Thermodynamics and reaction pathways of furfuryl alcohol oligomer formation

• Furfuryl alcohol monomer was converted into a broad range of oligomers.
• Methylene-bridged, ether-bridged, terminal CH2OH, and internal OH dimers were produced.
• The formation of terminal CH2OH is both kinetically and thermodynamically favored.

The acid-catalyzed transformation of furfuryl alcohol (FA) monomer to oligomers has been studied in the liquid phase to investigate the reaction mechanisms and intermediate species by using a combination of quantitative reaction product measurements and density functional theory calculations. FA monomer was converted into oligomers with a broad range of carbon number: C9–C10, C14–C15, C19–C29, > C29. Based on the calculations, terminal CH2OH dimer formation is both kinetically and thermodynamically favored, consistent with the experimental results. The order for dimer production in the C9–C10 range follows terminal CH2OH > ether bridged–methylene bridged dimer > OH-carbon bridge.