Acid-Catalyzed Furfuryl Alcohol Polymerization: Mechanism Investigation by the Raman Spectroscopy and Density Functional Theory Calculation

The Raman spectra for acid-catalyzed polymerization of furfuryl alcohol (FA) were investigated and the results were compared with computed spectra at the B3LYP level of theory. Comprehensive thermodynamic investigations of the protonation of furfuryl alcohol, polymerization initiation, and formation of diene and diketone were performed with B3LYP level theory. Based on the thermodynamics, the formation of diene structure from difurfuryl furan is preferred over the diketone structure formation. Quantitative and qualitative Raman spectra analysis clearly indicate the stability of FA at room temperature regardless of the concentration of water/furfuryl alcohol in the absence of acid catalyst, while in the presence of a mineral acid the FA monomer under goes vigorous reaction to produce polymers. Based on the measured and calculated Raman spectra, diene structure formation was predicted and this is further supported by density functional calculations.

This material is based upon work supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.