Macromolecules, Vol.32, No.15, 4838-4848, 1999
A morphological study of well-defined smectic side-chain LC block copolymers
The influence of smectic level ordering on domain morphology has been studied in a series of monodisperse side-chain liquid-crystalline (LC) diblock copolymers. These systems, which consist of a polystyrene-b-methacrylate-based side-chain LC, were investigated using electron microscopy and room temperature X-ray scattering. A morphological phase diagram based on volume fraction and molecular weight has been determined for molecular weights up to 40 000 Da. A broad lamellar regime was identified that extends to unusually low LC compositions. At intermediate LC volume fractions around 0.48-0.56, morphologies were predominately lamellar but included many transitional defects in the form of modified layer or hexagonal perforated layer morphologies. The formation of large domains and focal-conic superstructures is shown to depend on the length of the PS block and the overall molecular weight. Samples of lamellar and cylindrical morphologies were oriented using roll casting from solvent and tiber drawing. SAXS diffractograms of oriented samples indicated that in roll-cast films of the copolymer with a hexyl spacer smectic layers were oriented perpendicular to the lamellar morphology, but the longer decyl spacer system resulted in orientation of the smectic layers parallel to the lamellae. These results imply that the degree of decoupling of the mesogen from the backbone is critical to LC orientation within the layers.
Keywords:LIQUID-CRYSTALLINE BLOCK;ASYMMETRIC DIBLOCK COPOLYMERS;AMORPHOUS A-BLOCK;ANIONIC-POLYMERIZATION;PHASE-BEHAVIOR;ORIENTATION;MELT;METHACRYLATE;TRANSITION;LAMELLAE