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

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.

Gel permeation chromatography of poly(dimethyl siloxane). I. The universal calibration

“…The calibration curve of polystyrene is shown in 4. Calibration curves for polystyrene (0) and polydimethylsiloxane ( 0 ) .…”

Characterization of the extremely high molecular mass polystyrene by gel permeation chromatography

“…mass range• From the constants of the Kuhn-Mark-Houwink (KMH) equation at 25°C for PS in THF K= 6.8x10-3dl/g, a = 0.766 (20) or in a binary mixture of MEK and MeOH, 89•0:11.0, K= 7.3x10 -2 dl/g, a = 0.5 (21), neglecting the interval of mol. mass range• From the constants of the Kuhn-Mark-Houwink (KMH) equation at 25°C for PS in THF K= 6.8x10-3dl/g, a = 0.766 (20) or in a binary mixture of MEK and MeOH, 89•0:11.0, K= 7.3x10 -2 dl/g, a = 0.5 (21), neglecting the interval of mol.…”

Relation between intrinsic viscosity and molecular weight

“…To determine the corresponding molecular weight we assume that the resin is polystyrene with a Mark-Houwink relation? 1 is the intrinsic viscosity of fraction 1 of weight fraction w1, etc. The summation of Table I yields for the whole resin an intrinsic viscosity of 0.812.…”