One-Pot Preparation of Autonomously Self-Healable Elastomeric Hydrogel from Boric Acid and Random Copolymer Bearing Hydroxyl Groups

Self-healable hydrogels based on the dynamically reversible boronate ester or borate ester bonds are usually prepared by reacting boronic acid or boric acid with diol compounds or polymer-like poly­(vinyl alcohol) bearing a hydroxyl group in each monomer unit. Herein, we report a finding that not only facilitates the preparation but also extends the range of self-healable hydrogels of this kind. By simply copolymerizing commercially available <i>N</i>,<i>N</i>-dimethylacrylamide and 2-hydroxyethyl acrylate (8:2 weight ratio) in the presence of boric acid in a one-pot fashion, the resulting random copolymer can gel in aqueous solution at pH = 9, giving rise to a solid hydrogel (tensile strength >0.5 MPa at water content of 30%) that, on the one hand, can autonomously self-heal (near 100% fracture stress recovery within 48 h in air at room temperature) and, on the other hand, shows the characteristics of elastomer (little stress relaxation under loading and small residual deformation after unloading upon repeated 300% elongation cycles). The results reveal that it can be sufficient to have a random copolymer with comonomer units bearing hydroxyl groups for reacting with boric acid to generate dynamically reversible borate ester bonds. This finding thus points out a general, facile, and cost-effective method to obtain and explore new borate ester bond-based self-healable hydrogels