Immobilization of the Cholesteric Structure Formed by Cellulose Phenylcarbamates and CaCO<sub>3</sub> Mineralization in the Liquid-Crystalline Composite Films

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  • –セルロースフェニルカルバメート類が形成するコレステリック液晶構造の固定化と液晶呈色フィルムにおけるCaCO<sub>3</sub>ミネラリゼーション
  • セルロースフェニルカルバメート類が形成するコレステリック液晶構造の固定化と液晶呈色フィルムにおけるCaCO₃ミネラリゼーション
  • セルロースフェニルカルバメートルイ ガ ケイセイ スル コレステリック エキショウ コウゾウ ノ コテイカ ト エキショウ テイショク フィルム ニ オケル CaCO ₃ ミネラリゼーション

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<p>Liquid-crystalline behavior of phenylcarbamate derivatives of cellulose in vinyl monomer solvents was investigated, and then calcium carbonate (CaCO3) mineralization was conducted in colored films wherein a cholesteric structure of the cellulosic derivatives was immobilized by polymerization and cross-linking of the solvent monomer(s). Two sorts of derivatives, cellulose phenylcarbamate (CPC) and cellulose 3-chlorophenylcarbamate (3Cl-CPC), were used. Although both derivatives were hardly soluble in anionic monomers such as acrylic acid (AA) at high concentrations (>30 wt%), CPC formed a left-handed cholesteric mesophase in a mixture of N-vinyl pyrrolidone (VP)/ AA (10:0–9:1 in wt.) and 3Cl-CPC assumed a right-handed cholesteric arrangement in VP/AA/dimethyl sulfoxide (DMSO) (5:0:5, 3:2:5, or 2:3:5 in wt.); each mesomorphic solution imparted a vivid cholesteric color. By UV-induced polymerization and subsequent washing processes for the lyotropics, the original cholesteric architectures were successfully fixed into the resulting films of CPC/poly(N-vinyl pyrrolidone) (PVP), CPC/poly(N-vinyl pyrrolidone- co-acrylic acid) (P(VP-co-AA)), 3Cl-CPC/PVP, and 3Cl-CPC/P(VP-co-AA). After soaking the liquid-crystalline films in an aqueous salt solution containing Ca2+ and HCO3−, we obtained calcic mineral-hybridized polymer composites. Wide-angle X-ray diffractometry (WAXD) and energy-dispersive X-ray (EDX) spectroscopy revealed that CaCO3 crystals (in calcite form) were deposited inside the films when the anionic AA was present as a matrix component. In thermogravimetric analysis (TGA), it was observed that the flame resistance of the mineralized films was improved in the high-temperature range (>300°C), although the decomposition temperature tended to fall. </p>

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