Effect of plasticizers and polymer blends for processing softwood kraft lignin as carbon fiber precursors

Plasticizers depress the glass transition temperature (T_g) of polymers and produce a flowable material at lower temperatures. The use of plasticizers to depress T_g of lignin is important, since at high processing temperatures lignin crosslinks, making it intractable. The goal of this study was to assess plasticizers and polymer blends for the ability to retard a commercial softwood kraft lignin from crosslinking and also serve as thermal and rheological property modifiers during thermal processing in the attempt to produced moldable and spinnable lignin for lignin and carbon fiber products. The T_g of the lignin and the lignin mixed with various amounts of plasticizers and with different thermo-mechanical mixing were determined using differential scanning calorimetry. The T_g and the change in heat capacity at the glass transition (ΔC_p) decreased and increased, respectively, about linearly within this plasticizers range with increased plasticizer weight percentage. Gel permeation chromatography results for extruded lignin as well as extruded lignin-plasticizer blends with glycerol, N-allyurea, citric acid with and without sodium hypophosphite, and oleic acid indicate that the presence of these materials reduced the rate of molecular weight increase at temperatures between 100 and 200 °C. Continuous, homogenous films and fibers could be produced by thermal processing with plasticized lignin samples and plasticized lignin-polymer blends, but not with lignin alone. These fibers could be carbonized, yielding up to about 50% of carbon. The present findings have shown the advantages of plasticizers in thermally processing a commercial softwood kraft lignin.