The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers Mike Himmel

Background: Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes Methods: Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. Results: At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Conclusions: Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.