A series of side-chain liquid-crystalline polymers was prepared containing disiloxane units in the spacer. The polymers consist of a polymethacrylate backbone and several kinds of mesogenic side groups. For the synthesis of the desired monomers, silanol compounds carrying a mesogenic group were prepared as the intermediates. The polymers were obtained by ordinary free-radical polymerization. As the mesogenic groups, linear-type p-or p'-substituted phenyl and biphenylyl benzoates, p-or m-substituted benzoyloxybiphenyl groups and laterally attached biphenylyl benzoate-type mesogens were chosen, and the structural effects on the thermal properties of the polymers were investigated. In the case of linear-type mesogens, only when triple-core mesogens were introduced a stable smectic mesophase was observed with a wide range of phase stability, while no mesophase was observed for the linear double-core and the laterally attached mesogens.On the other hand, a highly ordered smectic phase was observed for polymers having linear-type triple-core mesogens with p-alkoxy and m-cyano end groups. Furthermore, it was revealed that the introduction of a disiloxane unit in the spacer lowered the temperature range of the mesophase, in comparison with polymers having an alkylene spacer with the same backbone component and mesogens.
Copolymerization of monomers containing the disiloxane unit in the spacer component and linear triple-core mesogens with comonomers containing linear double-core mesogens, or laterally attached triple-core mesogens was carried out radically. The effect of copolymer composition and monomer structure on the mesomorphic properties of the obtained copolymers was investigated in detail. The copolymers with a comonomer content up to 50 mol-%, exhibit an enantiotropic nematic phase, whereas the parent homopolymers containing triple-core mesogens exhibit a smectic phase. The copolymer containing more than 50 mol-To of the comonomer shows no mesophase. The isotropization temperature of the copolymers decreases with increasing comonomer content. However, the glass transition temperature is almost unchanged upon introduction of the comonomer unit. In case of copolymers containing laterally attached mesogens, a smectic phase was observed below the temperature range of the nematic phase. Consequently, the mesophase and the temperature range of the liquid-crystalline state can be controlled by the introduction of the comonomer unit whose parent homopolymer does not exhibit any mesophase.
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