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Sugarcane straw (SCS) lignin is extracted by SO 2 -Alcohol-Water (SAW) fractionation (155 °C, 1 h) using methanol, ethanol or isopropanol as pulping solvent (SO 2 /Alcohol/Water = 12/44/44 wt%). The SAW fractionation removes 90–95% lignin from SCS of which only 30–45% is isolated as precipitated lignin after solvent evaporation. The precipitated and pulp residual lignin (5–10%) are analyzed for their degree of sulfonation (S/C9) while precipitated lignin is further analyzed in terms of molecular weight distribution (MWD) and alkoxylation reactions. Similar S/C9 values for methanol, ethanol and isopropanol lignin show that the degree of sulfonation is independent of fractionation solvent. However, the sulfonated lignin is comparatively less soluble in the methanol-based liquor compared to the corresponding lignins in the ethanol- and isopropanol-based liquors. The mass average molecular weight, M w , is highest for isopropanol lignin (∼3800) while the numbers for methanol and ethanol lignins are comparatively smaller but nearly equal in magnitude (∼3000). Alkoxyl groups and nuclear magnetic resonance (NMR) analyses are performed to interpret the differences in lignin M w and alkoxylation reactions. Different ether and ester type linkages are identified in NMR spectra confirming lignin alkoxylation. Lignin carbohydrate complexes (LCC) are also found in NMR spectra confirming that some of the detected carbohydrates are covalently bound to lignin. [ABSTRACT FROM AUTHOR]