Bioinspired ‘phenol-amine’ cross-linking and mineral reinforcement enable strong, tough, and formaldehyde-free tannic acid-based adhesives

Abstract

Conventional tannin-based adhesives have limitations such as formaldehyde emission, inadequate strength and toughness, which restrict their practical applications. Herein, motivated by the natural mechanisms of ‘phenol-amine’ cross-linking and biomineralization, a strong, tough and formaldehyde-free tannic acid-based adhesive was prepared by using all-biomass feedstock. The adhesive was prepared by integrating tannic acid-Zn nanoparticles (TA-Zn NPs), hyperbranched polyamide-grafted dialdehyde chitosan (HPCS), and triglycidylamine (TGA), which formed the fundamental cross-linking network of the prepared adhesive through a Schiff base reaction. The dry and wet bonding strength of the adhesive achieved 1.91 MPa and 1.54 MPa, respectively. The presence of sacrificial bonds such as N…Zn complexation and hydrogen bonding in the adhesive significantly enhance its toughness with a debonding work of 0.595 J. Benefiting from the exceptional antimicrobial properties of TA, chitosan, and Zn2+, the prepared adhesive demonstrated excellent mechanical properties even after being stored in a humid environment for 2 days, with wet and dry bond strength of 1.42 MPa and 1.10 MPa, respectively. Moreover, this adhesive exhibited remarkable resistance to mildew for a duration of 30 days and emitted lower volatile organic compounds compared to other synthetic and biomass adhesives. This innovative bionic strategy holds great potential in enhancing the toughness and functionality of adhesives and composites.