Molecular mass characterization of polymers with strongly interacting groups using gel permeation chromatography-light scattering detection.

This work is aimed at studying dilute solution behavior and developing techniques for the proper Mr characterization of polymers with strongly interacting groups. In particular, we have studied ionomers based on poly(dimethylcarbosiloxane) with carboxylic groups and hydrophobically modified polyacrylamide and its charged terpolymer. Gel permeation chromatography-light scattering (GPC-LS) study of organosilicon ionomers allowed us to follow molecular mass distribution evolutions during approximately a week that evidenced the gradual dissolution of clusters formed in bulk polymers. The rate of this process depends on the polymer composition and its preliminary treatment. Observed aggregates arre found to be stable during the procedure of chromatographic analysis. For characterization of hydrophobically modified polyacrylamide and its charged derivatives, we have used aqueous NaNO3-acetonitrile mixed solvent. Fluorescence spectroscopy with pyrene as a probe did not reveal any hydrophobic association in this solvent in contrast to aqueous solutions. Reversed-phase retention as well as polyelectrolyte exclusion were suppressed at GPC analysis. GPC-LC and classical LS methods gave consistent results for uncharged and weakly charged polymers. In the case of highly charged and highly hydrophobic terpolymers LS results evidenced association, while OPC-LC gave credible Mr values. We can conclude that in the last case, the observed association was weak enough to be disrupted in the coarse of chromatography.

Two types of hydrophobic aggregates in aqueous solutions of chitosan and its hydrophobic derivative.

The aggregation phenomena in aqueous solutions of hydrophobically modified (HM) chitosan, containing 4 mol % of n-dodecyl side chains, were studied by viscometry and fluorescence spectroscopy with pyrene as a probe. The results are compared with those for unmodified chitosan. Surprisingly, fluorescence data reveal the appearance of intermolecular hydrophobic aggregates both in chitosan and in HM chitosan. Nevertheless, these polymers exhibit quite different rheological properties: upon the formation of aggregates the viscosity of HM chitosan sharply increases, while that of unmodified chitosan raises only slightly. The aggregation models for both chitosan and its hydrophobic derivative were proposed. It was shown that in solutions of HM chitosan two types of hydrophobic domains exist: hydrophobic domains typical for different associating polymers with hydrophobic side chains and hydrophobic domains inherent to chitosan itself.