Comparison of Number—Average Molecular Weights Calculated by GPC and Membrane Osmometry
Abstract Data are presented which show that when a polymer contains an appreciable amount of low molecular weight species below the diffusion limit of the osmometer membrane, the osmotic molecular weight, Mn, is generally higher than the Mn calculated from gel-permeation chromatography (GPC). Experiments were performed on samples of poly(vinylchloride) (PVC) and high-cis poly (butadiene) polymers. Osmotic data were obtained in the usual manner, while GPC data were obtained using the universal calibration approach. It was found that when all polymer species below approximately 10,000 molecular weight were excluded from the calculation of Mn by GPC, agreement in Mn was obtained between membrane osmometry and GPC. The data obtained suggest that the choice of Mn as measured by membrane osmometry in the calibration of the GPC should not be done casually, as the measured Mn may not reflect the “true” value of that sample, especially when the polymer sample contains an appreciable amount of low molecular weight material.