Effect of Composition Distribution on Microphase-Separated Structure from Diblock Copolymers

Abstract

Microphase-separated structures of diblock copolymers with narrow molecular weight distributions but with various composition distributions were investigated. Monodisperse nine parent block copolymers composed of polystyrene and poly(2-vinylpyridine) having almost the same molecular weight but with different polystyrene volume fraction, φ s, covering 0.1−0.9, were prepared. Successively they were blended variously to produce samples with various composition distributions but with constant average composition; that is, φ s was kept constant at approximately 0.5. Structures from solvent-cast and well-annealed films were observed through transmission electron microscopy and small-angle X-ray scattering. It has been found that the blends with wide composition distributions show periodic alternating lamellar structure up to 1.7 in terms of M w (S)/ M n (S), where M w (S) and M n (S) denote weight-average and number-average molecular weights of polystyrene block, respectively, and that the microdomain spacing increases with increase of polydispersity of each block. Further, it was clarified that the blend shows macrophase separation in between two kinds of regular microphase-separated structures if M w (S)/ M n (S) reaches approximately 1.8.