Kinetic investigation of a complex curing of the guaiacol bio-based benzoxazine system

Abstract

AbstractCuring kinetics of guaiacol based benzoxazine synthesized from guaiacol, furfurylamine and formaldehyde forming bio-based polybenzoxazine was investigated. The curing process showed complex polymerization behavior, as the exothermal signal consisted of several overlapped peaks. Differentiation and fitting of overlapped peaks was performed by Pearson VII distribution obtaining two separate exothermal signals further associated to stage 1 and stage 2. The apparent activation energies of both stages were determined to be 113.8 kJ mol-1 and 117.5 kJ mol-1, respectively, according to Kissinger. The first could be explained by benzoxazine ring-opening and electrophilic substitution, whereas the second stage corresponds to the rearrangement and diffusion-controlled step. Kinetics of each stage was studied separately. As a result, the first stage was described by Šesták-Berggren autocatalytic model, whereas the second stage appeared to follow nth order kinetics proved by the Friedman method. Application of both kinetic models demonstrated that the predicted curves fit well with the non-isothermal DSC thermograms and as such sufficiently describes the complex curing behavior of guaiacol based benzoxazine.