Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers.
Hydrogen bonds (H-bonds) constitute highly relevant structural units of molecular self-assembly. They bridge biological and synthetic sciences, implementing dynamic properties into materials and molecules, not achieved via purely covalent bonds. Phase segregation on the other hand represents another important assembly principle, responsible for, e.g., cell compartimentation, membrane-formation, and microphase segregation in polymers. Yet, despite the expanding elegant synthetic strategies of supramolecular polymers, the investigation of phase behavior of macromolecules driven by H-bonding forces still remains in its infancy. Compared to phase segregation arising from covalently linked block copolymers, the generation of phase segregated nanostructures via supramolecular polymers facilitates the design of novel functional materials, such as those with stimuli-responsive, self-healing, and erasable-material properties. We here discuss the phase segregation of H-bonding polymers in both the solution and solid state, wherein the molecular recognition elements are based on multiple H-bonding moieties, such as thymine/2,6-diamino-pyridine (THY/DAP), thymine/diamino triazine (THY/DAT), and barbiturate/Hamilton wedge (Ba/HW) elements. The specific aggregation of a series of different H-bonding polymers in solution, both linear and dendritic polymers, bearing heterocomplementary H-bonding moieties are described, in particular focusing on the issue of phase segregation. The exploitation of H-bonded supramolecular dendrons with segregating polymer chains leads to the formation of three-phase segregated hierarchical micelles in solution, purely linking the components via H-bonds, in turn displaying a versatile spectrum of segregated morphologies. We also focus on segregation effects of H-bonded amorphous and crystalline polymers: thus the formation of nanostructures, such as disordered micelles and well-ordered body centered cubic (BCC) packed spheres from telechelic polymers bearing H-bonding moieties at the chain ends is observed. Finally, we discuss the discovery of novel functional microphase separated self-healing supramolecular architectures, illustrating dynamic and self-healing properties with an almost complete recovery of the initial mechanical performances healing within 24h at 30 °C. Collectively, our studies prove that phase segregation in H-bonding polymers is an important principle, capable to generate nanostructures and dynamic properties not achieved in covalently linked polymers. The results discussed illustrate that a rational architectural design within H-bonding polymer systems in interplay with phase segregation in both the amorphous and crystalline state opens perspectives to develop artificial supramolecular systems approaching the level of complexities and properties present in nature's biomaterials.
Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics and Mathematics), Martin-Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
Senbin
S
Chen
Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics and Mathematics), Martin-Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
Wolfgang H
WH
Binder