Hydrogen-Bonded Polymers with Bent-Shaped Side Chains and Poly(4-vinylpridine) Backbone: Phase Behavior and Thin Film Morphologies

We investigate the self-assembly behavior of a series of supramolecular hydrogen bonded polymer complexes P4VP­(nCBP)_<i>x</i> in which bent-shaped molecules (nCBP, <i>n</i> = 10,12,14) are attached to a poly­(4-vinylpridine) (P4VP) backbone via hydrogen bond interaction in both bulk and thin films. The formation of lamellar and hexagonal columnar (Φ_H) phases are dependent on the blending ratio of nCBP per vinylpridine unit (<i>x</i>), aliphatic tail length (<i>n</i>), and temperature. When increasing the grafting density <i>x</i>, the phase structure of polymer complexes transform from lamellar to Φ_H phase. A nonreversible lamellar to Φ_H phase transition appears in the heating process for P4VP­(10CBP)_<i>x</i> with <i>x</i> ≥ 0.4, P4VP­(12CBP)_<i>x</i> with <i>x</i> ≥ 0.3, and P4VP­(14CBP)_<i>x</i> with <i>x</i> ≥ 0.2. The lamellar and Φ_H phase are oriented parallel to the substrate in the thin film as verified by both GISAXS and AFM.