Thermoresponsive Surface-Grafted Gels: Controlling the Bulk Volume Change Properties by Surface-Localized Polymer Grafting with Various Densities.

We prepared poly(N-isopropylacrylamide-r-N-3-(aminopropyl)methacrylamide) (poly(NIPAAm-r-NAPMAm)) gels with poly NIPAAm (PNIPAAm) grafted only in the surface region (so-called thermoresponsive surface-grafted gels) with various graft densities and investigated the effect of the graft density on the bulk volume change properties, shrinking and swelling, in response to temperature changes. Initiators for atom-transfer radical polymerization (ATRP) and structurally analogous compounds were introduced at certain ratios onto the surface regions of the gels, and a subsequent activator regeneration by electron transfer ATRP of NIPAAm was conducted in aqueous media. The graft densities and molecular weights of the grafted polymers were evaluated from the increment in the dry mass of the gels and the amount of introduced ATRP initiators, which was measured by elemental analyses. Three-dimensional measuring laser microscopy revealed that the prepared gels had graft-density-dependent fine wrinkle structures on their surfaces. The surface-grafted gels induced the formation of skin layers during the shrinking process in response to a temperature increase, and their permeability strongly depended on the graft density. The graft density also controlled the kinetics of the swelling behavior in response to a temperature decrease. These physical properties were discussed on the basis of Young's modulus of the surface determined by an atomic force microscopy force curve measurement and the homogeneity of the surface polymer network observed by cryo-scanning electron microscopy. This makes it possible to arbitrarily control the characteristics of gels as open or semiclosed systems, which was uniquely determined by the designs of the surface gel networks.