Development of gel permeation chromatography for polymer characterization. II. Universal calibration

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Abstract
GPC appearance volumes have been determined for a series of linear polyethylene, polystyrene, and polybutadiene fractions (Mw/Mn < 1.1) in trichlorobenzene at 130°C. and for the latter two series in tetrahydrofuran at 23°C. A polymer‐type independent relationship between appearance volumes and the equivalent hydrodynamic radii of the polymer molecules has been demonstrated. The equivalent hydrodynamic radius is calculated from intrinsic viscosity data. It is proposed that this relationship can be used to construct a universal GPC calibration curve for polymers that assume a spherical conformation in solution. Methods for applying the universal curve to the determination of molecular weight averages and molecular weight distribution are described. In addition, a method is outlined by which the universal calibration curve can be empolyed for determining number‐average Mark‐Houwink constants from polydisperse samples.