Dynamic Self-Assembly Induced Rapid Dissolution of Cellulose at Low Temperatures

• Published in: Macromolecules Vol. 41; no. 23; pp. 9345 - 9351
• Main Authors: Cai, Jie, Zhang, Lina, Liu, Shilin, Liu, Yating, Xu, Xiaojuan, Chen, Xuming, Chu, Benjamin, Guo, Xinglin, Xu, Jian, Cheng, He, Han, Charles C, Kuga, Shigenori
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 09.12.2008
• Subjects: Applied sciences; Cellulose and derivatives; Exact sciences and technology; Natural polymers; Physicochemistry of polymers; Self assembly; Urea; Hydrodynamic radius; Basic solution; Cellulose; Temperature effect; Aqueous solution; Experimental study; Dissolution; Mechanism; Low temperature
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma801110g

Cellulose can be dissolved in precooled (−12 °C) 7 wt % NaOH−12 wt % urea aqueous solution within 2 min. This interesting process, to our knowledge, represents the most rapid dissolution of native cellulose. The results from 13C NMR, 15N NMR, 1H NMR, FT-IR, small-angle neutron scattering (SANS), transmission electron microscopy (TEM), and wide-angle X-ray diffraction (WAXD) suggested that NaOH “hydrates” could be more easily attracted to cellulose chains through the formation of new hydrogen-bonded networks at low temperatures, while the urea hydrates could not be associated directly with cellulose. However, the urea hydrates could possibly be self-assembled at the surface of the NaOH hydrogen-bonded cellulose to form an inclusion complex (IC), leading to the dissolution of cellulose. Scattering experiments, including dynamic and static light scattering, indicated that most cellulose molecules, with limited amounts of aggregation, could exist as extended rigid chains in dilute solution. Further, the cellulose solution was relatively unstable and could be very sensitive to temperature, polymer concentration, and storage time, leading to additional aggregations. TEM images and WAXD provided experimental evidence on the formation of a wormlike cellulose IC being surrounded with urea. Therefore, we propose that the cellulose dissolution at −12 °C could arise as a result of a fast dynamic self-assembly process among solvent small molecules (NaOH, urea, and water) and the cellulose macromolecules.