Vitrimers endow cross-linked polymers with malleability and reprocessability via exchange reactions. However, designing of reprocessable, shape-memory polymer materials with high strength via a catalyst-free method remains a challenge under mild conditions. Here, we propose a facile strategy to address this dilemma by introducing the exchangeable imine bond and N-coordinated boroxine into a polybutadiene (PB)-based network. Specifically, PB grafted with 2-aminoethanethiol is reacted with the formyl group of phenylboronic acid and dehydrated to form a dual-dynamic covalently cross-linked network at room temperature. The dynamic network draws on the advantage of imine (toughness) and N-coordinated boroxine (strength), making the PB-based materials exhibit favorable malleability, mechanical property, reprocessability, and thermal-induced shape-memory behavior. We can obtain customized high mechanical properties by tuning the cross-linking density, and the tensile strength reaches a high value (12.35 MPa) without fillers or any other additives. Meanwhile, the unique network framework makes the material recycle over several times without sacrificing its property. This work presents a facile and effective approach to achieve a multifunctional polymer with customized attributes. Besides, this strategy can recycle end-of-life rubber to alleviate environmental pollution and provide inspiration for fabricating targeted materials by uniting the dynamic covalent or noncovalent bonds.

A covalent adaptable network can endow rubber materials with recyclability and reprocessability and is expected to alleviate black pollution caused by end-of-life rubber. However, the loss of traditional vulcanization systems severely sacrifices their strength, and the tensile strength in the current study rarely exceeds 10 MPa unless fillers are added. In this work, we proposed a self-strengthening process based on dual-dynamic units (imine and disulfide), briefly, under heating, phenylsulfur radicals generated from aromatic disulfide bonds can react with double bonds (mostly vinyl) and/or couple with allyl sites, thus reforming a stronger cross-linked network. The neighboring imine unit is not affected and provides excellent thermal reprocessability and chemical recyclability. The result shows that the tensile strength can reach 19.27 MPa via self-strengthening without adding fillers or any other additives, and this ultra-high-strength is much higher than those of all known recyclable polybutadiene-based rubber materials. In addition, the material also has malleability, shape memory, and self-welding properties. By doping carbon nanotubes, a recyclable conductive composite can also be achieved. In general, we envision that this enhanced strategy has great potential to be generalized for all elastomers containing double bonds (such as styrene–butadiene rubber, nitrile rubber, isoprene rubber, and their derivatives). The reprocessability and self-welding are practical for on-site assembly or repair of composite parts and extend the service life of materials.