Highly Crosslinked Polybenzoxazines from Monobenzoxazines: The Effect of Meta-Substitution in the Phenol Ring

It is possible to control the crosslink density of polymers derived from monobenzoxazines by switching the type of substituents in the phenolic ring and their relative position with respect to the phenol group. We prepared several substituted monobenzoxazines in the para and meta positions of the phenolic ring and studied how these substituents affected the polymerization temperature of monomers and the thermal stability of the final polymers and, more extensively, how they affected the crosslink network of the final polymers. Gel content and dynamic mechanical analysis confirm that ortho- and para-orienting substituents in the meta position generate highly crosslinked materials compared to para ones. This fact can lead to the design of materials with highly crosslinked networks based on monobenzoxazines, simpler and more versatile monomers than the commercial bisbenzoxazines currently in use.