INFLUENCE OF ORDER IN SOLUTIONS OF POLYVINYLCARBANILATE ON LIGHT SCATTERING MEASUREMENTS

In solutions of polyvinylcarbanilates in diethyl ketone, methyl ethyl ketone and in acetone the Zimm plots show unusual inflections at low angles. These inflections are interpreted by external interferences. They arise from a certain order within the solutions, whereby the phases of scattered rays, belonging to different molecules, keep relative definite relationships. Quantitatively the measurements are evaluated by a formula due to Fournet, which was derived from a well known relationship of Zernicke and Prins. According to Fournet a repulsion potential between the macromolecules is effective and prevents the overlapping of segment clouds. Two possibilities for the explanation of the repulsion potential are discussed. The one consists in the facility of intramolecular hydrogen bonds, which will fix the coil like wire netting, and the other possibility in strong solvation, whereby the solvent molecules become adsorbed within the coil. Furthermore it is shown that the intrinsic viscosities need up to three hours to reach a constant value if the temperature is suddenly changed. From this relaxation process an energy of activation of about 12 kcal per mole macromolecule is calculated. © 1969.