The intramolecular aggregation of phosphaphenanthrene groups and benzene-terminated effect within linear phosphonate oligomers effectively enhanced the flame retardancy and toughness of epoxy resin

Abstract

To explore the potential of a flame retardant molecular structure that simultaneously enhances the flame retardancy and physical properties of epoxy resin (EP), benzene-terminated linear phosphonate oligomers Bz-DQPC-n were synthesized. Compared with the previously prepared linear bisphenol phosphonate oligomers DQPC-n, the benzene-terminated effect of Bz-DQPC-n molecules endows EP composites with better flame retardancy and toughness. In the vertical combustion (UL 94) test, Bz-DQPC-n/EP reached a V-0 rating. For the Bz-DQPC-2 molecule, the results revealed that under the same phosphorus contents, the limiting oxygen index (LOI) value of the Bz-DQPC-2/EP reached 38.2 %, which was higher than that of DQPC-2/EP. Furthermore, the peak heat release rate (pk-HRR) and total heat release rate (THR) of Bz-DQPC-2/EP were 677 kW/m² and 83 MJ/m². These values decreased by 54.7 % and 27.2 % in comparison to pure EP, respectively. In addition, the incorporation of Bz-DQPC-n can enhance the glass transition temperature (T_g) of EP composites. The flame retardant mechanism research demonstrated that Bz-DQPC-n molecules produced phosphorus-containing free radicals and aromatic compound fragments during gas-phase pyrolysis. These phosphorus-containing free radicals can interrupt or inhibit the combustion chain reaction process. A proportion of the aggregated phosphaphenanthrene groups decomposed to produce aromatic compounds that remained in the condensed phase, thereby enhancing the quality of the char layer. The investigation of the impact of the end-capping effect within Bz-DQPC-n molecules on the flame retardant behavior of EP composites offers a valuable reference for designing phosphaphenanthrene compounds with high flame retardant efficiency.