In this work, a novel functionalization strategy for ZIF-67-modified layered MXene was proposed, aiming at improving the fire safety of thermoplastic polyurethanes (TPU). The ZIF-67@MXene was verified by microscopic morphology, elemental composition, functional group species and crystal structure, and then the successfully prepared ZIF-67@MXene was introduced into the TPU material. When ZIF-67@MXene content was only 0.5 wt%, the peak heat release rate, total heat release rate, peak smoke release rate, total smoke release rate, and CO yield of the TPU/ZIF-67@MXene composites were reduced by 26%, 9%, 50%, and 22%, respectively, compared with the pure TPU. The thermogravimetric tests showed that the residual char of TPU/ZIF-67@MXene composites was the most in all samples. In short, the high-quality carbon layer of TPU/ZIF-67@MXene composites acts as a physical barrier to the transfer of heat and toxic gases, greatly improving the flame retardant properties of the TPU polymer.

Designing eco-friendly fireproof rigid polyurethane foam (RPUF) that can completely stop fire ignition or spread has significant technological implications, which has been proved to be extremely challenging. Herein, a novel green strategy based on double network hydrogel coating was developed to enhance the flame retardancy of RPUF via a facile casting and curing process. This strategy can create a homogeneous hydrogel fire-resistant layer with strong adhesion on the outermost surface of the substrate. Due to good water holding capacity and excellent thermal management properties, the hydrogel coating showed excellent fire retardancy. As a proof-of-concept, polyacrylic–polydopamine (PAAm–PDA) double network hydrogel coating was applied to an extremely flammable RPUF substrate. Compared with the neat foam, the PAAm–PDA coated RPUF exhibited an overall improvement in fire-safety performance, including a rapid self-quenching behavior, a six-fold enhancement in time to ignition (TTI), and 39.7% and 42.2% decreases in the mean heat release rate (HRR) and total smoke production (TSP), respectively. Furthermore, the tough hydrogel-coated RPUF possessed enough mechanical properties to meet the requirement of its practical applications. Benefiting from its low cost, easy-to-process and eco-friendly characteristics, this hydrogel fireproof coating strategy provides a new direction for developing green and safe structural materials with widespread use.