화학공학소재연구정보센터
Macromolecules, Vol.29, No.10, 3597-3602, 1996
Chain Stiffness and Excluded-Volume Effects in Dilute Polymer-Solutions - Cellulose Tris((3,5-Dimethylphenyl)Carbamate)
Nineteen fractions of cellulose tris[(3,5-dimethylphenyl)carbamate] (CTDC) ranging in weight-average molecular weight M(w) from 2.5 x 10(4) to 7.5 x 10(6) have been studied by static light scattering, sedimentation equilibrium, and viscometry in 1-methyl-2-pyrrolidone at 25 degrees C. Since this cellulose derivative exhibits pronounced optical anisotropy, light-scattering data are corrected for the anisotropy effect on the basis of Nagai theory for the Kratky-Porod (KP) wormlike chain with cylindrically symmetric polarizabilities. It is shown that the data for [S-2](z), (the z-average mean-square radius of gyration), delta (the optical anisotropy factor), and [eta] (the intrinsic viscosity) and those reported previously for 11 fractions are described accurately by the known theories for the unperturbed KP chain if M(w) is lower than 7 x 10(5). From the comparison, the persistence length and the monomeric projection of the CTDC chain are estimated to be 7.8 and 0.52 nm, respectively. When M(w) exceeds 10(6), i.e., when n(K) (the Kuhn segment number) increases above 50, excluded-volume effects on [S-2](z) and [eta] become experimentally observable. Though such a large n(K) value for the appearance of volume effects has been considered inconsistent with the Yamakawa-Stockmayer-Shimada (YSS) theory for KP or helical wormlike chains, the observed excluded-volume effects are found to be explained quantitatively in the YSS scheme, i.e., by the YSS perturbation theory combined with the Domb-Barrett function for the radius expansion factor and the Barrett function for the viscosity expansion factor. Thus, this theoretical scheme should have a wider applicability than what might be anticipated from earlier studies.