화학공학소재연구정보센터
Macromolecules, Vol.40, No.17, 6206-6216, 2007
Smectic ordering in main-chain siloxane polymers and elastomers containing p-phenylene terephthalate mesogens
Main-chain liquid crystalline polymers that form low-temperature smectic mesophases are prepared by linking terephthalic acid, bis(4-allyloxyphenyl) ester (PPT) mesogens with 1,1,3,3,5,5-hexamethyltrisiloxane (F3) spacers via Pt-catalyzed hydrosilylation. Significant differences in thermal behavior and mesomorphic ordering are found between the polymer having unsubstituted PPT mesogens (F3-PPT-H) and the polymer having methyl substituents on the terminal rings of the mesogens (F3-PPT-CH3). Combined evidence from polarized light optical microscopy, differential scanning calorimetry, and X-ray diffraction reveals S-CA ordering in both polymers. Smectic elastomers are prepared by nonlinear polymerization of PPT-H or PPT-CH3 mesogens with F3 spacers and a tetrafunctional cross-linker, tetrakis(dimethylsiloxy)silane (A(4)). The dynamic mechanical response of unoriented, polydomain elastomers is characterized in small-strain, oscillatory shear. A prominent peak in tan delta (equivalent to G''(omega)/G'(omega)) associated with the smectic-isotropic clearing transition dominates the mechanical loss spectrum. Mesogen ring substitution is a simple synthetic approach to tuning the dynamic mechanical response of smectic elastomers for possible applications in vibration isolation or impact absorption.