Core-shell flame retardant/APP-PEI@MXene@ZIF-67: A nanomaterials self-assembly strategy towards reducing fire hazard of thermoplastic polyurethane

Ammonium polyphosphate (APP) is the most commercially valuable phosphorus-based flame retardant, but poor interaction with the polymer interface limits the flame-retardant efficiency. In this work, a new type of multi-layered nanomaterial coating APP (APP-PEI@MXene@ZIF-67) was prepared and introduced into thermoplastic polyurethane (TPU) polymers by a simple and green assembly strategy. The effects of different loading shells of modified APP on the flame retardancy of TPU composites were investigated, as well as their gas/condensed phase thermal degradation products and their flame-retardant mechanisms. The results showed that APP-PEI@MXene@ZIF-67 was more favorable for catalytic char formation than APP, and the residual char formed by its composites was denser and more continuous. Compared with the pure TPU, the pHRR, THR, pSPR, and TSP of TPU/APP-PEI@MXene@ZIF-67-2BL composites were decreased by 72.75%, 87.25%, 59.58%, and 85.97%, respectively, which significantly reduced the heat and smoke release during the combustion process. The gas-phase and condensed-phase flame retardant mechanisms synergized to construct a possible approach to address the fire risk and heat/smoke hazards of TPUs and promote the extensive application of TPU polymers.