Sustainable Process for the Depolymerization/Oxidation of Softwood and Hardwood Kraft Lignins Using Hydrogen Peroxide under Ambient Conditions

The present study demonstrated a sustainable and cost-effective approach to depolymerize/oxidize softwood (SW) and hardwood (HW) kraft lignins using concentrated hydrogen peroxide at temperatures ranging from 25 to 35 °C, in the absence of catalysts or organic solvents. The degree of lignin depolymerization could be simply controlled by reaction time, and no further separation process was needed at the completion of the treatment. The obtained depolymerized lignin products were comprehensively characterized by GPC–UV, FTIR, (31)P-NMR, TGA, Py-GC/MS and elemental analysis. The weight-average molecular weights (M(w)) of the depolymerized lignins obtained from SW or HW lignin at a lignin/H(2)O(2) mass ratio of 1:1 after treatment for 120 h at room temperature (≈25 °C) were approximately 1420 Da. The contents of carboxylic acid groups in the obtained depolymerized lignins were found to significantly increase compared with those of the untreated raw lignins. Moreover, the depolymerized lignin products had lower thermal decomposition temperatures than those of the raw lignins, as expected, owing to the greatly reduced M(w). These findings represent a novel solution to lignin depolymerization for the production of chemicals that can be utilized as a bio-substitute for petroleum-based polyols in polyurethane production.