOPO–HPM, triglycidyl isocyanurate (TGIC) and 4,4′-diamino-diphenyl sulfone (DDS). Thermal and flame retardant properties of the cured epoxy resins were investigated by differential scanning calorimeter (DSC), thermogravimeric analysis (TGA), limited oxygen index (LOI) measurement, UL94 test and cone calorimeter. The DSC results indicated that the modified epoxy resins showed little fluctuation in glass transition temperatures (197–205 °C). The results of combustion tests indicated that the modified epoxy resin systems exhibited excellent flame retardant properties. The P-1 and P-1.25 systems acquired LOI values of 37% and 38.5%, respectively, and achieved a UL94 V-0 rating. Compared with the P-0 system, the peak of heat release rate (pk-HRR), average of effective heat of combustion (av-EHC) and total heat release (THR) of P-1.25 system decreased by 61.4%, 23.4% and 34.9%, respectively. In addition, the total smoke production (TSP) of the modified epoxy resin systems decreased with the increasing content of flame retardants, indicating the smoke suppression effect of the flame-retardant systems. Through visual observation, the char residues after cone calorimetry test exhibited intumescent structures with continuous and compact surfaces. The flame retardant mechanism was studied by FTIR, scanning electron microscope (SEM), cone calorimeter and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS).