Persistent Formation of Self-Assembled Cylindrical Structure in a Liquid Crystalline Block Copolymer Constructed by Hydrogen Bonding

A series of supramolecular liquid crystalline block copolymers (SLCBCPs) were prepared by hydrogen-bonding interaction between poly(dimethylsiloxane)-b-poly(2-vinylterephthalic acid) (PDMS-b-PM1H) and [4-(4′-hexyloxy)styryl]pyridine (NC6). PDMS-b-PM1H serves as the hydrogen-bonding donor and NC6 as the hydrogen-bonding acceptor. The SLCBCPs are obtained by mixing the hydrogen-bonding acceptor and donor in pyridine. Through increasing the molar ratio of pyridine to carboxyl, the SLCBCPs can transform from coil–coil block copolymers (BCPs) to rod–coil ones. When the ratio of pyridine to carboxylic acid is 0.50 or lower, the SLCBCPs are coil–coil-like. However, when the ratio exceeds 0.50, the SLCBCPs behave like rod–coil BCPs because the supramolecular block PM1H(NC6) exhibits liquid crystalline (LC) behavior owing to the “jacketing” effect. Small-angle X-ray scattering and transmission electron microscopy experiments were employed to characterize the microphase-separated nanostructures of the SLCBCPs. Inte...