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)_x in which bent-shaped molecules (nCBP, n = 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 (x), aliphatic tail length (n), and temperature. When increasing the grafting density x, 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)_x with x ≥ 0.4, P4VP­(12CBP)_x with x ≥ 0.3, and P4VP­(14CBP)_x with x ≥ 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.