Air‐Stable Polyphosphazene‐Functionalized Few‐Layer Black Phosphorene for Flame Retardancy of Epoxy Resins

Abstract Similar to graphene, few‐layer black phosphorus (BP) features thermal stability, mechanical properties, and characteristic dimension effects, which has potential as a new member of nanofillers for fabricating polymer nanocomposites. Herein, a cross‐linked polyphosphazene‐functionalized BP (BP‐PZN) is developed with abundant –NH 2 groups via a one‐pot polycondensation of 4,4′‐diaminodiphenyl ether and hexachlorocyclotriphosphazene on the surface of BP nanosheets. Whereafter, the resulting BP‐PZN is incorporated into epoxy resin (EP) to study the flame‐retardant property and smoke suppression performance. Cone results show that the introduction of 2 wt% BP‐PZN distinctly improves the flame‐retardant property of EP, for instance, 59.4% decrease in peak heat release rate and 63.6% reduction in total heat release. The diffusion of pyrolysis products from EP during combustion is obviously suppressed after incorporating the BP‐PZN nanosheets. Meanwhile, the EP/BP‐PZN nanocomposites exhibit air stability after exposure to ambient conditions for four months. The air stability of the BP nanosheets in EP matrix is assigned to surface wrapping by PZN and embedded in the polymer matrix as dual protection. As a new member of the 2D nanomaterials, BP nanosheets have potential to be a new choice for fabricating high‐performance nanocomposites.