Creation of Hierarchical Nanophase-Separated Structures via Supramacromolecular Self-Assembly from Two Asymmetric Block Copolymers with Short Interacting Sequences Giving Hydrogen Bonding Interaction

Polystyrene (S) having short poly(4-hydroxystyrene) (H) on one end (SH, Mw = 71.4K, ϕH = 0.04) and polyisoprene (I) having short poly(2-vinylpyridine) (P) on one end (IP, Mw = 57.6K, ϕP = 0.04) were mixed at various molar ratios, where H and P form a complex by hydrogen bonding interaction. The variation of phase-separated structures of solvent cast films depending on casting solvent and also on pH with heating time at elevated constant temperature were investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Asymmetric morphology for the H/P stoichiometric blend film obtained by casting from polar solvent can be easily transformed into symmetric nanophase-separated structure by the addition of nonpolar solvent. All samples cast from THF/toluene solutions reveal ordered nanophase-separated structures even though the contents of interacting H and P sequences are both merely 4%. The hierarchical three-phase lamellar structure from equimolar SH/IP blend is maintained ev...

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