Co‐flame retarding effect of ethanolamine modified titanium‐containing polyhedral oligomeric silsesquioxanes in epoxy resin

A metal‐doped organic and inorganic hybrid polyhedral oligomeric silsesquioxanes (POSS) with a titanium atom in the POSS cage and an ethanolamine substitute group in the corner, namely MEA‐Ti‐POSS, was synthesized through simple condensation reaction and substitute reaction. It was blended with 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) to form a kind of blending‐type flame retardant system for the modification of epoxy resins. The thermal stability, flame retardancy and mechanical properties of cured epoxy resin composites were studied. Comparing with pure epoxy resin, the LOI value of EP/MEA‐Ti‐POSS/DOPO composites was raised from 25.2% to 32.7%, and the UL‐94 grade reached V‐0 level at a loading of the mixture of 5% MEA‐Ti‐POSS and 5% DOPO. In addition, the cone calorimetry results showed that the heat release rate, total heat release and total smoke production as well as smoke production rate were all reduced during the combustion of EP/MEA‐Ti‐POSS/DOPO composites. The residual char analysis revealed that carbon residues of EP/MEA‐Ti‐POSS/DOPO composite served as a physical protective layer to insulate the oxygen and combustible gases to reduce the ablation of the matrix. It was concluded that the mixture of MEA‐Ti‐POSS and DOPO not only effectively raised the thermal stability and flame retardancy of epoxy composited materials, but also improved their mechanical properties, which expanded a promising application of the metal‐POSS derivatives as non‐halogen additives in the flame retardant polymers.