Polyphosphazene derivatives are gaining popularity due to their eco-friendly character and high content of flame-retardant components. Herein, a polyphosphazene derivative (PZAF) microsphere was successfully synthesized utilizing an in-situ template approach, which was then employed as an additive flame retardant in polyethylene terephthalate (PET) to improve the fire safety. Thermogravimetric analysis revealed that PZAF promoted the pyrolysis of PET in advance to generate a stable char layer that protects the matrix from heat, consequently increasing char residues. With addition of 10 wt% PZAF, the PET nanocomposites obtained a V-0 grade in vertical combustion test and its LOI value increased from 24.2 vol% to 32.1 vol%. Moreover, the peak heat release and carbon monoxide production decreased by 46.6% and 50.6%, respectively. This was because the phosphonic acid fragments and pyridine ring compounds produced by the PZAF pyrolysis encouraged the development of a robust char layer. Meanwhile, the •PO radicals generated by the pyrolysis of PZAF could capture free radicals in the gas phase, ultimately ending the chain reaction of combustion. Also, mechanical properties of the PET nanocomposites were noticeably enhanced by the addition of 3 or 5 wt% PZAF.
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