Low-temperature dynamic light scattering. I. Structural reorganization and physical gel formation in cellulose triacetate/methyl acetate dilute solution at -99 - 45 degrees C.
Curious low-temperature solubility of cellulose triacetates (CTA; here we use nominally "CTA," but the sample still contains 7% of C-6 position hydroxyls) in an organic solvent, methyl acetate (MA), was studied by a newly designed low-temperature type of DLS apparatus, which enabled for the first time to investigate the structural change of CTA in solution from 45 degrees C down to -100 degrees C. A molecularly dissolved CTA was found to coexist with three types of self-assemblies over all the temperature ranges except for the three specific temperatures T* of 30, -10, and -75 degrees C. However, these multiple self-assemblies are not in real thermodynamic equilibrium but in a metastable state, which could be stabilized effectively by the intermolecular hydrogen bonding (HB) with the help of the dipole interaction at low temperatures. In more detail, with decreasing temperature, these assemblies performed the structural reorganization drastically at three T*'s and would finally be frozen in a physical gel structure at -99 degrees C; around the freezing temperature of MA, CTA molecules could be trapped homogeneously in the frozen MA. The crucial role in such structural reorganizations is played by the balance between the intermolecular HB and the dipole interaction worked in the highly electronegative solvent. Because these interactions, which are mediated by the solvent electronegativity, change drastically with temperature, they result in the control of not only the single CTA chain conformation (= the intramolecular HB) but also the binding ways of the intermolecular HBs between CTA molecules and they induce multitudinous metastable structures in solution. Here it is noted that HB could work mainly between the C-6 position hydroxyls in the anhydroglucose units of CTA and are essentially effective at low temperatures.
Tsunashima
Yoshisuke
Y
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan. yh-tsunashima@r7.dion.ne.jp
Ikuno
Masaya
M
Onodera
Gen
G
Horii
Fumitaka
F
D000085:Acetates / Q000737:chemistry*; D002482:Cellulose / Q000031:analogs & derivatives* / Q000737:chemistry; D005782:Gels / Q000138:chemical synthesis*; D008956:Models, Chemical; D012542:Scattering, Radiation; D013696:Temperature; D013816:Thermodynamics
D000085:Acetates; D005782:Gels; D002482:Cellulose; C024671:cellulose triacetate; C046923:methyl acetate