Chitosan quaternary ammonium salt-oxidized sodium alginate-glycerol-calcium ion biobased self-healing hydrogels with excellent spontaneous repair performance†

Abstract

Self-healing hydrogels have attracted wide attention because of their potential applications in various fields. However, the complex processes, environmental requirements, and insufficient functionality limit their practical application. Herein, we synthesized a chitosan quaternary ammonium salt-oxidized sodium alginate-glycerol-calcium ion (HACC-OSA-Gly-Ca²⁺) biobased hydrogel with a multi-network structure that exhibits excellent self-healing abilities. This was achieved by utilizing reversible dynamic imine bonding, electrostatic interactions, Ca²⁺ ions as crosslinking points, and hydrogen bonding. The oxidation of sodium alginate (SA) with sodium periodate was carried out to obtain oxidized sodium alginate (OSA) with varying oxidation degrees. The resulting OSAs were then introduced into a glycerol–water solvent system containing chitosan quaternary ammonium salt (HACC) and calcium chloride, and this reaction successfully prepared the biobased eco-friendly self-healing hydrogel. The impacts of the oxidation degree (OD) of OSA on the microscopic morphology, mechanical properties, viscoelastic properties, swelling properties, and self-healing properties of the corresponding synthetic hydrogels were investigated. The outcomes indicated that the optimal HACC-OSA-Gly-Ca²⁺ hydrogel possessed good mechanical properties, with a tensile stress of 0.0132 MPa and elongation at break of 551.38%. Furthermore, the multiple bond interactions led to a high self-healing ratio (100%), with an elongation at break of about 614.29%, and excellent adhesion ability (average peel strength of 6.38 kN m⁻¹) on various substrates. Additionally, the composite hydrogels exhibited excellent water retention, thermal stability, and resilience, making them promising for various potential applications. Moreover, the properties of the composite hydrogels could be facilely and finely tuned by varying the oxidation degree of OSA and ratio of each component. Thus, the presented strategy could enrich the construction as well as application of biopolymer-based self-healing hydrogels.