Hierarchical Self-Assembled Structures from Diblock Copolymer Mixtures by Competitive Hydrogen Bonding Strength

In this work we prepared poly(styrene–b–vinylphenol) (PS-b-PVPh) by sequential anionic living polymerization and poly(ethylene oxide-b-4-vinylpyridine) (PEO-b-P4VP) by reversible addition fragmentation chain transfer polymerization (RAFT) by using poly(ethylene oxide) 4-cyano-4-(phenylcarbonothioylthio)pentanoate (PEO-SC(S)Ph) as a macroinitiator with two hydrogen bonded acceptor groups. When blending with disordered PEO-b-P4VP diblock copolymer, we found the order-order self-assembled structure transition from lamellar structure for pure PS-b-PVPh to cylindrical, worm-like, and finally to PEO crystalline lamellar structures. Taking the advantage of the ΔK effect from competitive hydrogen bonding strengths between PVPh/P4VP and PVPh/PEO domains, it could form the hierarchical self-assembled morphologies such as core–shell cylindrical nanostructure.