Improving the flame retardancy of waterborne polyurethanes based on the synergistic effect of P–N flame retardants and a Schiff base

A novel reactive intumescent fire retardant hexa-[4-[(2-hydroxy-ethylimino)-methyl]-phenoxyl]-cyclotriphosphazene (HEPCP), containing both cyclotriphosphazene and Schiff base structures, is successfully prepared. The chemical structures of HEPCP and flame-retardant waterborne polyurethane (WPU) (FR-WPU) were characterized via31P, 1H NMR and FT-IR. Thermogravimetric (TG) analysis showed that HEPCP exhibited excellent thermal stability and produced rich char residue under high temperature compared with the control sample. The Schiff base and cyclotriphosphazene had a synergistic effect on the WPU. Limiting oxygen index (LOI) values of up to 26.7% were recorded; the dripping behavior was simultaneously improved and achieved a V-1 rating in the UL-94 test by incorporating 0.5 wt% phosphorus. In contrast to the pure WPU, the peak heat release rate (pHRR) of the FR-WPU/HEPCP5 decreased by 43.8%. The char residues increased from 0.63% to 6.96%, and scanning electron microscopy (SEM) showed a relatively continuous and membranous substance, with few holes. The results of TGA-FIR, Py-GC/MS and SEM indicated that HEPCP displayed a fire-retardant mechanism in the condensed-phase. In addition, the thermomechanical behaviors and the mechanical properties indicated that both mechanical properties and Tgh increased.