Reactivity of lignin in supercritical methanol studied with various lignin model compounds

• Published in: Wood science and technology Vol. 37; no. 3-4; pp. 299 - 307
• Main Authors: Tsujino, J, Kawamoto, H, Saka, S
• Format: Journal Article
• Language: English
• Published: Berlin Springer 01-12-2003; Springer Nature B.V
• Subjects: Alcohols; Applied sciences; Aromatic compounds; Biphenyl; Depolymerization; Exact sciences and technology; Guaiacol; Lignin; Lignin and derivatives; Macromolecules; Methanol; Natural polymers; Phenolic compounds; Phenols; Physicochemistry of polymers; supercritical fluid extraction; Supercritical fluids; Tin; Degradation; Depolymerization; Lignin; Guaiacol; Reactivity; HPLC chromatography; Supercritical state; Experimental study; Methanol
• ISSN: 0043-7719; 1432-5225
• DOI: 10.1007/s00226-003-0187-3

Behavior of lignin in supercritical methanol (250–270°C, 24–27 MPa) was studied by using lignin model compounds at the tin bath temperature of 270°C with a batch-type reaction vessel. Guaiacol and veratrole were selected as a guaiacyl type of aromatic ring in lignin, while 2,6-dimethoxyphenol and 1,2,3-trimethoxybenzene as a syringyl one. In addition, biphenyl and β-O-4 types of dimeric lignin model compounds were, respectively, studied as condensed and ether linkages between C6-C3 phenyl propane units. As a result, both guaiacyl and syringyl types of aromatic rings were very stable, and the biphenyl type was comparatively stable under supercritical conditions of methanol. However, β-ether linkage in the phenolic β-O-4 model compound was cleaved rapidly into guaiacol and coniferyl alcohol, which was further converted to its γ-methyl ether. Non-phenolic β-O-4 model compound was, on the other hand, converted initially into its α-methyl ether and degraded further to produce guaiacol. These lines of evidence imply that in lignin macromolecules, the new phenolic residues are continuously formed and depolymerized repeatedly in supercritical methanol into the lower molecular products, mainly by the cleavage of the dominant β-ether structure in lignin.