Enhancing char formation of flame retardant epoxy composites: Onigiri-like ZIF-67 modification with carboxymethyl β-cyclodextrin crosslinking

To enhance char formation of flame retardant epoxy (EP) composites, carboxymethyl β-cyclodextrin (CM-β-CD) is employed as an etchant for or ZIF-67 derivatives. In the early stage, etching plays a dominant role. The mismatch in size between CM-β-CD opening and ZIF-67 pore leads to the stacking of carboxyl cobalt complexes on the shell. When the reaction time is prolonged, crosslinking occurs between carboxyl and hydroxyl groups. Crosslinked CM-β-CD weakens and eventually stops the etching process. Triethyl phosphate (TEP), an additive to improve flame retardancy, is also absorbed on the shell in this one-pot synthesis. Herin, the synthesis of metal-organic framework (MOF) derivatives can impart multiple functions to MOF. This novel nanohybrid significantly improved flame retardancy of EP composites with only 2.0 wt% loading. The peak heat release rate (pHRR) and total smoke production (TSP) were reduced by 54.8 and 46.9%, respectively. The integrated multi-element system resulted in an expanded and reinforced char layer. This study proposes a simple and precise method for controlling the structure of MOF-carbohydrate hybrids through competition between chemical reactions.