The development of polymeric nanocomposites with dynamic covalent adaptable networks and biobased nanomaterials has been a promising approach toward sustainable advanced materials, enabling reprogramming and recycling capabilities. Herein, a core-shell nanohybrid of functionalized cellulose nanocrystals (CNCs) is explored to provide crucial interfacial compatibility for improving the covalent adaptable networks of epoxy-thiol vitrimers in fracture resistance. The poly(ε-caprolactone) (PCL) shells grafted from CNC surfaces can be cross-linked with the covalent adaptable networks via a hot-pressing transesterification process. According to the additive concentration and annealing temperature, the stress relaxation behavior of nanohybrid vitrimer composites can be effectively regulated by the core-shell PCL-grafted CNC (CNC-PCL) nanohybrids from a dispersed to cross-linked interaction. The addition of 15 wt % of the core-shell CNC-PCLs exhibits the reinforced improvement of nanohybrid vitrimer composites in the average Young's modulus of 2.5×, fracture stress of 5.4×, and fracture strain of 2.0×. The research findings might have profound implications for developing synergistic interfacial compatibility between dynamic vitrimer networks and functional nanoparticles for advanced polymeric nanocomposites.
Keywords: cellulose nanocrystals; covalent grafting; elastomeric nanocomposites; fracture resistance; poly(ε-caprolactone); transesterification; vitrimer.