A bio-based reactive phosphate flame retardant derived from iso-eugenol was synthesized and fully characterized (1 H, 13 C, 31 P NMR, FTIR, MS) with the aim of improving flame retardancy behavior of bio-based epoxy thermosets. This new green flame retardant, diepoxy-iso-eugenol phenylphosphate (DEpiEPP) was then copolymerized either with conventional diglycidylether of bisphenol A resin (DGEBA) or with a totally bio-based glycidylether epoxy iso-eugenol (GEEpiE) resin using a bio-based camphoric anhydride (CA) as hardener. Resulting thermosets with varying rates of flame retardant (1.0 to 4.3 w% phosphorus) were then characterized (FTIR, DSC, nanoindentation, 3-point bending test, TGA, PCFC, cone calorimeter). By this way, a new solution was proposed allowing (i) to increase the bio-based content of thermosets (ii) to improve the flame retardancy properties by a reactive way and (iii) to provide epoxy thermosets with high Tg, excellent mechanical properties and a curing temperature compatible with the use of vegetable fibers. For instance, with a weight content of 2.0 w% P, both GEEpiE-CA-DEpiEPP (95% bio-based content) and partially bio-based DGEBA-CA-DEpiEPP (57% bio-based content) epoxy thermosets possess high Tg (respectively 129 and 105°C), bending elastic modulus and strength of respectively 4.08 GPa and 90 MPa and demonstrate good flameretardant properties due to char promotion showing high promise for application.
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