Influence of Oxygen and Mediators on Laccase-Catalyzed Polymerization of Lignosulfonate

Industrial utilization of lignin is of high interest since it represents around 30% of all nonfossil-based carbon sources worldwide. For various applications of lignosulfonates such as for dispersants or adhesives a larger molecular weight is essential. Here, we investigated laccase-catalyzed polymerization of lignosulfonate directly from the pulp and paper industry in the presence and absence of natural and synthetic mediators with and without oxygen supply. For example, laccase-mediated polymerization in the presence of a 2.5 mM TEMPO as mediator with a 10 cm3 min–1 oxygen flow rate led to a 12-fold increase of the molecular weight, while without TEMPO a 13-fold increase was achieved. In contrast, without an external oxygen supply, only a 7-fold increase in molecular weight was achieved compared to a 4-fold increase for the TEMPO–laccase system. Fluorescence intensity, phenol content, and size exclusion chromatography measurements indicate that generally in the presence of high concentrations of mediators, such as TEMPO, vanillin, HBT, and 2,6-dimethoxyphenol, oxidation of other structural units in lignosulfonates may counteract desired polymerization reactions. In summary, for laccase-catalyzed polymerization of lignosulfonates, an external oxygen supply was found to be much more beneficial than the presence of laccase mediators.