Assembly of Miscible Supramolecular Network Blends Using DDA·AAD Hydrogen-Bonding Interactions of Pendant Side-Chains

The formation of polymer blends can result in materials with superior properties through combination of homo- or co-polymers with divergent functionalities. However, the contrasting physical properties of different polymers often result in phase separation. Herein we induce miscible blend formation of immiscible poly(methyl methacrylate) and polystyrene polymers through triple donor–donor–acceptor and acceptor–acceptor–donor (DDA·AAD) hydrogen bonding between complementary heterodimers on pendent side-chains. RAFT polymerization is used to synthesize a series of poly (methylmethacrylate) and polystyrene co-polymers bearing complementary side-chain hydrogen bonding motifs. Mixing of these polymers promoted miscible blend formation as demonstrated by atomic force microscopy and differential scanning calorimetry. The effectiveness of blend formation was shown to depend upon the extent of incorporation of hydrogen-bonding motif bearing co-monomer; lower degrees of incorporation lead to ineffective blending, whereas higher degree of incorporation, suppress phase separation and promote miscibility.