Molecular weight-functional group relations in softwood residual kraft lignins

An integrated picture of the distribution of functional groups should be provided as a function of molecular size within residual kraft lignins. With this goal we developed a reliable and reproducible method for determination of the molecular weight and molecular weight distribution of residual kraft lignins (RKLs) over the whole delignification range. In general, our data indicate that for reliable measurement of the molecular weight and its distribution of residual lignin in pulps, the lignin-carbohydrate bonds have to be cleaved prior to size exclusion chromatography. The recently developed method for isolating residual lignins, which involves cellulolytic treatment followed by a mild acid hydrolysis step, was found to be the most suitable approach to achieve this. The molecular weight and polydispersity of all RKLs decreased as a function of delignification. As anticipated, the observed decrease in molecular weight was clearly reflected in the concomitantly decreasing amount of b-O-4 structural linkages present. Similarly, the total phenolic hydroxyl content increased as the molecular weight of the RKLs decreased during kraft pulping. Despite the smaller size of the lignin remaining on the kraft fiber at the end of delignification, the preponderance of condensed phenolic structures within these lignins offers an explanation for delignification problems during bleaching.