We investigated the effects of chain architecture and hydrogen-bonding interaction on the phase behavior of binary mixtures containing nearly symmetric polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer and highly asymmetric polystyrene-graft-poly(acrylic acid) (PS-g-PAA) graft copolymer. When PS-g-PAA was added to PS-b-P2VP, hydrogen bonds between PAA and P2VP chains improved the miscibility of the copolymers and facilitated localization of PS-g-PAA at the PS-b-P2VP interface, which reduced the interfacial free energy of the blends. However, positioning PS-g-PAA with one PS main chain and two PAA grafted chains at the PS-b-P2VP interface increased the stretching free energy of PS-b-P2VP. Consequently, the interfacial coverage of PS-g-PAA reached saturation. Residual PS-g-PAA was segregated into the PS microdomains formed by PS-b-P2VP to regain translational entropy and reduce the stretching free energy. When the molecular weight ratio of PS-b-P2VP to PS-g-PAA (R) was smaller than 8, PS-g-PAA could not swell the PS microdomains formed by PS-b-P2VP. Therefore, the morphology of PS-b-P2VP/PS-g-PAA blends remained lamellar. By contrast, when R > 8, PS-g-PAA effectively swelled the PS microdomains formed by PS-b-P2VP. This behavior amplified the asymmetry effect caused by the branched-chain architecture of PS-g-PAA on altering the interfacial curvature of PS-b-P2VP. Consequently, the morphology of the blends transformed into a cylindrical structure.
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