The ubiquity of polymeric materials in daily life comes with an increased fire risk, and sustained research into efficient flame retardants is key to ensuring the safety of the populace and material goods from accidental fires. Phosphorus, a versatile and effective element for use in flame retardants, has the potential to supersede the halogenated variants that are still widely used today: current formulations employ a variety of modes of action and methods of implementation, as additives or as reactants, to solve the task of developing flame-retarding polymeric materials. Phosphorus-based flame retardants can act in both the gas and condensed phase during a fire. This Review investigates how current phosphorus chemistry helps in reducing the flammability of polymers, and addresses the future of sustainable, efficient, and safe phosphorus-based flame-retardants from renewable sources.

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Molecular Firefighting—How Modern Phosphorus Chemistry Can Help Solve the Challenge of Flame Retardancy

Enzyme-mediated free radical polymerization of styrene.

The flammability of a gaseous fuel can be investigated by finding the limiting mixture with air which just propagates a flame. For example,(1) mixtures of hydrogen and air burn only if the molecular ratio, O2/2H2, lies in the range 0.15–10. Mixtures of n-hexane and air burn only over a narrower range of compositions containing 0.3–1.8 times the stoichiometric amount of oxygen. The hydrocarbon may therefore be considered less flammable than hydrogen.

Candle-Type Test for Flammability of Polymers

Chemical modification of polymers with flame‐retardant compounds

A flame retardant synergism of organic disulfides and phosphorous compounds

Vinyl aromatic polymers such as polystyrene can be made nonflammable by the addition of halogen compounds. The amount of halogen required to make such polymers nonflammable can now be greatly reduced by the addition of small amounts of certain free radical initiators. Normally about 5 phr of acetylene tetrabromide (parts of additive per hundred parts of polymer) must be added to polystyrene to obtain a self-extinguishing polymer. Only 0.5 phr of acetylene tetrabromide is required if 0.5 phr dicumyl peroxide is added. This synergistic effect has been observed with a series of peroxides, hydroperoxides, azo compounds, quinone imines, benzothiazole sulfenamides, disulfides, and a bibenzyl compound. The synergistic mechanism seems to be based on a series of reactions involving attack of the polymer by the initiator and subsequent reaction between polymer fragments and the halogen compound. The result is a delay in the loss of halogen from the polymer mass and thus a more efficient use of the halogen additive for flame quenching. Known inhibitors of free radical reactions have a detrimental effect on the synergistic mechanism.

Synergism of free radical initiators with self‐extinguishing additives in vinyl aromatic polymers

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Synergism of free radical initiators with self‐extinguishing additives in vinyl aromatic polymers