Hyphenation of size-exclusion chromatography to mass spectrometry for precision polymer analysis – a tutorial review

Abstract

With the ever-increasing complexity of polymeric structures obtained via contemporary synthetic strategies, their precision analysis is a challenging task. Thus, powerful analytical techniques must be explored to allow for an in-depth characterization of complex polymers, yielding chemical information at a sensitivity beyond that of commonly applied analysis methods such as conventional size exclusion chromatography (SEC) and NMR spectroscopy. Here, a tutorial overview on the hyphenation of SEC to electrospray ionization mass spectrometry (ESI-MS) is presented, highlighting the resulting benefits in the context of polymer characterization. First, the capability of obtaining structural information of polymers as well as verifying polymer analogous transformations via SEC-ESI-MS is outlined. Importantly, the wide applicability of SEC-ESI-MS is highlighted, e.g. by its use for the determination of radical polymerization rate coefficients, the detailed investigation of radical photoinitiations systems and the examination of absolute molecular weight distributions of polymers. The current tutorial review thus aims to demonstrate the power of SEC-ESI-MS for the characterization of complex polymers and to underline the high potential it has to become a powerful and popular analytical technique in polymer chemistry.