Flame Retardancy of Vinyl Acetate–Ethylene Emulsion Adhesives Modified with Intumescent Flame Retardants and Fly Ash

Vinyl acetate–ethylene copolymer emulsion (VAE) adhesives are widely used in formaldehyde-free wood-based panels and coating systems, but their inherent flammability limits broader application in fire-safety-demanding fields. In this work, fly ash (FA), an industrial solid waste rich in Si- and Al-containing inorganic components, was introduced into a conventional ammonium polyphosphate/melamine/pentaerythritol (APP/MEL/PER) intumescent flame-retardant (IFR) system to prepare flame-retardant VAE emulsion adhesives. The results showed that the incorporation of IFR effectively improved the flame retardancy of VAE, while FA further enhanced the condensed-phase protective effect. The limiting oxygen index (LOI) of VAE/IFR/FA increased to 28.5% from 18.3% for neat VAE, and the sample achieved a UL-94 V-0 rating. Cone calorimetry results showed that the peak heat release rate and total heat release were significantly reduced after flame-retardant modification, accompanied by an increase in residual char. The VAE/IFR/FA sample exhibited the highest char residue and the lowest total smoke production, indicating the positive role of FA in promoting char formation and smoke suppression. The addition of KH403 further regulated the combustion behavior, mainly improving early-stage heat release suppression and fire performance index rather than increasing the final char yield. The KH403-containing formulation also showed improved tensile properties and plywood bonding strength, indicating its potential as a flame-retardant adhesive for wood-based panels. The KH403-containing formulation also showed improved tensile properties and plywood bonding strength, indicating its potential as a flame-retardant adhesive for wood-based panels. SEM-EDS, XPS, Raman, and TG-FTIR analyses confirmed that FA and KH403 contributed to the formation of a phosphorus-rich organic–inorganic hybrid char layer containing Si/Al inorganic structures. This reinforced char layer effectively inhibited heat transfer, oxygen diffusion, and the release of combustible volatiles. This study provides a feasible strategy for developing low-cost flame-retardant VAE adhesives while promoting the high-value utilization of fly ash.