Thermoresponsive properties of polymer hydrogels induced by copolymerization of hydrophilic and hydrophobic monomers: comprehensive study of monomer sequence and water affinity

In order to raise the possibility of the practical use of thermoresponsive hydrogels in various fields, it is imperative to achieve on-demand control of responsive behavior especially by using a simple synthetic method with common monomers. To this end, we synthesized various hydrophilic/hydrophobic copolymer hydrogels from common acrylamide derivatives and acrylate monomers via free radical copolymerization, and examined the correlation between the structure and the swelling properties of the obtained gels, specifically from the viewpoint of the monomer sequence in the network chains and the affinity to water molecules. The obtained gels with a hydrophobic acrylamide monomer were shown to exhibit a sharp volume change in water upon heating at suitable monomer compositions. In contrast, the gels consisting of a hydrophobic acrylate monomer only decreased the swelling degree with no significant thermoresponsive volume change. The formation of a local amphiphilic structure without a long hydrophobic sequence is critical for achieving sharp thermoresponsiveness. Moreover, the water affinity was drastically changed at a sharp volume transition with the copolymer gels of a hydrophobic acrylamide. This transition was most likely driven by an entropic factor because of the strong contribution of the hydration/dehydration of the network chains. The comparison of the temperature-responsive behavior of the gels with that of the corresponding linear copolymers demonstrated that the crosslinking structure made significant hydrophobic contribution to the responsive behavior. Structure-swelling property correlation of thermoresponsive copolymerization hydrogels is discussed from the viewpoint of monomer sequence and water affinity.