Study on Flame Retardancy Behavior of Epoxy Resin with Phosphaphenanthrene Triazine Compound and Organic Zinc Complexes Based on Phosphonitrile

A novel flame retardant phosphorus-containing organozinc complex (Zn-PDH) was prepared using zinc and iron as the metal center and 4-aminopyridine, with low steric hindrance, as the organic ligand, then using phosphazene to modify the organometallic complex (Zn-4APD). The flame retardant properties and mechanism of Zn-PDH/Tris-(3-DOPO-1-propyl)-triazinetrione (TAD) in epoxy resin (EP) were investigated. Flame inhibition behavior was studied by the vertical combustion test (UL94), while limiting oxygen index (LOI) measurement and flame retardant properties were studied by the cone calorimeter test (CONE). The flame retardant modes of action were explored by using the thermogravimetry–Fourier transform infrared (TG-FTIR) test, X-ray photoelectron spectrometer (XPS), and Raman spectroscopy (LRS). When TAD and Zn-PDH were added to the epoxy resin in the ratio of 3:1, the system achieved a balance between the gas-phase and condense-phase actions of the flame retardant effects, and the 3%TAD/1%Zn-PDH/EP composite system achieved not only good flame inhibition but also obtained good smoke and heat suppression performance, showing a comprehensive flame retardant performance. The gas phase and Zn-PDH mostly promoted charring with a barrier and protective effect in the condensed phase. As for the mechanism, TAD released the phosphorus-containing radicals and phenoxy radicals during decomposition and mainly exerted a gas-phase quenching effect. While in the condense phase, Zn-PDH promoted the decomposition of the polymer matrix to produce more aromatic structures and rapidly formed a complete and dense carbon layer rich in P-O-C crosslinked structures at high temperatures. Meanwhile, more N entered the gas phase in the form of inert gas, which diluted the concentration of the combustible fuel and helped to inhibit the combustion reaction.