Two-dimensional tools for analyzing polymer microstructure; coupling non-aqueous ion-exchange chromatography to size-exclusion chromatography

Abstract

Traditional liquid-chromatographic techniques, such as size-exclusion chromatography, (critical) interaction chromatography, and hydrodynamic chromatography, can all reveal certain aspects of polymers and the underlying distributions. The distribution of incorporated acid groups present in polyacrylates can be determined by non-aqueous ion-exchange chromatography, independent of other distributions present. The microstructural details on how this number of acid groups is incorporated in the polymer remains unknown. A low-molar mass polymer molecule with high acid content and a high-molar mass polymer with a low acid content may have the exact same number of acid groups. To take a next step towards understanding the polymer microstructure of water-borne resins, the distribution of incorporated acid groups over the molar-mass distribution has been investigated. For this purpose, an on-line coupling of non-aqueous ion-exchange chromatography (NAIEX) to size-exclusion chromatography (SEC) was established. Practical considerations regarding the system setup with respect to chromatography modes and column- and valve switching dimensionality are discussed. The orthogonality of NAIEX and SEC is demonstrated. Both liquid chromatography modes may be calibrated using polymer standards, yielding a calibrated separation plane. Cross-sectional data on either the molar mass distribution or the acid group distribution at a certain point of the separation plane is obtained. The value of the designed setup was demonstrated by the detailed characterization of the combined acid-group and molar-mass distribution in polymers with a low acid content, in the order of a few mass-%. Several stages of the emulsion polymerization process could be identified using the combined power of NAIEX and SEC.

Keywords: Heterogeneity analysis; On-aqueous ion-exchange chromatography; Two-dimensional liquid chromatography; Water-borne polymers.