Cationic amphiphilic acrylic copolymer retanning agent for metal-free eco-leather production

Producing metal-free leather is an effective approach to eliminate Cr pollution and achieve sustainable development of the leather industry. However, the high water sorption of the metal-free leather and the mismatching of the charge properties between the metal-free tanned leather and anionic post-tanning chemicals result in the unsatisfactory properties of the leather products, thereby restricting the industrial application of metal-free tanning technologies. Herein, a series of cationic amphiphilic acrylic copolymers (PSD) with different molar ratios of hydrophobic monomer to cationic hydrophilic monomer were synthesized and applied in the retanning of a metal-free tanned leather. PSD can effectively penetrate to the hierarchy of collagen fibril of leather and firmly bind to collagen carboxyls to form a thin hydrophobic coating on the fibril surface due to their small particle size (< 70 nm), excellent surface activity and cationic amine groups (3-27 mu mol/g). Molecular dynamics (MD) simulations confirm that the primary driving force between PSD and collagen is electrostatic interaction. MD simulations and water resistance tests demonstrate that the amphiphilic PSD provides the metal-free leather with moderate hydrophobicity, which indicates the upgrade of the comprehensive properties of leather. PSD retanning enhances the uptake rate of anionic dyes and fatliquors (> 90 %) and endows the metal-free leather with excellent filling effect and bright color. The molar ratio of hydrophilic monomer and hydrophobic monomer plays an important role in the performance of PSD. The hydrophobic segments contribute to the hydrophobicity enhancement of leather, and the cationic hydrophilic segments in PSD contribute to the charge regulation of leather and robust binding of post-tanning chemicals. Hence, the multifunctional PSD retanning agents can fulfill the demands for versatile metal-free leather types and promise to boost the sustainable development of the leather industry.