Fractional Precipitation of Softwood Kraft Lignin: Isolation of Narrow Fractions Common to a Variety of Lignins

In a manner similar to crude oil, technical lignins need refining if their potential as reactive polyphenols of well-defined molecular weight polymers and oligomers is to be actualized. In this paper, we demonstrate that a continuum of narrow fractions can be isolated by the incremental addition of a nonpolar solvent (hexanes) in a polar (acetone) solution of softwood wood kraft lignin. Three distinct commercial samples of softwood kraft lignin were used to examine the validity of the developed protocol using detailed chromatographic and quantitative functional group analytical methods. It was shown that all samples contain a common relatively monodisperse fraction of a polyphenolic material that can be isolated from the different lignins in yields ranging between 10 and 20% w/w. The versatility of the developed fractional precipitation protocol was further validated by creating artificial physical mixtures of the examined lignins in different proportions and isolating from them precisely calculated fractions of nearly identical molecular weight distributions and composition. Overall, the fractional precipitation approach described here offers the possibility that representative specific narrow fractions, common to a variety of softwood kraft lignins, can be isolated irrespective of the manufacturing details of the pulping process. As such, the otherwise known heterogeneous kraft lignin material, whose composition is relatively unpredictable due to manufacturing variations in making pulp, may now offer consistently homogeneous lignin streams with significant commercial ramifications.