An Effective Green Porous Structural Adhesive for Thermal Insulating, Flame-Retardant, and Smoke-Suppressant Expandable Polystyrene Foam

To develop an efficient way to overcome the contradiction among flame retardancy, smoke suppression, and thermal insulation in expanded polystyrene (EPS) foams, which are widely used insulation materials in buildings, a novel “green” porous bio-based flame-retardant starch (FRS) coating was designed from starch modified with phytic acid (PA) that simultaneously acts as both a flame retardant and an adhesive. This porous FRS coating has open pores, which, in combination with the closed cells formed by EPS beads, create a hierarchically porous structure in FRS–EPS that results in superior thermal insulation with a lower thermal conductivity of 27.0 mW·(m·K) − 1 . The resultant FRS–EPS foam showed extremely low heat-release rates and smoke-production release, indicating excellent fire retardancy and smoke suppression. The specific optical density was as low as 121, which was 80.6% lower than that of neat EPS, at 624. The FRS–EPS also exhibited self-extinguishing behavior in vertical burning tests and had a high limiting oxygen index (LOI) value of 35.5%. More interestingly, after being burnt with an alcohol lamp for 30 min, the top side temperature of the FRS–EPS remained at only 140 °C with ignition, thereby exhibiting excellent fire resistance. Mechanism analysis confirmed the intumescent action of FRS, which forms a compact phosphorus-rich hybrid barrier, and the phosphorus-containing compounds that formed in the gas phase contributed to the excellent flame retardancy and smoke suppression of FRS–EPS. This novel porous biomass-based FRS system provides a promising strategy for fabricating polymer foams with excellent flame retardancy, smoke suppression, and thermal insulation.