Phosphorus-containing reactive compounds to prepare fire-resistant vinyl resin for composites: Effects of flame retardant structures on properties and mechanisms

[Display omitted] •Synthesis of six novel phosphorus-containing liquid reactive flame retardants.•Low viscosity, flame retardant and toughened vinyl resin for CF composites.•Valence state and group of phosphorus affect the flame retardant mechanism. The traditional flame-retardant method for carbon fiber reinforced vinyl ester resin composites is to add a large amount of solid flame retardants, which not only leads to the deterioration of the material's mechanical properties, but also increases the resin viscosity and affects the molding process of composites. In addressing this issue, this work adopts a liquid reactive flame retardant strategy and synthesizes six novel liquid phosphorus-containing reactive compounds as flame retardants. A comparative study is conducted on the effects of the structure of compounds (valence and group of phosphorus and number of reaction groups) on the properties of materials. The results demonstrate significantly improved flame retardancy and toughness, as well as unaffected viscosity and strength of the resin. When the phosphorus content does not exceed 3 wt%, the limiting oxygen index (LOI) of the resin can reach over 30% and UL-94 passes the V-0 rating. The structure of compounds significantly affects their flame retardancy mechanism. Especially, compounds rich in P-O-C structure have more outstanding condensed phase flame retardancy (promoting charring) and are more favorable for improving the LOI; Compounds rich in P-Ph and P-C structures have higher thermal stability and mainly exert gas phase flame retardancy, which is more beneficial for improving the self-extinguishing properties of materials. Furthermore, a synergistic flame retardant effect is observed between carbon fiber and compounds rich in P-Ph.