Side-Chain Liquid Crystalline Block Copolymers with Well Defined Structures Prepared by Living Anionic Polymerization IV. Microphase Morphology in Blends with Coil Homopolystyrenes

The microdomain structure in the blends of liquid crystal (LC)-coil block copolymer with coil homopolymers was studied. The LC-coil block copolymer used is composed of poly(6-[4-(4’-methoxyphenyl) phenoxy] hexyl methacrylate) as a LC segment and polystyrene as a coil segment. It has the molecular weight Mn=47000 with the LC segment fraction of 45 wt%. As a coil homopolymer, three polystyrenes with different molecular weights of 37000, 26000, and 8200 were used. In all the blends with LC segment fractions of 35% to 10%, the microphase segregation is clearly recognized and LC segment in resulting microdomain undergoes the well defined crystal-SmA-isotropic phase transitions. The microdomain structure depends on both the molecular weight of homopolystyrene blended and the phase structure of LC segment. When the highest molecular weight polystyrene with Mn=37000 was blended (so called in a “dry-brush” regime), a lamellar type of morphology is invariably observed even if the composition and temperature are varied. In contrast, when the lowest molecular weight polystyrene with Mn=8200 was used (in a “wet-brush” regime), the type of morphology is significantly altered. At the isotropic temperatures of LC segment, the lamellar morphology is observed for the blends with LC contents from 45% to 35%, but the cylindrical or spherical domain becomes predominant with a decrease in the LC content. On the other hand, the lamellar morphology is commonly observed at the crystal temperatures. In some blends with the lower weight fractions of LC segment, hence, there can be seen the order–order transition from sphere or cylinder to lamella on decreasing temperature. This morphological transformation is caused by the formation of the layered structure that tends to orient perpendicularly to the interface of microdomain. The results show that the structural order of LC segment affects both the microdomain morphology and the solubility style of the homopolymer into the block copolymer.