Bulletin of the Chemical Society of Japan p. 1649 - 1657 (1997)
Update date:2022-09-26
Topics:
Ogawa, Hiroshi
Kanoh, Shigeyoshi
Motoi, Masatoshi
Polyoxetanes anchoring the mesogen cores of p-spacer-substituted phenyl 4-(4-alkoxyphenylazo)benzoates through a pendant spacer, -CH2O(CH2)4O-, were prepared by a BF3-initiated cationic ring-opening polymerization of the corresponding oxetanes, followed by a fractional reprecipitation of the raw polymer products containing oligomer fractions. The polyoxetanes separated from the oligomers had their peak tops at molecular weights of around 10000-23000 in nearly mono- or dimodal molecular-weight dispersity curves determined by gel permeation chromatography, and indicated fan-shaped textures due to a smectic mesophase over a wide temperature range from about 250 °C to room temperature on heating and cooling processes by polarized optical microscopy. The formation of highly ordered assemblies of the pendant mesogens is ascribable to a cohesion of the 4-(4-alkoxyphenylazo)benzoate moiety in the mesogen core, which can form a larger dipole, due to forming a longer conjugated system from the ester carbonyl to the alkoxy tail, than that of the simple 4-alkoxybenzoate moiety of the mesogen core previously reported by us.
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