Features of Microphase-Separated Structures in Asymmetric Triblock Copolymers $A_{1}-B-A_{2}$

Equilibrium behavior of ABA triblock copolymer with different lengths of endblock A chains was examined using self-consistent field theory by Matsenl. It was found that at small asymmetries, the A block bidispersity reduces the stretching energy of the A domains. This effect causes a slight increase in the domain spacing and shifts the order-order transitions toward higher A volume fractions. At large asymmetries, the short A blocks pull free of their domains allowing their B blocks to relax. A feature of microphase-separated structure of asymmetric poly(methyl acyrylate) (PMA)-b-polystyrene-b-PMA using SAXS, DSC and ESR was experimentally examined. These measurements gave an evidence of the solubilization of short A chains to the B domains.