Study of the formation of structures in solutions of chitosan – polyvinyl alcohol polymer blends

The aim of this work was the investigation of the formation of structures in solutions of individual polymers, as well as their blends with each other in buffer solvents with different values of pH. In this study we used a sample of chitosan (degree of deacetylation ~ 84 %, M = 130,000), which is a polycation when dissolved, and polyvinyl alcohol (r = 1.25 g/cm3, M = 5000). Buffer systems based on acetic acid and sodium acetate with pH = 3.8, 4.25, and 4.75 were used as solvents. Viscosimetry was used to determine the intrinsic viscosity, the degree of structuring, and the Huggins constant. The Kriegbaum method was used to determine the nature of the aggregates formed by the blend of the studied polymers. In the course of the research, it was shown that an increase in the pH of the acetate buffer used as a solvent was accompanied by a compression of the macromolecular coil (a decrease in intrinsic viscosity values), a deterioration in the quality of thesolvent (an increase in Huggins constant values), and an increase in the degree of polymer aggregation in a solution for chitosan polyelectrolyte. At the same time for a solution of polyvinyl alcohol the pH of the buffer practically did not affect the nature of the polymer-solvent interaction. It has been proved that polymer blends are characterized by an increase in aggregation processes and a decrease in the thermodynamic quality of the solvent in comparison with solutions of individual polymers. The size of the “combined” macromolecular coil, characterized by the intrinsic viscosity value for the polymer blend, which can be both above (buffer solvent with pH = 3.80) and below (buffer solvent with pH = 4.25 and 4.75) additivevalues, changed depending on the type of formed polymer-polymer aggregates (homo- or hetero-). It was established that the type of aggregates (homo- or hetero-) formed in solutions of polymer blends was determined not only by the thermodynamic quality of the used solvents, but also by the concentration of the polymers in the initial solutions

Some Approaches to Viscometric Study of Chitosan in Acetic Acid Solution

Some ways of estimating the values of the intrinsic viscosity of chitosan were analyzed. It was shown that the method of Irzhak and Baranov for estimating the current value of the intrinsic viscosity allows to adequately estimates the conformational state of the macromolecular coil and its degree of swelling.

The dependence of the chain branching degree on molecular weight: Fractal analysis

The fractal analysis methodology allows the clear structural identification of both chemical and physical factors controlling a chain branching degree. The effective number of branching centers per one macromolecule m is controlled by four factors: polymer molecular weight, MW, maximal 'chemical' density of reactive centers, cch, dimension of non-screening surface of macromolecular coil, du, and its fractal dimension, D. The presented research allows the determination of the critical value, Dcr = 1.10, the lower of which branching degree is equal to zero (i.e., branching does not occur).