A novel halogen-free co-curing agent with linear multi-aromatic rigid structure as flame-retardant modifier in epoxy resin

A novel halogen-free 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing co-curing agent, 6,6′-(1,4-phenylenebis(((4-(phenylamino)phenyl)amino)methylene))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (DPN) was synthesized via a simple 1-pot or 2-step procedure with yield of 86.2% and 70.8%, respectively. The molecular structures of 4,4′-((1,4-phenylenebis(methanylylidene))bis(azanylylidene))bis(N-phenylaniline) (DPN intermediate) and DPN are characterized by FTIR, NMR, and MS. TGA tests show that the char yield of DPN/EP composites raises to 30.9% when the molar ratio of DPN to 4,4-diaminodiphenyl methane(DDM) is 20:80. T g values of DPN/EP composites tested by DSC and DMA are similar to neat epoxy resin (EP), which is due to the secondary amine in DPN that participates in the cross-linking reaction of epoxy resin. The storage modulus in the rubber stage (E′-190 °C) of flame-retardant epoxy resin is close to that of neat EP, while their tanδ's are lower, which indicates the similarity of samples' cross-linking density due to the participation of DPN in the cross-linking reaction. The results show that when the molar ratio of DPN and DDM is 5:95, the epoxy has a higher T g value and better mechanical properties than other samples. The introduction of DPN efficiently improves the flame-retardant properties of epoxy resin with V-0 rating of UL-94 vertical burning test, non-dripping, 41% of limit oxygen index (LOI) value, low peak heat release rate (PHRR), and total heat release (THR).