This study aimed to investigate the intrinsic efficiency of renewable alcohols, applied under autocatalytic conditions, for removing lignin from aspen and hot-water-extracted aspen while substantially preserving the lignin structure so as to facilitate various valorization strategies. Ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol (BDO), ethanol (EtOH), and tetrahydrofurfuryl alcohol (THFA) were evaluated based on their lignin solubilization ability, expressed as the relative energy difference (RED) following the principles of the Hansen solubility theory. The findings indicate that alcohols with a higher lignin solubilization potential lead to increased delignification, almost 90%, and produce a lignin with a higher content of β-O-4 bonds, up to 68% of those found in aspen milled wood lignin, thereby indicating their potential for valorization through depolymerization. However, these alcohols also produce lignin with a higher content of β-β and β-5 bonds, resulting in a higher molecular weight and polydispersity, due to readily occurring homolytic reactions. Hot-water extraction (HWE) conducted prior to alcohol treatment reduced the delignification efficiency and resulted in a lignin with a lower β-O-4 bond content. The lignins produced in these experiments exhibited a superior UV-A absorption capacity compared with synthetic benzophenone, as well as a greater radical quenching ability than synthetic butylated hydroxytoluene, indicating their potential for use in the protection of polymers against degradation.
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