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Renewable alternatives for common thermoset resins are demanded to go for sustainability. The objective is to create a flame retarded epoxy resin from a commercial bio epoxy resin with halogen free inorganic and organic flame retardants, respectively. Alumina trihydrate, aluminum diethyl phosphinate, a DOPO-based phosphonamidate and ammonium polyphosphate seem to have promising performances. Properties are enhanced with different bio fillers: pyrolyzed cocoa shells and plant waste (provided by Otto A. Müller Recycling GmbH, thanks!), short fibers and nonwovens of the natural fiber kenaf, hydroxypropyl-ß-cyclodextrin and sulfobutylether-ß-cyclodextrin.
Fire performance is investigated by cone calorimeter examinations, LOI and UL-94 ratings. Thermal analysis is given by TG-FTIR and DSC measurements.
Combinations of flame retardants and bio-fillers lead to reduced PHRR and THR, reach V0 in UL-94 and have a significant increase in LOI of up to 37 vol.-%. 10 % ammonium polyphosphate with 10 % pyrolyzed cocoa shell performs best, builds a magnificent protective layer, and shows good intumescence.
Recycling of crosslinked fiber-reinforced polymers is difficult. Moreover, as they are often based on flammable resins, additional additives are needed. So-called “vitrimers” open the possibility of Recycling and reprocessing and repairing with dynamically crosslinked chemistries. To date, vitrimer-based composites still need flame retardant additives, such as organophosphates. An additive-free vitrimer composite has not been reported. Herein, we synthesized an intrinsic flame-retardant vitrimer, relying on vinylogous polyurethanes containing covalently installed phosphonates as flame-retardant units and prepared glassfiber-reinforced composites. We studied recycling and flame retardant properties and compared the data to phosphorus-free vitrimers and conventional epoxy resins (with and without additive flame retardant).
Our phosphonate-based vitrimer proved in first tests, a flame retardant effect comparable to commercial flame retardant resins. The bending strength and bending modulus for the phosphorus-vitrimer glass fiber composites were comparable to glass fiber composites with permanently cross-linked epoxies. In summary, we were able to prove that the covalent installation of phosphonates into vitrimers allows the preparation of recyclable and intrinsic flame retardant composites that do not need flame retardant additives. We believe this concept can be expanded to other polymer networks and additives to generate recyclable and sustainable high-performance materials.