This work focused on providing a molecular understanding of the way the polymeric properties of kraft lignin and its derivatives are affected by various thermal treatments. This information was then correlated with the polymeric properties of the materials (glass transition temperature (T g ), molecular weight characteristics, and thermal stability) for a series of selectively and progressively derivatized softwood kraft lignin samples. Softwood kraft lignin was highly susceptible to thermally

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... nduced reactions that caused its molecular characteristics to be severely altered with the concomitant formation of irreversible cross-linking. However, by fully methylating the phenolic OH groups from within the structure of softwood kraft lignin, the thermal stability of these materials was dramatically enhanced and their T g reduced. While optimum thermal stability and melt re-cycling was observed with the fully methylated derivatives, fully oxypropylated phenolic substitution did not offer the same possibilities. The accumulated data is aimed at providing the foundations for a rational design of single component, lignin-based thermoplastic materials with reproducible polymeric properties when thermally processed in a number of manufacturing cycles.