Betula alnoides lignin, recovered as a byproduct in autocatalyzed ethanol-water pulping process, was converted into viscous polyether polyols through oxypropylation and liquefaction methods, with the aim of adding value to this byproduct. The oxypropylation reaction was performed by reacting autocatalyzed ethanol-water lignin (AEL) with propylene oxide under the acidic and alkaline conditions at room temperature, respectively. In contrast, the liquefaction reaction was carried out using the mixed solvents of polyethylene glycol and glycerol at 160 degrees C with sulfuric acid as a catalyst. The resulting polyether polyols from each method was characterized by Fourier transform-infrared (FTIR), 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and thermogravimetric analysis. Quantitative 31P NMR indicated that all the aliphatic hydroxyl group values of polyols increased significantly by the above two methods. More secondary hydroxyl groups (2.016 mmol/g) were obtained in the alkaline oxypropylation reaction, whereas more primary hydroxyl groups (4.296 mmol/g) were found in the liquefied product. GPC analysis showed that the alkaline oxypropylated product (Mw 3130 g/mol, Mn 2080 g/mol) and liquefied product (Mw 4990 g/mol, Mn 4630 g/mol) have higher molecular weights than AEL (Mw 2560 g/mol, Mn 1530 g/mol). Thermal stability analysis suggested that the polyether polyols have a lower degradation temperature than AEL. These polyols used as precursors in polyurethane synthesis give promising properties, which open new avenues of exploitation of AEL. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013