Investigation of the thermal deconstruction of β-β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT)

Model compounds that represent important substructures in lignin have popularly been used to gain a better understanding of the behavior of lignin during thermal deconstruction, such as fast pyrolysis. The β-O-4 linkage of lignin has previously been the focus of many model compound studies as it is the most prevalent linkage found in native lignin. In this work, two lesser studied linkages, the β-β′ and 4-O-5, were investigated with density functional theory (DFT). Bond dissociation enthalpies (BDEs) were calculated for the relevant bonds along each interunit linkage for two model compounds containing these linkages. Conformational analysis of the first model oligomer has a relative enthalpy difference of 1.55 kcal mol −1 . For the β-β′ linkage, the alpha carbons had the lowest BDEs of the ring opening reactions due to excessive electron delocalization around the aromatic rings. The bonds of the 4-O-5 linkage had similar BDEs but were appreciably higher than the BDEs for other ether linkages, such as β-O-4 and α-O-4. The higher BDEs of the 4-O-5 bonds is a result of the radical being formed on an aromatic carbon compared to an aliphatic carbon. Our results indicate the ring-opening reactions around the alpha-carbon of the β-β′ linkage would be a major reaction point during thermal deconstruction of the chosen oligomers. This work provides valuable information on the thermal deconstruction behavior of two lesser studied interunit linkages that builds on the authors' previous work, on β-O-4, α-O-4, and β-5 linkages, to develop a library of reaction information for various lignin interunit linkages. Density functional theory (DFT) simulations were performed on two lesser understood linkages in lignin. The C α -containing bonds look to be the primary points of reaction along the β-β′ linkage during thermal conversion.