Polymers crosslinked via furan/maleimide thermo-reversible chemistry have been extensively explored as reprocessable and self-healing thermosets and elastomers. For such applications, it is important that the thermo-reversible features are reproducible after many reprocessing and healing cycles. Therefore, side reactions are undesirable. However, we have noticed irreversible changes in the mechanical properties of such materials when exposing them to temperatures around 150 °C. In this work, we study whether these changes are due to the self-reaction of maleimide moieties that may take place at this rather low temperature. In order to do so, we prepared a furan-grafted polyketone crosslinked with the commonly used aromatic bismaleimide (1,1′-(methylenedi-4,1-phenylene)bismaleimide), and exposed it to isothermal treatments at 150 °C. The changes in the chemistry and thermo-mechanical properties were mainly studied by infrared spectroscopy, ¹H-NMR, and rheology. Our results indicate that maleimide self-reaction does take place in the studied polymer system. This finding comes along with limitations over the reprocessing and self-healing procedures for furan/maleimide-based reversibly crosslinked polymers that present their softening (decrosslinking) point at relatively high temperatures. On the other hand, the side reaction can also be used to tune the properties of such polymer products via in situ thermal treatments.

Both shape memory and self-healing polymers have received significant attention from the materials science community. The former, for their application as actuators, self-deployable structures, and medical devices; and the latter, for extending the lifetime of polymeric products. Both effects can be stimulated by heat, which makes resistive heating a practical approach to trigger these effects. Here we show a conductive polyketone polymer and carbon nanotube composite with cross-links based on the thermo-reversible furan/maleimide Diels–Alder chemistry. This approach resulted in products with efficient electroactive shape memory effect, shape reprogrammability, and self-healing. They exhibit electroactive shape memory behavior with recovery ratios of about 0.9; requiring less than a minute for shape recovery; electroactive self-healing behavior able to repair microcracks and almost fully recover their mechanical properties; requiring a voltage in the order of tens of volts for both shape memory and self-healing effects. To the best of our knowledge, this is the first report of electroactive self-healing shape memory polymer composites that use covalent reversible Diels–Alder linkages, which yield robust solvent-resistant polymer networks without jeopardizing their reprocessability. These responsive polymers may be ideal for soft robotics and actuators. They are also a step toward sustainable materials by allowing an increased lifetime of use and reprocessability.

In this work, we prepared electrically conductive self-healing nanocomposites. The material consists of multi-walled carbon nanotubes (MWCNT) that are dispersed into thermally reversible crosslinked polyketones. The reversible nature is based on both covalent (Diels-Alder) and non-covalent (hydrogen bonding) interactions. The design allowed for us to tune the thermomechanical properties of the system by changing the fractions of filler, and diene-dienophile and hydroxyl groups. The nanocomposites show up to 1 × 10⁴ S/m electrical conductivity, reaching temperatures between 120 and 150 °C under 20–50 V. The self-healing effect, induced by electricity was qualitatively demonstrated as microcracks were repaired. As pointed out by electron microscopy, samples that were already healed by electricity showed a better dispersion of MWCNT within the polymer. These features point toward prolonging the service life of polymer nanocomposites, improving the product performance, making it effectively stronger and more reliable.

Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant moiety can be introduced into the backbone and used as a diene for a temperature reversible Diels-Alder reaction with bismaleimide. The Diels-Alder adduct is formed at around 50 °C and broken at about 120 °C, giving an intrinsic, stimuli-responsive self-healing material triggered by temperature variations. Also, reduced graphene oxide (rGO) is added to the polymer matrix (1.6–7 wt%), giving a reversible OFF-ON electrically conductive polymer network. Remarkably, the electrical conductivity is activated when reaching temperatures higher than 100 °C, thus suggesting applications as electronic switches based on self-healing soft devices.