Recent developments in the detailed characterization of polymers by multidimensional chromatography

Synthetic polymers as well as biopolymers reveal complex structures, such as variations in functionality, chain length and architecture. Therefore, combinations of different chromatographic techniques are a prerequisite for a detailed characterization. One possible approach is the combination of high performance liquid chromatography at critical conditions (LCCC) and size-exclusion chromatography, also named as two-dimensional chromatography, which allows the separation of the polymers according to different properties, like molar mass, chemical composition or functionality. In addition, LCCC hyphenated with different mass spectrometry techniques, e.g. MALDI-TOF or ESI-TOF, leads to additional information about molecular details of the polymeric structure. We summarize in this article the recent developments in two-dimensional chromatography of synthetic polymers and biopolymers since 2005.

► Synthetic polymers as well as biopolymers reveal complex structures, which need the usage of advanced characterization techniques.
► An overview about the possibilities using HPLC in different separation modes, such as LCCC, LEAC, LC LCD or others, is represented in this review article.
► Using combined analysis techniques, such as LC(CC) × SEC, LC(CC) × LC or LC(CC) × MS is necessary to gain further information about the polymer composition and the polymerization process itself.