The current study is motivated by the need to develop moderate-to-high temperature benzoxazine vitrimers following the established cost-effective solventless one-pot Mannich condensation method , incorporating fast catalyst-free bond exchange. The hypothesis in this work is that this is achievable if the phenolic and amine precursors are endowed with molecular structural functionalities that could translate into moderate-to-high crosslinking density upon polymerisation of the potential benzoxazine monomer, and the precursors exhibit a high level of solvency without solidifying prior to the end of the anticipated synthesis reaction. Combined with disulphide chemistry, this would deliver a benzoxazine system featuring high glass transition and fast catalyst-free stress relaxation leading to vitrimeric functionalities. A formulated monomer following this route is characterised using FTIR spectroscopy whilst calorimetric analyses of both monomer and polymer are carried out to establish the curing behaviour and glass transition temperature. The degradation behaviour and fire retardancy potential of the polymer are investigated using thermogravimetric analysis, applying the van Krevelen model for limiting oxygen index (LOI) calculation. Furthermore, swelling experiments are performed to establish the thermosetting character of the polymer. Dynamic mechanical analysis (DMA) is used to measure the glassy modulus and glass transition temperature, whereas stress relaxation is used to estimate the vitrimer topological freezing transition temperature. Scratching and self-healing experimentsquantified through profilometric analysis of surface profiles before and after healing a scratched specimenare utilised to demonstrate the functionality of the vitrimer as an autonomously repairable matrix system.