AbstractAmmonium polyphosphate is shown to be an effective flame retardant for homopolymeric and selected fibre‐forming copolymers of acrylonitrile. Compared with other phosphates and phosphorus‐containing species, it significantly increases both limiting oxygen index and char levels. The mechanism of retardancy is shown to be both physical and chemical in character. When heated to 300°C, the polyphosphate melts and converts to polyphosphoric acid which acts as a physical barrier to surface polymer oxidation and promotes nucleophilic oligomerization of pendant, adjacent nitrile groups. A reduction in the activation energy of this first stage of acrylic polymer degradation suggests that the favoured decomposition route gives rise via oligomerization to char‐promoting precursors. Char analyses indicate an empirical formula of C30H13N7P2, which compares favourably with that of a proposed phosphorylated, polynuclear, aromatic heterocyclic str
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