Self‐healing reversible network from furfuryl‐functionalized copoly(triazine‐r‐polypropylene glycol‐r‐polydimethylsiloxane)

New shape‐memory networks composed of both reversible Diels–Alder covalent crosslinks and the hydrogen and π–π stacking bonds of triazine functional groups, with self‐healing properties as a result of the reversibility of these dynamic bonds were achieved from a furfuryl‐functionalized copoly(triazine‐r‐polypropylene glycol‐r‐polydimethylsiloxane), crosslinked with a maleimide end‐capped polycaprolactone and a long polycaprolactone‐based chain extender. The presence of multiple dynamic bonds, including the Diels–Alder and triazine‐derived π–π stacking and H‐bond interactions as well as the enhanced network mobility arising from polypropylene glycol, polydimethylsiloxane and polycaprolactone segments upon triggering the shape memory effect resulted in a material with high toughness (~200 MPa J−1) and efficient healing ability (with a recoveries of tensile strength and toughness after being cut and healed of 87% and 94%, respectively).Highlights Furfuryl dichlorotriazine was coupled with PPG and PDMS forming a copolymer. The copolymer was crosslinked with PCL‐dimaleimide and PCL‐difuran extender. Multiple dynamic bonds (Diels–Alder, π–π stacking and H‐bond) were present. The network showed high toughness and good healing performance.