Nonturbid Fast Temperature-Responsive Hydrogels with Homogeneous Three-Dimensional Networks by Two Types of Star Polymer Synthesis Methods

Temperature-responsive polymer gel can rapidly and reversibly switch its various physical properties and has been used in practical applications including reservoirs for drug delivery systems, cell sheet preparation base materials for regenerative medicine, and switching elements for microchannels. However, the sudden volume shrinkage in the gel with rapid temperature change may cause the formation of a skin layer and the macrophase separation phenomenon of the polymer network. Due to this phenomenon, it usually takes a very long time to reach a thermodynamically stable shrunken state of the gel. By adjusting the heterogeneity of the network structure of the conventional temperature-responsive polymer gel and the monomer arrangement of the polymer, the polymer gel may shrink faster without causing skin layer formation or macrophase separation phenomenon. In this study, almost ideal homogeneous temperature-responsive polymer gels could be synthesized by combining two types of synthetic methods for well-defined star-shaped polymers, i.e., the core-first method with a multifunctional initiator and linking method with a divinyl compound as the cross-linker, using a polymerization system with extremely high living fashion to afford polymer chains with narrow molecular weight distributions. As a result, the temperature-responsive polymer gels derived from N -isopropylacrylamide (NIPA) with almost uniform network structure were successfully prepared, in which the number of polymer chains bonded to the cross-linking points and the molecular weight between them are quite uniform. Due to the high living fashion of the polymerization used in this method, a temperature-responsive copolymer gel composed of NIPA and other hydrophilic monomers could also be synthesized. The polymer gel consisting of star-shaped block polymers of NIPA and dimethylacrylamide (DMA) responded much faster than that with an uncontrolled network structure and uncontrolled monomer sequence distribution, which shrank completely in less than 1/60 time as fast with optical transparency and without either skin layer formation or macrophase separation of the polymer network during shrinkage.