Tailoring the molecular and thermo-mechanical properties of kraft lignin by ultrafiltration

This study has shown that ultrafiltration allows the selective extraction from industrial black liquors of lignin fraction with specific thermo-mechanical properties, which can be matched to the intended end uses. Ultrafiltration resulted in the efficient fractionation of kraft lignin according to its molecular weight, with an accumulation of sulfur-containing compounds in the low-molecular weight fractions. The obtained lignin samples had a varying quantities of functional groups, which correlated with their molecular weight with decreased molecular size, the lignin fractions had a higher amount of phenolic hydroxyl groups and fewer aliphatic hydroxyl groups. Depending on the molecular weight, glass-transition temperatures (Tg) between 70 and 170C were obtained for lignin samples isolated from the same batch of black liquor, a tendency confirmed by two independent methods, DSC, and dynamic rheology (DMA). The Fox-Flory equation adequately described the relationship between the number average molecular masses (Mn) and Tg's-irrespective of the method applied. DMA showed that low-molecular-weight lignin exhibits a good flow behavior as well as high-temperature crosslinking capability. Unfractionated and high molecular weight lignin (Mw>5 kDa), on the other hand, do not soften sufficiently and may require additional modifications for use in thermal processings where melt-flow is required as the first step. Copyright © 2014 Wiley Periodicals, Inc.