Composite Flame Retardants Based on Conjugated Microporous Polymer Hollow Nanospheres with Excellent Flame Retardancy

The development of polymer materials with excellent flame retardancy has been paid increasing attention for their valuable applications in saving energy in modern architecture. Herein, conjugated microporous polymers hollow nanospheres (CMPs-HNS) were prepared by Sonogashira-Hagihara cross-coupling reaction with 1,3,5-triacetylenebenzene, 3-amino-2,6-dibromopyridine, and 2,4,6-tribromoaniline as building blocks using SiO₂ nanoparticles as hard templates. To enhance the flame-retardant performance of the CMPs-HNS, antimony pentoxide solution (Sb₂O₅) and bisphenol A-bis (diphenyl phosphate) (BDP) were coated onto the as-prepared CMP-HNS (CMPs-HNS-BSb) by a simple immersion method. The peak heat release (pHRR) from microscale combustion colorimeter (MCC) of CMPs-HNS-BSb was 76.5 and 73.05 W g^-1, respectively. By introducing CMPs-HNS-BSb into the epoxy resin (EP) matrix, the CMP2-HNS-BSb/EP (0.5) composites show that the pHRR values were 809.3 and 645.2 kW m^-2, reduced by 21% as measured by conical calorimetry (CC), and total heat release (THR) reduced by 29.7%, going from 101 to 70.8 MJ/m² when compared to the pure sample. Besides, total smoke production (TSP) reduced about 23.7%. The hollow structure can enhance the thermal insulation performance. As measured, the thermal conductivity of CMP1-HNS-BSb and CMP2-HNS-BSb is 0.044 and 0.048 W m^-1 K^-1. Based on the advantages of simple manufacture, superior thermal insulation, and flame retardancy, our CMPs-HNS-BSb/EP composites may find useful applications in various aspects such as building energy saving in future development.