This comprehensive review article summarizes the key properties and applications of advanced carbonaceous materials obtained from polybenzoxazines. Identification of several thermal degradation products that arose during carbonization allowed for several different mechanisms (both competitive ones and independent ones) of carbonization, while also confirming the thermal stability of benzoxazines. Electrochemical properties of polybenzoxazine-derived carbon materials were also examined, noting particularly high pseudocapacitance and charge stability that would make benzoxazines suitable as electrodes. Carbon materials from benzoxazines are also highly versatile and can be synthesized and prepared in a number of ways including as films, foams, nanofibers, nanospheres, and aerogels/xerogels, some of which provide unique properties. One example of the special properties is that materials can be porous not only as aerogels and xerogels, but as nanofibers with highly tailorable porosity, controlled through various preparation techniques including, but not limited to, the use of surfactants and silica nanoparticles. In addition to the high and tailorable porosity, benzoxazines have several properties that make them good for numerous applications of the carbonized forms, including electrodes, batteries, gas adsorbents, catalysts, shielding materials, and intumescent coatings, among others. Extreme thermal and electrical stability also allows benzoxazines to be used in harsher conditions, such as in aerospace applications.

An atomic-oxygen-erosion-resistant fluorinated benzoxazine resin and composite were developed. The benzoxazine resin, abbreviated as “BAF-oda-fu,” consists of four benzoxazine rings, and was synthesized from bisphenol AF (BAF), 4,4′-oxydianiline (oda), furfurylamine (fu), and paraformaldehyde. The resin was characterized by infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). An analysis of the solvent-washed product showed a technical grade purity (>95%) and a yield of approximately 85%. Subsequent polymerization of the resin was successfully performed by heating step-wise and opening the benzoxazine rings to form a crosslinked network. Thermal analyses showed a melting temperature of 115 °C and polymerization temperature of 238 °C, both being characteristic values of benzoxazine monomers. The benzoxazine resin was also blended with polyoctahedral sisesquoxane (POSS) and reinforced with alumina fibers. The Tg of the resin, as determined by DMA of the composite, could reach as high as 308 °C when post-curing and the POSS additive were utilized. The low-Earth orbit atomic-oxygen erosion rate was simulated by an RF plasma asher/etcher. The atomic-oxygen resistance of poly(BAF-oda-fu) fell along an established trend line based on its fluorine content.