Effect of macromolecular architecture on the self-assembly behavior of copolymers in a selective polymer host.

We present a detailed simulation study of the structural and dynamical behavior of star-shaped mikto-arm (polystyrene)8(poly(ethylene oxide))8, (PS)8(PEO)8, copolymers with eight arms of each type, versus that of a linear polystyrene-block-poly(ethylene oxide), PS-b-PEO, diblock, in a selective homopolymer host. Both copolymers are blended at the same weight fraction 33% with an oligomeric PEO host. We use atomistic molecular dynamics simulations to account for the molecular interactions present in the blends and to study quantitatively the dynamical and structural properties of these systems. The presence of the selective oligomeric PEO host leads to the formation of complex self-assembled structures. While cylindrical structures are formed in the case of linear diblock copolymers, mikto-arm star copolymers form percolated interconnected assemblies within the PEO host. The cylindrical objects formed by the linear diblock copolymers exhibit a higher degree of compactness and a weaker temperature dependence than the percolated network formed by their star-shaped analogues. The dynamics is governed primarily by the local structural heterogeneity, i.e., the environment around a segment, which is determined by the interaction between the different components, the macromolecular architecture of the copolymer as well as the associated geometrical constrains. Our data further stress the fact that the structural and dynamical properties in these blends may be controlled/tuned by the macromolecular architecture of the copolymer and/or by adjusting the temperature.