A discovery for phosphorus valence and unsaturated bonds in polyphosphate/polyphosphonate: Promotion or inhibition for its flame-retardant mode of action in PET

Four polyphosphate/polyphosphonate flame retardants (PAP, POP, PAP-UB and POP-UB) have been designed and synthesized to study the effects of phosphorus valence states and the presence of unsaturated carbon-carbon double bonds on self-cross-linking impacting flame-retardant modes of action. It was found that phosphorus valence states affect the proportion of flame-retardant activity between the gas phase and condensed phase. A phosphonate containing +3-valence phosphorus is primarily effective as a gas-phase flame-retardant, while the one containing +5-valence phosphorus mainly exerted an impact in the condensed phase. The introduction of an unsaturated bond enhances the carbon-forming effect promoted by polyphosphates/polyphosphonates in a degrading polymer matrix and increases the melt viscosity for blends at high temperature. The phosphorus-containing fragments which might have been released into the gas phase are locked in the condensed phase due to CC bonds cross-linking, thus forming more high-quality phosphorus-rich char layers. This effect balances the distribution of gas-phase and condense-phase flame-retardant effects and is especially obvious in PET/polyphosphonate blends containing +3-valence phosphorus, which originally plays mainly the role of a gas-phase flame retardant. PET blends containing unsaturated carbon-carbon double bonds display better carbon formation, flame-retardant activity and anti-dripping behavior than these do without this feature.