✍ Scribed by Katsunari Yasuda; Masatoshi Saito; Kenji Kamide
No coin nor oath required. For personal study only.
An attempt was made to study the flow birefringence and the viscosity of the systems of cellulose in aqueous sodium hydroxide and cadoxen solutions. For this purpose alkali‐soluble cellulose samples with crystal form I (simply denoted as cellulose I sample), prepared from conifer wood pulp by the steam‐explosion method, and alkali‐soluble cellulose samples with crystal form of cellulose II (cellulose II sample), regenerated from cuprammonium cellulose solution under specific conditions, were used. The extinction angle χ of aqueous alkali solutions of the cellulose I sample is significantly less shear rate (γ) dependent as compared with that of the cellulose II sample. In the latter system the χ versus γ relations for a given cellulose sample shifted to the higher γ side with decrease in the average molecular weight. The viscosity of the cellulose II sample in aqueous sodium hydroxide solutions is approximately twice that of the cellulose I sample in the same solvent if compared at the same molecular weight, same concentration, and same temperature. The latter solution showed a non‐Newtonian property at relatively smaller γ than the former solution did. Spin‐lattice relaxation time T~1~ (by ^13^C‐NMR) of cellulose in cadoxen solution was smaller in cellulose I, suggesting the existence of intra‐ and intermolecular hydrogen bondings at the C~6~ position of cellulose molecules in cellulose I solution. A dynamic light scattering study on cellulose in cadoxen showed that in a 5 wt % solution of cellulose I cellulose particles are dispersed with time into smaller particles and the larger particles could be excluded by ultracentrifuge and in cellulose II solutions the cellulose particles had almost the same size during storage. The above findings indicate that in 5 wt% cellulose I solutions in aqueous alkali or in cadoxen, cellulose I is not dissolved molecularly, but a supra‐molecular structure of the solid is at least partly reserved in the above solutions.
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