Phosphorus-containing flame retardants synthesized from renewable resources have had a lot of impact in recent years. This article outlines the synthesis, characterization and evaluation of these compounds in polyesters and epoxy resins. The different approaches used in producing biobased flame retardant polyesters and epoxy resins are reported. While for the polyesters biomass derived compounds usually are phosphorylated and melt blended with the polymer, biobased flame retardants for epoxy resins are directly incorporated into the polymer structure by a using a phosphorylated biobased monomer or curing agent. Evaluating the efficiency of the flame retardant composites is done by discussing results obtained from UL94 vertical burning, limiting oxygen index (LOI) and cone calorimetry tests. The review ends with an outlook on future development trends of biobased flame retardant systems for polyesters and epoxy resins.

Novel polymeric flame retardants based on two acrylamides and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 5,5-dimethyl-[1,3,2]dioxaphosphinane-2-oxide (DDPO) are described for several applications in HexFlow® RTM6, a high-performance epoxy resin. Neat resin samples and carbon fiber-reinforced composites were tested for their glass transition temperatures (dynamic mechanical analysis), thermal stability (thermogravimetric analyses), flammability (UL94) and flame-retardant performance (Cone Calorimetry). Additionally, the fiber degradation occurring during combustion of carbon fiber-reinforced epoxy resins was observed by scanning electron microscopy to show the fiber protecting effect of these flame retardants. Whereas DOPO-containing polyacrylamides acting mainly in the gas phase showed the best flame retardant efficiency, DDPO-containing polyacrylamides acting mainly in the condensed phase showed the best fiber protection. A mixed polyacrylamide was synthesized to combine these effects. This thermoplastic is soluble in the resin and, therefore, suitable for injection molding processes. Interlaminar shear strength measurements showed no negative effect of the flame retardant. The versatility of these flame retardants is shown by investigations dealing with boehmite as synergist in neat resin samples.

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Novel polymeric acrylate-based flame retardants (FR 1–4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations with the synthesized compounds were investigated to evaluate the efficiency of these flame retardants and their mode of action by using TGA, UL94, and cone calorimetry. In order to compare the results a flame retardant polyester containing only one phosphorus group (ItaP) was also investigated in PLA regarding its flame inhibiting effect. Since the fire behavior depends not only on the mode of action of the flame retardants but also strongly on physical phenomena like melt dripping, the flame retardants were also incorporated into PLA with higher viscosity. In the UL94 vertical burning test setup, 10% of the novel flame retardants (FR 1–4) is sufficient to reach a V-0 rating in both PLA types, while a loading of 15% of ItaP is not enough to reach the same classification. Despite their different structure, TGA and cone calorimetry results confirmed a gas phase mechanism mainly responsible for the highly efficient flame retardancy for all compounds. Finally, cone calorimetry tests of the flame retardant PLA with two heat fluxes showed different flame inhibiting efficiencies for different fire scenarios.