Regular and inverse polyampholyte hydrogels: A detailed comparison

Abstract

Two series of polyampholyte (PA) hydrogels were prepared via reversible addition-fragmentation chain transfer polymerization, followed by removal of the protecting group of the acidic monomer repeating units (methacrylic acid, MAA), which were common in both series. One series bore (pyridin-2-yl)methyl methacrylate (2PyMMA) basic monomer repeating units, whereas the second series carried basic monomer repeating units of 2-(dimethylamino)ethyl methacrylate (DMAEMA). The 2PyMMA-MAA combination in the first series had the peculiarity that the basic 2PyMMA units were more acidic than the MAA units, thus resulting in so-called inverse PA hydrogels. The DMAEMA-MAA pair in the other series led to regular PA hydrogels in which the basicity and acidity of the two types of units were in the conventional sense. The swelling and hydrogen ion equilibrium properties of the two series were explored and thoroughly compared to each other. The aqueous degrees of swelling of inverse PA hydrogels were found to be generally lower than those of the regular ones due to the more hydrophobic character of the 2PyMMA basic units employed in inverse compared to those (DMAEMA) in regular PA gels. The aqueous swelling pH-profiles in both series of PA hydrogels presented a minimum. However, this swelling minimum was deeper and wider in the case of inverse PA hydrogels, because of the greater hydrophobicity of the basic (2PyMMA) units and the greater difference in the effective pK values of the two types of units (2PyMMA-MAA) in inverse PA hydrogels, respectively. This larger separation of the pK in inverse PA gels was directly confirmed from the hydrogen ion titration curves of all the gels. Finally, the isoelectric points of inverse PA hydrogels possessed no detectable dependence on PA composition, which must be contrasted to the strong composition-dependence of the isoelectric points of regular PAs. © 2016 American Chemical Society.