A polybenzoxazine obtained by the polymerisation of a two-component mixture of mainchain benzoxazine and polyether amine features characteristic stress-relaxation, dynamic bond exchange between primary and secondary amines, and reprocessability of vitrimeric systems with moderate 𝑇 𝑔 (97 -108°C) and topology freezing transition temperatures in the range 39 -97°C depending on polyether amine content, whilst a set of imine bond-enabled polybenzoxazine vitrimers with 𝑇 𝑔 in the range of 34 -160°C are synthesised via a solventless approach that involves multiple steps, more complex than the traditional benzoxazine synthesis route . A high-temperature benzoxazine vitrimer has been formulated from a main-chain benzoxazine and an epoxide-functionalised polyrotaxane, yielding a mechanically interlocked network and a covalent adaptable network with improved ductility and toughness, and bond exchange by a tin (II) 2-ethylhexanoate-catalysed transacetalation .