One-dimensional and two-dimensional liquid chromatography of sulphonated lignins.

One- and two-dimensional separation methods have been developed for the analysis of lignosulphonates and sulphonated kraft lignins. The evaluated sulphonated lignins are all used as dispersants in agrochemical formulations, where some give rise to physical instabilities of formulations. It is of interest to identify the properties of the sulphonated lignins that determine the formulation characteristics. Tetrapentylammonium bromide has been used as an ion-pair reagent in a gradient-elution reversed-phase liquid-chromatographic (IP-RPLC) method, as well as in aqueous size-exclusion chromatography (SEC). Clear differences in the size distribution were observed between different batches of sulphonated lignins. The RPLC and SEC methods were combined in a comprehensive two-dimensional liquid chromatography system. The retention times in the two dimensions were highly correlated. Therefore, the full potential of comprehensive two-dimensional liquid chromatography was not yet realized. However, the results did reveal that retention in IP-RPLC was not determined by the degree of sulphonation of similar-size molecules. Rather, molecules were separated according to size and the degree of sulphonation appears to be approximately constant. The information obtained in this study represents a significant step towards meaningful correlations between the requirements of surfactants within an agrochemical formulation and structural parameters, such as the size and the degree of sulphonation of lignin oligomers.