Titrametric Characterization of pH-Induced Phase Transitions in Functionalized Microgels

The chain and radial functional group distributions in carboxylic acid-functionalized poly(N-isopropylacrylamide)-based microgels have significant impacts on the types of swelling responses exhibited by the microgels upon the application of a temperature and/or pH stimulus. Potentiometric, conductometric, and calorimetric titration approaches are used in this work to characterize the chain distributions of -COOH groups in five microgels prepared using different -COOH-functionalized monomers. A direct correlation is observed between the kinetically predicted formation of functional monomer blocks within the microgel, the excess Gibbs free energy of ionization, and the apparent pK(a) versus degree of ionization profiles generated from potentiometric titration. Isothermal titration calorimetry (ITC) can be used to quantify the relative number of functional groups present in microgels prepared with the same functional monomer and/or identify differences between microgels with the same bulk -COOH content but different chain distributions. In particular, microgels prepared with diacid-functionalized monomers exhibit a characteristic two-step ITC profile. For microgels with the same bulk -COOH content, the heat of ionization measured via ITC increases systematically with the overall change in both the pK(a) and the excess Gibbs free energy for microgels prepared with monoacid-functionalized monomers. Diacid monomer-functionalized microgels have lower ionization enthalpies attributable to the break-up of hydrogen-bonded intramolecular ring complexes upon carboxylic acid ionization. The inferred chain functional group distributions can be used to understand differences in microgel swelling across the pH-induced phase transition.