Glassy polymers are extremely difficult to self-heal below their glass transition temperature (T_g) due to the frozen molecules. Here, we fabricate a series of randomly hyperbranched polymers (RHP) with high density of multiple hydrogen bonds, which show T_g up to 49 °C and storage modulus up to 2.7 GPa. We reveal that the hyperbranched structure not only allows the external branch units and terminals of the molecules to have a high degree of mobility in the glassy state, but also leads to the coexistence of “free” and associated complementary moieties of hydrogen bonds. The free complementary moieties can exchange with the associated hydrogen bonds, enabling network reconfiguration in the glassy polymer. As a result, the RHP shows amazing instantaneous self-healing with recovered tensile strength up to 5.5 MPa within 1 min, and the self-healing efficiency increases with contacting time at room temperature without the intervention of external stimuli. Significance Glassy polymers are widely used as structural materials in aerospace vehicles, airplanes, automobiles, biomedical devices, and so on. However, glassy polymers are difficult to self-heal at room temperature due to their frozen molecules. For example, the window glass of airplanes made of polycarbonate cannot repair mechanical damages autonomously, which could lead to a catastrophe. To impart glassy polymers with self-healing ability, we take advantage of the high mobility of hyperbranched polymers, and introduce hydrogen complementary moieties onto the hyperbranched structure, enabling the construction of a series of autonomous room-temperature self-healing glassy polymers.

The practical applications of organic phase change materials (PCM) are greatly limited, due to their leakage in the melted state and unacceptably low thermal conductivity.

A huge challenge for developing self-healing elastomers is achieving a compromise between mechanical properties and healing efficiency. Here, we report a class of high performance self-healing elastomers (HiSHEs) with an exceptional combination of strength (up to 30 MPa), toughness (up to 32 kJ m⁻²) and healing efficiency (>80%). The HiSHEs are made of polyampholytes synthesized through kinetically controlled copolymerization of an acrylate monomer with long alkyl side groups and a pair of oppositely charged monomers that forms precipitates slowly. The acrylate monomer enables the formation of polymer chains of high mobility, while the oppositely charged monomers form gradient interactions by segregating into ionic aggregates with a wide range of sizes and stiffnesses. The weak interactions sacrifice progressively to dissipate energy, thereby enhancing the toughness, and the strong interactions impart the elastomers with high strength and elasticity. Moreover, the reversible gradient interactions also enable self-healing and multi-shape memory functions. By harnessing these functions, we design a mendable strain sensor with remarkably improved sensitivity.

The hybrid filler network of GE/CNTs dissipates energy upon deformation and this leads to remarkable toughening and reinforcing effects on rubbers.