Hydrophilic/tert-Butanol-Repellent amine-modified glucose-Precipitated Polymer for Efficient Azeotrope Breaking and Water Treatment

The development of aminated polysaccharide materials is often hampered by a low amine grafting efficiency and high energy consumption. Herein, we report a novel one-pot precipitation polymerization strategy for the facile and scalable synthesis of amine-modified glucose (AMG) by synergistically integrating three distinct reactions: the epoxy-amine addition for oligomer formation, the condensation cross-linking for constructing robust networks, and the Maillard reaction for dramatically enhancing amine grafting sites. This synergistic approach enables a high nitrogen content (18.0%) and a positive surface charge (+31.3 mV) in the resulting AMG. More importantly, the AMG exhibits a unique “hydrophilic and tert-butanol (TBA)-repellent” effect, which is mechanistically unraveled by a significant disparity in binding energy with water (−296.16 kcal/mol) versus TBA (−15.93 kcal/mol), as confirmed by molecular dynamics simulations. Through this effect, AMG successfully breaks the water-TBA azeotropic equilibrium that has been unreported, increasing the TBA concentration by 5% from that of its azeotrope via a simple distillation process. Furthermore, the obtained AMG demonstrates excellent and selective adsorption capacity for anionic dyes. This work provides a novel strategy for designing functional amino polysaccharides and develops a new technology for TBA azeotrope separation.