A novel tetrafunctional mesogenic epoxy monomer with a cyclic-siloxane chain as a central part was successfully synthesized and characterized by proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, differential scanning calorimetry, and polarized optical microscopy. The transition temperature and liquid crystallinity of cyclic-siloxane type mesogenic epoxy were compared with those of linear-siloxane type mesogenic epoxy. Moreover, epoxy thermosets were prepared based on the cyclic- and linear-siloxane type mesogenic epoxy monomers and 4,4′-diaminodiphenylethane. The effects of epoxy backbone moiety on thermal and mechanical properties were investigated in detail. As a result, the cyclic-siloxane type mesogenic epoxy thermoset shows glass transition temperature-less behavior and low coefficient of linear thermal expansion without a decrease in toughness.
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