High-Resolution Profiling of the Functional Heterogeneity of Technical Lignins

[Image: see text] In technical lignins, functionality is strongly related to molar mass. Hence, any technical lignin exhibits concurrent functionality-type distribution (FTD) along its molar mass distribution (MMD). This study combined preparative size-exclusion chromatography with offline characterizations to acquire highly resolved profiles of the functional heterogeneity of technical lignins, which represent crucial information for their material use. The shape of these profiles showed considerable dissimilarity between different technical lignins and followed sigmoid trends. Determining the dispersity in functionality (Đ(F)) of lignins via their FTD revealed a rather homogeneous distribution of their functionalities (Đ(F) of 1.00–1.21). The high resolution of the acquired profiles of functional heterogeneity facilitated the development of a robust calculation method for the estimation of functional group contents of lignin fractions based simply on their MMD, an invaluable tool to simulate the effects of intended purification processes. Moreover, a more thorough evaluation of separations based on functionality becomes accessible.