Multiarm Star-Crosslinked Hydrogel: Polymer Network with Thermoresponsive Free-End Chains Densely Connected to Crosslinking Points.

Soft tissue in biological system is a hydrogel with elaborate structure exhibiting repeatable dynamic function. In order to approach such sophisticated system, precise construction of a designed network with multi-components is desired. This communication presents a novel hydrogel having highly dense stimuli-responsive free-end chains around crosslinking structure. A key molecule is a core-crosslinked star-shaped polymer with multiple thermoresponsive arms, which can be prepared by reversible addition-fragmentation chain transfer polymerization of divinyl crosslinker with poly(N-isopropylacrylamide) (PNIPAAm) macro-chain transfer agent and have a number of unreacted carbon-carbon double bonds in the core. These unreacted double bonds can be utilized as a crosslinker for poly(acrylamide) (PAAm) gel synthesis by free radical polymerization. The obtained gel contains homogeneously dispersed star PNIPAAms as crosslinking points and exhibits thermoresponsive swelling behavior in water depending on the star contents. In particular, the gel with low content of the star crosslinker shows localized responsive behavior with expansion and shrinkage of the star in one molecule. The mechanical properties of the star-crosslinked gel are significantly high compared to the conventional PAAm gels particularly in compressive strength (≈9 MPa). Moreover, the star-crosslinked gel has thermoresponsive mechanical toughening property.