Microphase separation and liquid-crystalline ordering of rod-coil copolymers

Microphase separation and liquid-crystalline ordering in diblock and triblock rod-coil copolymers (with rod-to-coil fraction f=0.5) were investigated using the dissipative particle dynamics method. When the isotropic disordered phases of these systems were cooled down below their order-disorder transition temperatures T_ODT, lamellar structures were observed. For rod-coil diblock copolymers, the lamellar layers were obtained below T=2.0. This temperature was found to be higher than the T_ODT for normal coil-coil diblock copolymers. Significant ordering of the rods was observed only below T=0.9 which is the isotropic-nematic transition temperature for rodlike fluids. For the triblock rod-coil copolymers, both microphase separation and rod ordering occurred at T=0.9. Normal coil-coil triblock copolymers were found to undergo microphase separation at T=0.8, which is about half the T_ODT of the normal diblock copolymers. Investigations of the mean square displacement and the parallel and the perpendicular components of the spatial distribution function revealed that at low temperatures, the rod-coil diblock copolymers exhibit smectic-A and crystalline phases, while the triblock copolymers show smectic-C and crystalline phases. No nematic phases were observed at the density and interaction parameters used in this study.