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Understanding the basic chemical structure of lignin macromolecules can facilitate the development of lignin-based materials. In this study, the lignin structure was regulated through different alkali cooking conditions. The acid precipitated lignin from the spent cooking liquor was purified and fractionated with different organic solvents. The lignin samples with different structures were obtained by regulating the cooking time. The structural characteristics of the lignin preparations were systematically investigated. The results revealed that the structure of lignin was regulated by the heating time and the residence time during the cooking process. Non-condensed lignin was achieved after a specific cooking condition; it had higher molecular weight (9686 g/mol), more β-O-4 linkages (25.3/100Ar), but lower phenolic hydroxyl content (1.51 mmol/g) than the counterpart pulping with longer time duration. The non-condensed lignin also had excellent thermal stability. Compared with industrial lignin, the lignin with non-condensed structure can be modified to obtain phenolic resin materials with better performance. The non-condensed structure with the specific characteristics can broaden the valorization of lignin for producing biochemical and biomaterials.

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