Amine‐Catalyzed Aldol Addition of Dihydroxyacetone for Bio‐Based Flame Retardants

Matthijssen, Joost;Rammal, Fatima;Scodeller, Ivan;Hickson, Matthew V.;Sels, Bert F.;et.al.
(2025) ChemCatChem — Vol. 17, n° 22 (2025)

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Abstract
A new catalytic method was developed for synthesizing a sustainable phosphorus-based flame retardant (PFR) from dihydroxyacetone (DHA), a triose derived from hexoses or glycerol oxidation, e.g., for PUR applications. The study first investigates alkyl amine catalysts for self-aldol addition of DHA to form the branched hexose dendroketose. Short-chain, non-functionalized secondary and tertiary amines showed the best balance between aldol activity and branching selectivity. Triethylamine (Et3N) was chosen for process optimization, enabling scale-up to a 10 L process using 500 g/L DHA and 1 mol % Et3N, achieving a productivity of 109 g/(L·h)—approximately 7.5 times higher than the current state of the art. The resulting dendroketose was hydrogenated to produce dendroketol, a branched hexitol with three primary alcohol groups suitable for further functionalization. To prevent product loss during hydrogenation due to base-catalyzed retro-aldol addition, various amine neutralization methods were evaluated, with equimolar HCl addition proving most effective and economical. Finally, dendroketol was purified and phosphorylated with P2O5 to yield the PFR. Flame-retardant testing, conducted under EU standard BS 7175 (for bedding materials), confirmed compliance, underscoring the industrial potential of the process.
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Matthijssen, J., Rammal, F., Scodeller, I., Hickson, M. V., Van Vaerenbergh, B., De Schrijver, B., Carreira, A. S., Teixeira, R. F. A., Debecker, D., Eloy, P., Poleunis, C., Makshina, E. V., & Sels, B. F. (2025). Amine‐Catalyzed Aldol Addition of Dihydroxyacetone for Bio‐Based Flame Retardants. ChemCatChem, 17(22). https://doi.org/10.1002/cctc.202501139 (Original work published 2025)