The structures of poly[oxy(N‐alkylsulfonylmethyl)ethylene]s (ASE‐Ns) were examined with X‐ray, IR, DSC, and polarized optical microscopy. The structures of ASE‐Ns were strongly dependent on the alkyl side‐chain length. ASE‐2 and ASE‐3, the shortest ones, were amorphous materials. ASE‐4 and ASE‐5 showed nematic characteristics. ASE‐6–ASE‐12 had smectic A structures. ASE‐14 and ASE‐16 could be labeled as more ordered structures higher than smectic A (probably smectic B or smectic E). The d‐spacings of the first small‐angle reflections were double the most extended side‐chain length and linearly increased with a slope of 2.50 Å per methylene unit, regardless of the structural phases. The maintenance of the double‐layered structure in all ASE‐Ns may be due to the strong dipole–dipole interactions at both sides of the layers against the main chain for all amorphous, nematic, and smectic phases of ASE‐Ns. The double‐layered structure was maintained above the isotropic temperature, indicating that dipole–dipole interactions were not destroyed although the alkyl side chains melted during the isotropic transition.
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Park et al. (2004) studied this question.