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Polyelectrolytes with ultra-low glass transition temperatures (Tg) are still a rarity. Herein, we report a series of free-flowing lignin polyelectrolytes with ultra-low Tg in the range of −57–9 °C, namely, deep eutectic supramolecular lignin (DESL). The enabling key principle is to couple the eutectic strategy with supramolecular polymerization, bypassing the exclusive reliance on the large size and flexible cation/anion pairs for flowable polyelectrolytes. Following this principle, various sugars have been successfully integrated with lignosulfonic acid via multiple hydrogen bondings, allowing for bulk yet free-flowing supramolecular materials. These DESLs are processible, adaptive, and compatible to serve as macromolecular solvents and are distinct from traditional polyelectrolyte solutions or chemical modification derivatives. The robustness and versatility of our approach provide a fresh opportunity for booming polyelectrolyte utilization, opening access to a yet unknown fluidic material class. [ABSTRACT FROM AUTHOR]

Developing green and effective solvents is of significant importance for the utilization of lignin. Here, we demonstrated that biomass-derived polar aprotic solvents can serve as co-solvents with poly-deep eutectic solvents (PDESs) for massively dissolving various lignin samples at room temperature. The pristine PDESs were composed of polyethylene glycol derivatives and levulinic acid, while all of them exhibited poor solubility to enzymatic hydrolysis lignin (EHL), sodium lignosulfonate (LS), and organosolv lignin (OL). With the further introduction of polar aprotic solvents, including dimethylisosorbide (DMI), dihydrolevoglucosenone (Cyrene), N-formylmorpholine (NFM), and propylene carbonate (PC), synergy between the polar aprotic solvents and PDESs dramatically increased lignin solubility to 96.82%. PC and DMI were more suitable for assisting the solubilization of EHL and OL, while Cyrene and PC were targeted at the solubilization of LS in PDESs, respectively. Moreover, a new unified co-solvent solubilization mechanism relative to the Kamlet–Taft empirical parameters was proposed. The novel polar aprotic/PDES systems provide a new avenue for boosting the high utilization of lignin. [ABSTRACT FROM AUTHOR]