Facile preparation of poly(N-isopropylacrylamide)-based hydrogels via aqueous Diels-Alder click reaction

The study reports a facile method of preparing poly(N-isopropylacrylamide)- based hydrogels by means of the Diels-Alder reaction. First, polymeric dienes were synthesized by free radical copolymerization between N-isopropylacrylamide (NIPA) and furfuryl methacrylate (FM), with 2, 2′-azobisisobutyronitrile (AIBN) as an initiator, and polymeric dienophile was obtained by a coupling reaction of poly(ethylene glycol) (PEG) and N-maleoyl-l-leucine (LMI) under N, N′-dicyclohexylcarbodiimide (DCC). Afterwards, the resultant dienes and dienophiles were dissolved in water and put in a refrigerator remaining a temperature of 9 °C, gelation via Diels-Alder reaction was observed after some time. The samples obtained at different steps were characterized by FTIR, NMR, GPC, SEM, CD, etc. It was found that LCST of copolymers decreases with the increase of FM content in copolymers. And the disassembly time of the hydrogels is closely related to the temperature and the solvents used. The swelling behavior study by gravimetric measurement indicates the hydrogels possess thermosensitivity and exhibit considerable swelling in water. Due to the simplicity of synthesis and no need for initiator or catalyzer and organic solvent, the strategy described here could find a promising application in the preparation of hydrogels.

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