Permanently cross-linked materials have outstanding mechanical properties and solvent resistance, but they cannot be processed and reshaped once synthesized. Non-cross-linked polymers and those with reversible cross-links are processable, but they are soluble. We designed epoxy networks that can rearrange their topology by exchange reactions without depolymerization and showed that they are insoluble and processable. Unlike organic compounds and polymers whose viscosity varies abruptly near the glass transition, these networks show Arrhenius-like gradual viscosity variations like those of vitreous silica. Like silica, the materials can be wrought and welded to make complex objects by local heating without the use of molds. The concept of a glass made by reversible topology freezing in epoxy networks can be readily scaled up for applications and generalized to other chemistries.

Rubbers exhibit enormous extensibility up to several hundred per cent, compared with a few per cent for ordinary solids, and have the ability to recover their original shape and dimensions on release of stress. Rubber elasticity is a property of macromolecules that are either covalently cross-linked or connected in a network by physical associations such as small glassy or crystalline domains, ionic aggregates or multiple hydrogen bonds. Covalent cross-links or strong physical associations prevent flow and creep. Here we design and synthesize molecules that associate together to form both chains and cross-links via hydrogen bonds. The system shows recoverable extensibility up to several hundred per cent and little creep under load. In striking contrast to conventional cross-linked or thermoreversible rubbers made of macromolecules, these systems, when broken or cut, can be simply repaired by bringing together fractured surfaces to self-heal at room temperature. Repaired samples recuperate their enormous extensibility. The process of breaking and healing can be repeated many times. These materials can be easily processed, re-used and recycled. Their unique self-repairing properties, the simplicity of their synthesis, their availability from renewable resources and the low cost of raw ingredients (fatty acids and urea) bode well for future applications.

Vitrimers, strong organic glass formers, are covalent networks that are able to change their topology through thermoactivated bond exchange reactions. At high temperatures, vitrimers can flow and behave like viscoelastic liquids. At low temperatures, exchange reactions are very long and vitrimers behave like classical thermosets. The transition from the liquid to the solid is reversible and is, in fact, a glass transition. By changing the content and nature of the catalyst, we can tune the transesterification reaction rate and show that the vitrimer glass transition temperature and the broadness of the transition can be controlled at will in epoxy-based vitrimers. This opens new possibilities in practical applications of thermosets such as healing or convenient processability in a wide temperature range.