Reorganization of dynamic self-assemblies of cellulose diacetate in solution: dynamical critical-like fluctuations in the lower critical solution temperature system.
Dynamics of cellulose diacetate (CDA, the total degree of substitution (TDS) = 2.44) in dimethylacetamide (DMAc) in dilute solution was investigated at 2, 10, 20, 30, 40, 49.7, and 61.5 degrees C through dynamic light scattering in the quiescent state. The following three facts were made clear. First, CDA existed in three types of structures in the polar solvent, DMAc; one is a single CDA chain, and the others are dynamic structures, or self-assemblies, which were formed temporarily and locally by the solvent-mediated hydrogen bonding between the intermolecular C-6 position hydroxyls of the anhydroglucose units in the CDA backbone. Second, CDA showed a nature of low-temperature solubility in DMAc, that is, CDA is expected to dissolve molecularly below -12 degrees C but to take a phase separation above 65 degrees C, where two structures such as collapses of a single CDA chain and an aggregate appear. Third, a reorganization in the dynamic structures was detected at the temperature T = 33.8 degrees C. At this temperature, two dynamic structures showed the discontinuity in their correlation lengths, whereas the single CDA realized an uncorrelated chain state in the dynamical sense. In view of the low-temperature solubility of CDA in DMAc, this abnormal behavior around T was explained by dynamical critical-like fluctuations if T were treated as a kind of lower critical solution temperature (LCST) in the CDA/DMAc system. Here, the self-assemblies arise as the dynamical fluctuations under the spinodal decomposition situation and the competition between the hydrogen bonding (HB) and the hydrophobic interaction (HPhI) makes the conformation of CDA chains change drastically. In this scheme, the solvent-mediated HB and HPhI play important roles in the structure reorganization of cellulose derivatives in strong electronegative solvents, though HB and HPhI cooperate with the inherent chain helicality.
Tsunashima
Yoshisuke
Y
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Kawanishi
Hiroyuki
H
Horii
Fumitaka
F
D002482:Cellulose / Q000031:analogs & derivatives* / Q000737:chemistry*; D003080:Cold Temperature; D019281:Dimerization; D008027:Light; D008956:Models, Chemical; D015394:Molecular Structure; D012542:Scattering, Radiation; D012996:Solutions; D013696:Temperature
D012996:Solutions; D002482:Cellulose; C026170:cellulose diacetate