Hydroxymethylfurfural as an Intermediate of Cellulose Carbonization.

Hydrogen bond donor solvents such as aromatic solvents inhibit the secondary degradation of cellulose-derived primary pyrolysis products. In a previous study, we found that the formation of solid carbonized products was completely inhibited during cellulose pyrolysis in aromatic solvents, with 5-hydroxymethylfurfural (5-HMF) recovered in certain yields instead. This indicated that 5-HMF is an intermediate in cellulose carbonization. To confirm this hypothesis, the thermal reactivity of 5-HMF was investigated. At 280 °C, pure 5-HMF polymerized into a hard glassy substance through OH group elimination, but further conversion was slow. When pyrolyzed in the presence of glycerol, a model of coexisting primary pyrolysis products from cellulose, a coupling reaction proceeded. Reactions characteristic of cellulose carbonization then occurred, including the formation of acidic groups and benzene-type structures in the solid products. These results confirmed the above hypothesis. The molecular mechanism of cellulose carbonization is discussed, focusing on the crystalline nature.