A series of copolymers of styrene and furfuryl methacrylate characterized by various molecular structures (linear and star, block and random) is synthesized via atom transfer radical polymerization, and cross‐linked with a bismaleimide by means of thermally reversible Diels–Alder (DA) reaction, to obtain self‐healing materials. The prepared materials are studied in terms of gelation, swelling, thermal, and dynamic‐mechanical analysis, with the aim of correlating relevant properties to their chemical structure. It is found that the furan/styrene ratio, as well as the molecular architecture, have a major influence on the properties. It is also found that the reversibility of the DA reaction is not complete in the solid state for materials with high cross‐linking density. This study provides some important tools for the design of materials characterized by thermally reversible behavior, which find usually application as self‐healing thermosets, coatings, or adhesives.

This study provides some important tools for the design of materials characterized by thermally reversible behavior, which find usually application as self-healing thermosets, coatings, or adhesives.