Simulation of the Chromatography of Oligomers and Polymers with HypercarbTM Column

Abstract

The retention time of a polymer in liquid chromatography depends on the details of its microstructure and topology. Despite the number of separation modes and methods available for polymers, gaining quantitative information from chromatograms remains a challenge. A model able to predict the LC retention time of a polymer accounting for all possible variations in its microstructure could provide some valuable insight during method development and produce the information necessary to establish unambiguous structure/property relationships. In a previous article, we reported on the separation of end-functionalized oligomers with the Hypercarb™ column using interaction polymer chromatography. In this article, the chromatograms for the oligomer were simulated using the general model for the partition coefficient of linear polymers in adsorbing pores developed by Gorbunov and Skvortsov [1]. The chromatograms of the oligomer were simulated under a variety of conditions mimicking the experimental ones. The results confirmed the predictive strength of the model. To explain some unexpected results for high molecular weight polymers under size exclusion conditions, hydrodynamic effects were considered as well as a sorbent consisting of two pore networks. This provided new insight into the Hypercarb™ column properties.