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A novel nitrogen–phosphorus flame retardant (P–N FR) based on phosphonamidate, dimethyl N,N′-1,3-phenylenebis(P-methylphosphonamidate) (DMPMP), was successfully synthesized and its flame-retarding performances and thermal degradation were compared with those of other P–N FRs and a phosphorus-based FR such as resorcinol bis(diphenyl phosphate) (RDP). DMPMP was applied to acrylonitrile–butadiene–styrene (ABS) and ethylene–vinyl acetate (EVA) to investigate the factors governing the flame-retarding behaviors of P–N FRs which would make them efficient for noncharrable polymers. V-0 ratings were achieved at 20 wt % loading of DMPMP for ABS and at a much lesser amount of DMPMP loading (10 wt %) for EVA. Meanwhile, no rating and V-2 were achieved even at 20–30 wt % loading of other P–N FRs or RDP for ABS and EVA, respectively. The results from thermogravimetric analysis, Fourier transform infrared, and UL-94V indicated that DMPMP is a highly efficient FR and acts mainly in a gas-phase flame-retarding mode of action. The condensed phase of DMPMP also contributed to the flame retardancy property through −NH– groups which tendentiously generate a nitrogen–phosphorus-rich residue because of the intermolecular coupling transesterification reaction. These results demonstrated the assumption that DMPMP has a high P content and good hydrostability, which exhibits good flame retardancy for noncharrable polymers such as ABS and EVA.

Rigid polyurethane foam (PUF) was successfully prepared from a novel oligo-ester-ether-diol obtained from the glycolysis of waste poly(ethylene terephthalate) (PET) bottles via reaction with diethylene glycol (DEG) in the presence of ZnSO4 7H2O. The LC-MS analysis of the oligodiol enabled us to identify 67 chemical homologous structures that were composed of zero to four terephthalate (T) ester units and two to twelve monoethylene glycol (M) ether units. The flame retardant, morphological, compression, and thermal properties of rigid PUFs with and without triphenyl phosphate (TPP) were determined. The Tg values showed that TPP played a role of not only being a flame retardant, but also a plasticizer. PUF with a rather low TPP loading had an excellent flame retardancy and high thermal stability. A loading of 10 wt % TPP not only achieved a UL-94 V-0 rating, but also obtained an LOI value of 21%. Meanwhile, the PUF without a flame retardant did not achieve a UL-94 HB rating; the sample completely burned to the holder clamp and yielded a low LOI value (17%). The fire properties measured with the cone calorimeter were also discussed, and the results further proved that the flame retardancy of the PUF with the addition of TPP was improved significantly. The polymeric material meets the demands of density and compression strength for commercial PUF, as well as the needs of environmental development. The current study may help overcome the drawback of intrinsic high flammability and enlarge the fire safety applications of materials with a high percentage of recycled PET.