Orientation- and cosolvent-induced self-assembly of amphiphilic homopolymers in selective solvents

Abstract

Self-assembly of single amphiphilic homopolymer in solvents with inverse selectivities, characterized by symmetric affinity and disgust to backbone and side groups, and their binary mixtures are studied by means of computer simulations and analytical theory, depending on composition and miscibility of components. In each of these two solvents separately, the polymer chain forms either multidomain or beads-on-a-string structures. Morphological contrast comes from the distinction in orientational mobility of side groups. In the backbone-selective solvent, the enhancing of orientational mobility of pendant groups due to merging of soluble shells of beads gives rise to a new type of attraction - orientation-induced attraction, which leads to close packing of intrachain micelles into the multidomain structure. In binary solvent the amphiphilic homopolymer manifests cosolvency behavior. At strong incompatibility of solvents variation of composition toward the equal concentrations of the solvents provokes series of morphological transitions, accompanied by gradual uptake of minor component of the solvent mixture into the assembly.