Photopolymerization of Langmuir monolayers composed of bifunctional acrylic liquid crystalline (LC) compounds was observed in situ by polarizing optical microscopy. In a dark state, monolayers of the LC compounds formed at an air-water or liquid-liquid interface exhibited liquid-like fluidity and in-plane optical anisotropy because of the coherent molecular tilt from the surface normal. Irradiated by UV light, the in-plane anisotropy and the liquid fluidity gradually disappeared with time, indicating the formation of the polymerized monolayers. Because the constituent molecules possess polymerizable acryloyl groups, under UV light, they are combined by acrylic polymer chains grown on the interface, which decreases the intermolecular distance and disturbs the coherent molecular tilt, resulting in the evanescence of the in-plane optical anisotropy and the fluidity. In contrast to the classical model of radical polymerization, the time taken for the monolayers to be photopolymerized was inversely proportional to the UV intensity, which is ascribed to the ideal two dimensionality of the reaction field. Because the polymerization degree is quantitatively estimated from the in-plane optical anisotropy of the LC monolayers, the process is traced, from moment to moment, by in situ microscopy observation.
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