Coacervation-Based Method for Constructing a Multifunctional Strain-Stiffening Crystalline Polyvinylamine Hydrogel

Strain-stiffening hydrogels are essential in the development of ionic skin, as human skin possesses a strain-stiffening property for self-protection. Semicrystalline polymers such as poly(vinyl alcohol) (PVA) have been widely investigated to fabricate strain-stiffening hydrogels via freeze-thaw cycling or chemical cross-linking but with limited adjustable properties. Compared with PVA, polyvinylamine (PVAm) has a higher reactive activity, making it easier to achieve multifunctionalities including strain-stiffening in a PVAm hydrogel. However, the amine moieties in the backbone tend to be ionized and form strong ionic hydrogen bonds with water, resulting in difficulties in forming crystalline hydrogels by conventional methods. Herein, a one-pot method to induce crystallinity and achieve multifunctional hydrogel is devised via coacervation of PVAm. Different from a published coacervation method to fabricate hydrogels with various properties via noncovalent interactions between different chemicals, coacervation occurs between PVAm to form aggregated and loose PVAm in our devised system. Such a strategy lowers the amine-water binding energy in the polymer-dense phase to achieve crystallinity and subsequently the strain-stiffening property; meanwhile, self-healability, self-adhesion, and ionic conductivity can be realized in the polymer-loose phase. The obtained hydrogel integrates stretchability (∼1300% elongation), toughness (227 kPa), the strain-stiffening property (∼10 times increase), self-adhesion (90 J m^-2), self-healability (∼80% healing efficiency in toughness), and ionic conductivity (0.22 mS m^-1). This convenient strategy will open a new horizon to design multifunctional skin-mimic materials.