Boron Lewis Acid Extraction of Wood Generates High Quality Lignin

The separation of lignocellulose into lignin, cellulose, and hemicellulose without significantly altering the chemical structures of these component biopolymers remains a modern chemical challenge. Lignin, in particular, has potential as a highly valuable feedstock material but remains underutilized due to the difficulty of generating lignin with low modification and condensation. This work investigates the lignin-rich solids ("boron lignin") generated from a previously reported boron Lewis acid-mediated lignocellulose separation and concludes that (1) boron Lewis acid extraction removes 80-85% of carbohydrates from the original lignocellulose sample, and (2) the resulting lignin possesses a low condensation level and high similarity to native lignin structure. Residual carbohydrate assessment, depolymerization efficiency analyses, heteronuclear single quantum coherence (HSQC) and solid-state nuclear magnetic resonance (NMR) analyses are discussed, including benchmarking results with alternate lignin sources known to possess low and high condensation levels. Further, two different wood sources (white pine, a softwood, and beechwood, a hardwood) were employed to generate lignin samples. Depolymerization of a white pine-derived boron-lignin produced 47% (±9.5) of extractable monomers, which compares well to a state-of-the-art method to generate low condensed lignin (56 ± 7.8%). An unexpected instability of the oil sample was observed following hydrogenolysis of boron lignin generated from beechwood. Dramatic color changes coupled with precipitation and lowered monomer yields were observed when samples were aged (11% decrease) or concentrated (30% decrease). Based on NMR spectroscopic analyses, this instability is postulated to arise due to boron-mediated demethylation of methoxy sites on the lignin scaffold.