A general method for the determination of “monomolecular property versus molar mass relationships” from measurements on polymolecular polymers

Abstract “Monomolecular property (p) versus molar mass (M) relationships” of the type p = Kp · Map as would result from an experimental determination of p and M of a polymer‐homologous series of strictly monomolecular polymers can also be obtained from a polymer‐homologous series of polymolecular samples or fractions, provided their correct corresponding averages p and M are determined (Principle of Corresponding Averages). In order to obtain the monomolecular intrinsic viscosity [η] vs. M relationship (Mark‐Houwink relationship), the corresponding averages weight‐average intrinsic viscosity ([η]w ≡ [η]) and viscosity‐average molar mass (M[η]) of a series of polymer‐homologous, polymolecular polymer samples or fractions have to be determined experimentally. Accordingly, the corresponding monomolecular relationships sedimentation coefficient s vs. M, diffusion coefficient D vs. M, and mean‐square radius of gyration 〈r2〉 vs. M are obtained by the determination of a series of couples of the corresponding averages s vs. M, D vs. M, and 〈r2〉 vs. M, respectively. The experimental determination of the corresponding averages presented is possible by different methods, including the determination of the molar mass distribution.