Functionality Distribution of Hydroxyl-Terminated Polybutadienes by Gel Permeation Chromatography. I. Method and Calibration Procedure

In recent years, considerable attention has been focused on the structural characterization of functionally terminated hydrocarbon prepolymers used in propellant binders and other applications. The molecular weight averages and molecular weight distributions of hydroxyl-and carboxyl-terminated poly butadienes have been determined by gel permeation chromatography (GPC). The functionality distribution of these prepolymers has also been previously studied by column fractionation and a procedure combining GPC and column fractionation of the polymer by stepwise elution from silica gel. The carboxyl or hydroxyl equivalent weights of the fractions were determined by infrared or near-infrared spectroscopy. The fractionation procedure is quite laborious, and multiple peaks were observed in the elution profile, making it difficult to decide how the fractions were to be grouped for subsequent analysis. Previously, a technique for determining the distribution of unsaturation in copolymers containing a small number of double bonds as a function of GPC elution volume was developed. The technique utilized a GPC equipped with uv photometer and differential refractometer detectors to determine the ratio of the weight fraction of olefinic bonds to the weight fraction of polymer by GPC analysis of the polymer after derivatization of the double bonds with 2,4-dinitrobenzenesulfenyl chloride. It was suggested that the technique should be applicable for the determination of the distribution of other functional groups with the choice of suitable reagents for derivatization. The purpose of this investigation was to attempt to extend our previous study to simultaneously determine the molecular weight averages, molecular weight distribution, hydroxyl equivalent weight, functionality averages, and functionality distribution of hydroxyl-terminated polybutadienes by a GPC technique.