Lignin was utilized as an environmentally friendly synergistic agent to augment the fire resistance and mechanical characteristics of rigid polyurethane foam (PUF)/melamine-formaldehyde resin ammonium polyphosphate (MFAPP). The incorporation of lignin significantly enhanced the charring capability and flame retardancy of PUF/MFAPP. Specifically, PUF/MFAPP12/A-lignin3 exhibited a charring residue of 23.1% at 800 °C, accompanied by an increase in the limiting oxygen index (LOI) to 23.1%, resulting in a UL-94 V-0 rating. The cone calorimeter test (CCT) revealed that the peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), and total smoke production (TSP) values of PUF/MFAPP12/A-lignin3 were all lower than for pure PUF. MFAPP and alkali lignin exerted a noticeable influence on the physical and mechanical properties, leading to increases in density (35.4 kg/m3), thermal conductivity (32.68 mW/(m·K)), and compressive strength (160.5 kPa). Observations of the morphology and elemental composition of char residues after combustion indicated the formation of an intact, thick, and continuous char layer enriched with nitrogen and phosphorus elements, which acted as a protective shield for the underlying foam.
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