Effect of Urea Concentration on the Viscosity and Thermal Stability of Aqueous NaOH/Urea Cellulose Solutions

Aqueous solutions of sodium hydroxide (NaOH) and urea are a known and versatile solvent for cellulose. The dissolution of cellulose occurs at subambient temperatures through the formation of a cellulose-NaOH-urea “inclusion complex” (IC). NaOH and urea form a hydrate layer around the cellulose chains preventing chain agglomeration. Urea is known to stabilize the solution but its direct role is unknown. Using viscometry and quartz crystal microbalance with dissipation monitoring (QCM-D) it could be shown that the addition of urea reduced the solutions viscosity of the tested solutions by almost 40% and also increased the gelation temperature from approximately 40°C to 90°C. Both effects could also be observed in the presence of additional cellulose powder serving as a physical cross-linker. Using Fourier transform infrared (FTIR) spectroscopy during heating, it could be shown that a direct interaction occurs between urea and the cellulose molecules, reducing their ability to form hydrogen bonds with neighbouring chains.

Insulated Polyacetylene Chains in an Inclusion Complex by Photopolymerization

ABSTRACTThe properties of a material often depend on the degree of order of their atomic, molecular, or crystalline domain components. This is expected to be especially true for the case of polyacetylene, whose properties are highly anisotropic. For many applications, it may be necessary to have macroscopic order but not necessarily crystalline order. Having polyacetyelene chains fully extended and aligned parallel to each other may be sufficient for these applications even without order of the chains around their long axis. We report here progress in the use of an inclusion crystal containing a photo-reactive precursor to prepare high molecular weight polyacetylene. Raman spectroscopy was performed to probe the resulting conjugated polyene chains. Ultraviolet irradiation of a 1,4-diiodo-1,3-butadiene/urea inclusion complex results in the appearance of new resonance-enhanced Raman modes at 1125 and 1509 cm-1. The Raman spectra of the resulting confined polyene chains are very similar to freestanding isolated trans-polyacetylene prepared by solution methods.