Method development in interaction polymer chromatography

Interaction polymer chromatography (IPC) is an umbrella term covering a large variety of primarily enthalpically-dominated macromolecular separation methods. These include temperature-gradient interaction chromatography, interactive gradient polymer elution chromatography (GPEC), barrier methods, etc. Also included are methods such as liquid chromatography at the critical conditions and GPEC in traditional precipitation-redissolution mode. IPC techniques are employed to determine the chemical composition distribution of copolymers, to separate multicomponent polymeric samples according to their chemical constituents, to determine the tacticity and end-group distribution of polymers, and to determine the chemical composition and molar mass distributions of select blocks in block copolymers. These are all properties which greatly affect the processing and end-use behavior of macromolecules. While extremely powerful, IPC methods are rarely employed outside academic and select industrial laboratories. This is generally because most published methods are “bespoke” ones, applicable only to the particular polymer being examined; as such, potential practitioners are faced with a lack of inductive information regarding how to develop IPC separations in non-empirical fashion. The aim of the present review is to distill from the literature and the author's experience the necessary fundamental macromolecular and chromatographic information so that those interested in doing so may develop IPC methods for their particular analytes of interest, regardless of what these analytes may be, with as little trial-and-error as possible. While much remains to be determined in this area, especially, for most techniques, as regards the role of temperature and how to fine-tune this critical parameter, and while a need for IPC columns designed specifically for large-molecule separations remains apparent, it is hoped that the present review will help place IPC methods in the hands of a more general, yet simultaneously more applied audience.