Aggregation Behavior of Rod–Coil–Rod Triblock Copolymers in a Coil-Selective Solvent

Abstract

Recent experiments have reported that the self-assembly of conjugated polymers mimicking rod-coil-rod triblock copolymers (BCPs) in selective solvents exhibits unique aggregate morphologies. However, the nature of the arrangement of the polymers within the aggregates and the spatial organization of the aggregates remain an unresolved issue. We report the results of coarse-grained Langevin dynamics simulations, which investigated the self-assembly behavior of rod-coil-rod BCPs in a coil-selective solvent. We observe a rapid formation of cylindrically shaped multichain clusters. The initial stages of formation of the aggregates was seen to be independent of the strength of the solvent selectivity. However, for higher solvent selectivities, the clusters were seen to merge into larger units at later stages. A reduction in rod to coil block ratio was observed to decrease the size and number of clusters. In the limit of a highly concentrated solution, we observe the formation of a networked system of distinct clusters, which however retain the cylindrical arrangement observed at lower polymer concentrations.