| Abstract: | A method is developed for the application of the Flory-Mandelkern equation to the determination of the weight-average molecular weights of individual, broad, unfractionated polymer samples. The method includes appropriate averaging of the sedimentation constants and of the intrinsic viscosity of an unfractionated polymer sample in a θ solution from the velocity sedimentation data. By means of the method, individual samples of polystyrene, poly(isooctyl methacrylate) and of the copolymer of styrene with 20% isooctyl methacrylate prepared under the same emulsion polymerization conditions from commercial monomers have been investigated. Appropriate θ solvents have been found by the Elias method. Equations for the dependence of the sedimentation constants and of the intrinsic viscosities in the θ solvents on the molecular weights have been established for the polymers without fractionation. Osmometric and light-scattering measurements as well as Archibald experiments have shown that by the proposed method the molecular weight cut-off effect is eliminated in the above equations and in the polydispersity parameter M w/M n. Molecular weight distributions have been determined for the polymer samples. |
