Equilibrium swelling of thermo-responsive copolymer microgels.

Thermo-responsive (TR) hydrogels with a lower critical solution temperature swell strongly at temperatures below their volume phase transition temperature T c and collapse above T c. Biomedical application of these materials requires tuning the critical temperature in a rather wide interval. A facile method for modulation of T c is to polymerize the basic monomers with hydrophilic or hydrophobic comonomers. Although the effectiveness of this method has been confirmed by experimental data, molar fractions of comonomers necessary for fine tuning of T c in macroscopic gels and microgels are unknown. A simple model is developed for the equilibrium swelling of TR copolymer gels. Its adjustable parameters are found by fitting swelling diagrams on several macro- and microgels with N-isopropylacrylamide as a basic monomer. Good agreement is demonstrated between the experimental swelling curves and results of numerical analysis. An explicit expression is derived for the volume phase transition temperature as a function of molar fraction of comonomers. The ability of this relation to predict the critical temperature is confirmed by comparison with observations.