DOPO-based derivatives with different phosphorous oxidation states as highly efficient flame retardants for epoxy resins

Over the past few decades, the development of highly efficient phosphorus-based flame retardants has become one of the research focuses in the field of halogen-free flame-retardant polymer technology. In this work, three kinds of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based derivatives were synthesized through integrating multiple phosphorous oxidation states into one molecular structure. The influence of DOPO-based derivatives on the thermal decomposition and flame-retardant properties of EP composites were investigated. DOPO-based derivatives promoted the slightly earlier decomposition of the epoxy matrix, resulting in better thermal stability at high temperatures and higher char yield. The unmodified EP showed a LOI value of 27.0% and no UL-94 rating, while all the EP composites containing 2 wt.% DOPO-based derivatives passed the UL-94 V-0 rating and achieved a LOI value of higher than 30.0%. Among the three DOPO-based derivatives, TDCA-DOPO-2 behaved the best flame-retardant efficiency owing to the highest synergistic effect. Specifically, the peak of heat release rate, total heat release and average effective heat combustion (av-EHC) of EP/TDCA-DOPO-2 was 62.0%, 54.2% and 39.9% lower than those of the unmodified EP, respectively. The high flame-retardant efficiency of DOPO-based derivatives was ascribed to the synergism between the barrier effect in the condensed phase (proved by the high yield and stability of char residues) and the flame inhibition effect in the gaseous phase (proved by the decreased av-EHC values).