Mesophase structure and alignment under different fields of liquid crystalline main-chain/side-group block copolymers

Liquid crystalline block copolymers are new materials in which multiple molecular interactions can provide the driving force for complex phase behaviors and states of order. Block copolymers containing both liquid crystalline main-chain polyester and side-group polymethacrylate blocks were investigated. They phase separated in the liquid crystalline state and their individual mesophases coexisted. The copolymers responded very differently when either a mechanical or a magnetic field was used for alignment. In the fibers the orientations of the side-group and main-chain smectic planes with respect to the fiber axis depended critically on the block lengths and on their distinct tendencies to align, whereas under a magnetic field the mesogens aligned collectively with their long molecular axis parallel to the field, independent of the copolymer structure

Phase and thermal behavior of liquid crystalline block copolymers

The phase behavior of liquid-crystalline (LC) block copolymers containing mesomorphic blocks with main-chain (MC) units and side-group (SG) substituents was investigated. The MC block consisted of an LC semiflexible polyester and the SG block was an LC polymethacrylate. Four different samples were prepared with the content of the SG blocks varying from 35 to 79 wt%. The thermal behavior of the copolymers was investigated using differential scanning calorimetry, and X-ray diffraction was used to characterize the phase structure. Both the MC and SG blocks formed smectic A and nematic mesophases. Thus, the occurrence of distinct and well-defined phase transitions clearly indicated that MC and SG blocks were phase-separated and showed their own phase behavior. Two different endothermic processes were identified in annealed samples that followed different kinetics. The low-temperature process is thought to involve the MC blocks in their own domains and was observed up to the smectic A to nematic transition temperature of these blocks. The high-temperature process involves the interface between MC and SG domains and is probably due to melting of crystallites grown during annealing. It is shown that the crystallization develops with kinetics affected by the degree of order of the LC state of the SG domains