Stable Oligomer Formation from Lignin by Pyrolysis of Softwood in an Aprotic Solvent with a Hydrogen Donor

Pyrolysis of Japanese cedar wood in diphenoxybenzene (an aprotic solvent) with a hydrogen donor was investigated between 270-380 °C. Under these conditions, re-condensation via radical and quinone methide intermediates was efficiently suppressed and a thermally stable oligomer was obtained. The oligomer was stable even after the treatment time was extended. Yields of lignin-derived products at 270 °C were limited to approximately 20 wt %, but increased to >80 wt % (lignin basis) at the higher temperatures. The oligomer yield increased directly with the extent of the cellulose degradation at 350 °C. Based on the NMR analysis results, the ether bonds in lignin were largely cleaved, but condensed linkages such as β-aryl and β-β and 5-5' types remained. The γ-hydroxypropyl group was identified as a typical side chain, formed by hydrogenation of the double bond of a coniferyl alcohol-type structure.