Effect of Macromolecular Architecture on the Morphology of Polystyrene–Polyisoprene Block Copolymers

The impact of block connectivity on the morphologies of four block copolymers of varying architecture containing polystyrene (PS) and polyisoprene (PI) has been studied. The volume fraction of PS and molecular weight are held constant while varying the architecture from a linear PS–PI diblock copolymer to three different miktoarm star architectures: PS 2 PI, PSPI 2, and PS 2 PI 2 . Morphologies of the PS 2 PI and PSPI 2 miktoarm stars are different from those observed for the linear copolymer and dependent on the connectivity of the copolymer blocks. The change in morphology with connectivity indicates that combining two chains at a junction point leads to chain crowding, where subsequent excluded volume effects drive the change in morphology for each sample. The PS 2 PI 2 miktoarm star exhibits the same morphology as the linear diblock but with a reduction in the size of the domains. The extent of the decrease in domain size indicates that chain stretching impacts the formation of this morphology. Experimentally observed morphologies for different chain architectures are generally consistent with three-dimensional self-consistent-field theory simulations, taking into account conformational asymmetry and experimental uncertainty in the copolymer composition. Furthermore, these results generally agree with analytical theory predictions that account for architectural and conformational asymmetry.