Thermal and liquid crystalline properties of cellulose β-ketoesters prepared by homogeneous reaction with ketene dimers |
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Authors: | Yutaka Yoshida Akira Isogai |
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Institution: | (1) Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan |
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Abstract: | Cellulose β-ketoesters having long alkyl or alkenyl chains were prepared by homogeneous reactions with alkyl or alkenyl ketene dimmers (OKD or AKD), and were characterized by X-ray diffractometory, differential scanning calorimetry, optical microscopy with cross polarizers and others. The Cellulose/OKD and AKD β-ketoesters with degrees of substitution (DS) of more than 1.5 were gummy solid at room temperature and had birefringence due to liquid crystalline structures in wide temperature range. The liquid crystalline/isotropic phase transition points were 150–175 °C, depending on the DS and substituents introduced into cellulose hydroxyls. X-ray diffraction patterns indicated that cellulose backbones had disordered structures at room temperature, while alkyl chains in the substituents formed ordered or crystalline domains in the cellulose β-ketoesters. Films of the cellulose/AKD β-ketoesters prepared by casting their chloroform solutions on glass plates had highly hydrophobic nature, and contact angles of water droplet on the films were more than 90°. The water-contact angles on the films decreased to some extent just after heating of the films at 105 °C, whereas they were gradually recovered to the initial values by conditioning at ambient temperature. |
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Keywords: | β -Ketoester Alkylketene dimer DSC Thermotropic liquid crystal X-ray diffraction |
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