Interlinking Lignin Molecules with Citric Acid: The Effect of Reaction Conditions on Lignin Properties

To increase the molecular weight (MW) and glass transition temperature (Tg) of lignin, thereby improving manufacturing for applications such as polymer blends and carbon fibers, lignin was crosslinked with a renewable interlinking agent, citric acid, via esterification. MW and Tg of a kraft (BioChoiceTM) lignin (BCL) and an alkaline‐pretreated hybrid poplar lignin (HPL) were increased by up to 7x (e.g., from 20 to 146 kDa) and up to 36 °C, respectively. Moderate decreases in polarity were obtained, as observed by the solubility of the esterified lignins in toluene and ethanol. Three reaction mechanisms involving one, two, or three of the carboxylic acids in citric acid are proposed. For both biomass sources, increasing the concentration of citric acid increased the MW (and Tg) of the lignin, whereas increasing the catalyst, sodium hypophosphite (SHP), beyond 1‐2 wt% decreased the MW due to an unwanted side reaction between citric acid and SHP. In fact, for HPL the highest Tg was obtained with no added catalyst, thus creating a green process that uses only renewable feed materials to build the MW and Tg of lignin.