Synthesis and thermal properties of a bio‐based polybenzoxazine with curing promoter

A fully bio‐based benzoxazine, 3‐furfuryl‐8‐methoxy‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Bzf), has been prepared using guaiacol, furfurylamine, and paraformaldehyde as raw materials. Its chemical structure has been characterized by 1H and 13C NMR, FTIR, and elemental analysis. The polymerization behavior of Bzf in the presence of methyl p‐toluenesulfonate (PTSM) has been studied by FTIR and DSC, and the thermal stability of the cured resin has been evaluated by thermogravimetric analysis. It was found that PTSM is a good promoter that serves to avoid thermal decomposition of the bio‐based monomer during the curing process at high temperature. In contrast to the situation with neat Bzf, the presence of PTSM (5 mol % for Bzf) significantly improves the polymerization behaviors, including a decrease in the polymerization temperature from 240 to 174 °C, a shortening of the time required to reach the gel point on heating at 200 °C from 47 to 20 min, and an increase in the char yield of the cured resin from 53 to 62%. Moreover, these observed experimental results on the promoting effect of PTSM are interpreted in terms of several possible mechanistic schemes, which involve a catalytic effect on the dissociation of C? O bonds in both the coordination ring‐opening reaction and the rearrangement from a phenoxy structure to a phenolic structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013