Abstract
A series of an ABA triblock copolymer with amorphous polymethacrylate A blocks and a main-chain liquid-crystal (LC) polyester center block were prepared with the molecular weight of the amorphous blocks (Mn am) ranging from 2300 to 10 000 and that of the LC block kept constant at 10 000. Irrespective of asymmetric compositions, all block copolymers invariably formed lamellar microstructures. The LC segments were more extended perpendicular to the interface to form smectic layers parallel to the lamellae and folded to be accommodated in lamellae, whereas the amorphous segments had dimensions similar to those of segments in amorphous block copolymer microdomains. Increases in Mn,am enlarge the interfacial area between the amorphous and LC segments and increase the number of folds in LC segments. Thus, LC lamellar thickness decreases and counterbalances the increase in amorphous lamellar thickness so as to suppress the lamellar spacing increase. When the LC segment was in the isotropic phase, the lamellae in the copolymers at asymmetric fractions were disordered and developed on cooling simultaneously with LC formation. The lamellar formation is attributed to the smectic layers that prefer a flat microdomain interface from an energetic perspective.
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