Metal‐Organic Frameworks as curing accelerators for benzoxazines

Abstract Benzoxazine resins, although exhibiting attractive properties; particularly high thermal stability and near zero‐ shrinkage, suffer from a major drawback associated with its high curing temperature. In view of the Lewis acidity associated with the Zn 4 O nodes in a zinc based metal organic framework [Zn 4 O(BDC) 3 , MOF5], we considered it of interest to explore its potential as a curing accelerator for a representative biobased benzoxazine resin. MOF 5 was solvothermally synthesized and characterized using different techniques including powder X‐ray diffraction (PXRD), Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA), Fourier transform infrared spectroscopy (FT‐IR) and Nitrogen physisorption measurements. Bio‐based benzoxazine resin was synthesized by mannich type condensation of cardanol and aniline with formaldehyde under solventless conditions, the structure of which was confirmed using FT‐IR and 1 H‐NMR. The curing behavior of the synthesized resin was systematically investigated using non‐isothermal Differential Scanning Calorimetry (DSC). Introduction of MOF 5 led to a shift in the curing profile to lower temperature, the extent of which was proportional to the amount of MOF 5 in the formulation. DSC studies were performed at different heating rates to establish the kinetic parameters associated with the curing of the resin. Activation energy, as calculated using Kissinger Akahira Sunose method, was found to concomitantly decrease from 98 kJ/mol to 58 kJ/mol upon addition of MOF 5 (5 % w/w).