Hetero-network hydrogels crosslinked with silica nanoparticles for strategic control of thermal responsive property

Two thermoresponsive copolymers with different lower critical solution temperatures (LCSTs) were crosslinked using silica nanoparticles to afford hybrid hydrogels exhibiting two distinct thermo-responsivities. The thermo-responsive copolymers were synthesised by free radical polymerisation from a monomer with a reactive side chain (3-methacryloxypropyl trimethoxysilane (S)) and water-soluble monomers with different thermo-responsivities (N-isopropyl acrylamide (N) or N-(3-methoxy propyl)acrylamide (M)). The obtained reactive copolymers, poly(N-isopropyl acrylamide-co-3-methacryloxypropyl trimethoxysilane) (pNS) and poly(N-(3-methoxy propyl acrylamide-co-3-methacryloxypropyl trimethoxysilane)) (pMS), were characterized by multiple techniques including 1H NMR and FTIR spectroscopy. The hetero-network hybrid hydrogels were easily prepared by mixing aqueous solutions of the copolymer with an aqueous colloidal silica suspension; their gelation properties could be tuned by varying the amounts of pNS, pMS, and Si. Differential scanning calorimetric analysis showed that the hetero-network hydrogel exhibited a critical two-step phase transition at temperatures around the LCST of each copolymer (33 °C for pNS, 73 °C for pMS), indicating that each polymer does not disturb the phase transitions of the other. The deswelling of the hetero-network hydrogel could be controlled with respect to temperature and time.