Kraft lignin (KL) was successfully depolymerized into polyols of moderately high hydroxyl number and yield with moderately low weight-average molecular weight (Mw) via direct hydrolysis using NaOH as a catalyst, without any organic solvent/capping agent. The effects of process parameters including reaction temperature, reaction time, NaOH/lignin ratio (w/w) and substrate concentration were investigated and the polyols/depolymerized lignins (DLs) obtained were characterized with GPC-UV, FTIR-ATR, (1)H NMR, Elemental & TOC analyzer. The best operating conditions appeared to be at 250°C, 1h, and NaOH/lignin ratio ≈0.28 with 20 wt.% substrate concentration, leading to <0.5% solid residues and ∼92% yield of DL (aliphatic-hydroxyl number ≈352 mg KOH/mg and Mw≈3310 g/mole), suitable for replacement of polyols in polyurethane foam synthesis. The overall % carbon recovery under the above best conditions was ∼90%. A higher temperature favored reduced Mw of the polyols while a longer reaction time promoted dehydration/condensation reactions.
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