Solvent- and Catalyst-Free In Situ Esterification of Citric Acid and Mannitol: Synergistically Enhancing the Dimensional Stability and Mechanical Strength of Poplar Wood

Wood is a sustainable material, but hygroscopicity can affect dimensional stability and mechanical durability. Recent research has increasingly focused on combining citric acid with various polyols as eco-friendly crosslinking systems to improve wood properties. Herein, a solvent-free and catalyst-free method was used to synthesize bio-based polyesters from citric acid and mannitol. In situ curing was carried out after vacuum-pressure impregnation of fast-growing poplar wood (Populus deltoides Marshall). Morphological characterization showed that the polyester filled the cell lumen and penetrated the cell wall structure. It was confirmed by Fourier Transform Infrared (FTIR) and cross-polarization/magic angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) analysis that the polyester formed covalent ester bonds with wood hydroxyl groups, which indicated successful chemical grafting. The dimensional stability and mechanical properties of the modified wood were greatly improved. The parallel compressive strength of the grain reached 41.5 MPa, which was 41.7% higher than that of the untreated wood. This research adopted a citric acid–mannitol polyester, providing a sustainable, economical, and scalable approach for the development of high-performance, degradable wood composites for construction/furniture applications.