POSS-Induced Dynamic Cross-Links Produced Self-Healing and Shape Memory Physical Hydrogels When Copolymerized with...

The hydrogel morphology and viscoelasticity and the two-way shape memory behavior of copolymers of N-isopropyl acrylamide-polyhedral oligomeric silsesquioxane (PNIPAm-POSS) were investigated. NIPAm-POSS copolymers are unentangled and exhibit a thermoplastic and thermoresponsive hydrogel behavior ( Romo-Uribe ; ; Albanil , Eur. Polym. J. 2018 , 99 , 350 - 360 ). Here, we demonstrated by high-resolution transmission electron microscopy that POSS segregated into crystals to form physical cross-links. The hydrogels exhibited significant swelling, higher than chemical hydrogels at the same POSS content. The morphology of the hydrogels consisted of a honeycomb structure, and the pore size and swelling were a decreasing function of POSS. Moreover, the hydrogels were self-healing, exhibiting a liquid-like behavior under large amplitude shear and rubber-like behavior immediately after cessation of shear, that is, the POSS aggregates break and re-form, acting as dynamic cross-linkers. Strikingly, the physical networks behaved as perfect networks, thus matching chemically cross-linked networks and holding the scaling |η*| ∼ ω^-1. Furthermore, the physical hydrogels exhibited a thermally activated shape memory (SM) behavior, without external stress and the lower critical solution temperature (LCST) being the only stimulus. The SM process involved swelling-deswelling, effectively opening opportunities for drug delivery. Furthermore, the SM was reversible, and no external stress was involved, therefore behaving as the two-way SM. Finally, POSS modulated the shear elastic modulus G' and LCST; therefore, the PNIPAm-POSS copolymers open opportunities for reusable, thermoformable SM hydrogels with tuned mechanical modulus and activation temperature.