Multiple Structure Reconstruction by Dual Dynamic Crosslinking Strategy Inducing Self-Reinforcing and Toughening the Polyurethane/Nanocellulose Elastomers

High-performance elastomers are expected to possess excellent healing and recycling ability, damage resistance in conjunction with high strength and toughness. Herein, a dual dynamic crosslinking strategy is implemented by multiple hydrogen and disulfide bonds to obtain a novel amorphous and transparent polyurethane/nanocellulose elastomer with excellent self-healing, self-reinforcing and toughening performance. First, hydrogen bonds are introduced in TEMPO-oxidized cellulose nanofibers (TCNF) by modification with 2-ureido-4[1H]-pyrimidone (UTCNF), while disulfide bonds (SS) are introduced in the polyurethane (PU) main chain, leading to the formation of dual dynamic cross-linking networks. The PU-SS-UTCNF elastomer can fully self-heal within 4.0 h at 50 °C. Surprisingly, for the first time, the PU-SS-UTCNF elastomer also self-strengthens and self-toughens after multiple hot-pressing, with tensile strength and toughness that increase by up to 401% and 257% compared to original elastomer samples, up to 50.0 MPa and 132.5 MJ m^-3. The self-strength and self-toughening effects are attributed to 1) reconstruction of dual dynamic networks that increase the cross-linking degree during the multiple hot-pressing processes; 2) multiple hydrogen bonds in the system are beneficial to the orientation of highly crystallized UTCNF, as a replacement of stress-induced process in deformation under external tensile force.