An analytical approach to elucidate the architecture of polyethyleneimines

Abstract Polyethyleneimine (PEI) is a common polymer used in many industrial applications and in research, especially in surface chemistry. It is available in a wide range of molecular weights and different degrees of branching. It is classified as linear or branched and sometimes the term hyperbranched is also used. This description, however, is quite rough, which limits the possibility to correlate the structure of the PEI to its properties. The aim of this study is to provide analytical tools to characterize the polymer at a level of detail not normally provided by the supplier of PEI. To this end, five commercially available polyethyleneimines were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and nuclear magnetic resonance spectroscopy to gain insight into the structure and the functional groups present in the polymers. Quantitative 13 C NMR analysis turned out to be particularly useful, revealing the degree of branching of the polymer based on the ratio of primary, secondary, and tertiary amino groups.