Dual nucleation sites induced by ZIF-67 towards mismatch of polyphosphazene hollow sub-micron polyhedrons and nanospheres in flame retardant epoxy matrix

Polyphosphazene has drawn an abundance of attention as a flame retardant due to its eco-friendliness and phosphorus-nitrogen synergistic effect. ZIF-67 and cobalt compounds derived from cobalt ions released by ZIF-67 were employed as dual templates for loading polyphosphazene. We skillfully designed a polyphosphazene hollow hybrid material via the polymerization of phosphazene accompanied by the etching of ZIF-67 and cobalt compounds by generated HCl. The hybrid material (CPPHS) was composed of cobalt-doped polyphosphazene hollow sub-micron polyhedrons (CP) and polyphosphazene hollow nanospheres (PHNS) with different dimensions and magnitudes of sizes. After adding 2.0 wt% CPPHS, the limiting oxygen index of epoxy resin increased to 27.6%, while the peak heat release rate and total smoke production decreased by 40.1% and 38.8%, respectively. The formation of a continuous and strongly extended dense char layer in the EP composites was fostered by the synergistic effect of Co-P-N flame retardant components, significantly decreasing the heat flow and combustible gas exchange rate and effectively hindering the combustion chain reaction. Furthermore, the unique dimensional mismatch structure of CPPHS enhanced its dispersion in the EP matrix, enabling the EP to have superior mechanical properties that match realistic application requirements, consequently expanding the variety of applications for fire-resistant EP composites.