Corrosion is a natural phenomenon that affects virtually every material, consumes billions of dollars annually worldwide and may result in catastrophic events. Coating is the most utilized technique to prevent corrosion. In this sense, epoxies are widely applied in all sectors of industry. Despite being high performance polymers, epoxies present issues, such as the use of toxic crosslinkers and long curing time. Benzoxazines are an emerging class of high performance self-curing thermosets. While typical monomers are based on mono- and difunctional derivatives, higher functional benzoxazines, prepared without using solvents, but purified with nontoxic solvents, are more desirable towards a greener synthesis of PBZ for high performance applications. Herein, we describe an environment-friendly approach to synthesizing a trifunctional benzoxazine from melamine, phenol, and paraformaldehyde. The chemical structure of the synthesized benzoxazine was confirmed by spectroscopic analyses, while the polymerization was monitored by thermal analysis. The synthesized benzoxazine monomer is, then, copolymerized with a commercial difunctional epoxy resin. We investigate the synergistic effect on improved thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results showed that a glass transition temperature of up to 268 Degrees C was obtained. A higher thermal stability was also achieved with an onset degradation of nearly 400 Degrees C and char yield of 22 wt (percentage) at 800 degrees C. Later, the copolymer was combined with silica to produce anticorrosion coatings. Results revealed superhydrophobic surfaces with great scratch resistance and adhesion to steel substrate. Electrochemical test proved high effectiveness of the coatings as anti-corrosion barrier, with increasing performance with the incorporation of silica.