Hexagonally Perforated Layer Morphology in PS-b-P4VP(PDP) Supramolecules

Supramolecular complexes of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers and small molecules such as pentadecylphenol (PDP) have been studied extensively in recent years. In the present study, PS-b-P4VP(PDP) complexes with a minority P4VP(PDP) block are morphologically characterized focusing on the region between the lamellar and cylindrical phase. Dynamic mechanical measurements and small-angle X-ray scattering are used to follow the transitions between the ordered states upon heating/cooling. The self-assembled state at various temperatures is determined by small-angle X-ray scattering and transmission electron microscopy. In contrast to the opposite case of majority P4VP(PDP) blocks, where the transition from lamellar to cylindrical structures frequently occurs via the gyroid morphology, the complexes adopt the hexagonally perforated layered morphology in a broad range of compositions. Although known as a metastable phase in pure diblock copolymers, the hexagonally perforated layered phase appears as an equilibrium phase in PS-b-P4VP(PDP) complexes, being stabilized by the presence of the hydrogen-bonded PDP side chains in the minority component domains

Flow and conductivity properties of comb-shaped self-organized supramolecules

Structures, which are significantly smaller than e.g. in the present day microelectronics, are pursued in nanotechnology. Structures near molecular level can be constructed for example by imitating biological systems where self-organization and molecular recognition are used to form supramolecules. In this work hierarchically self-organized supramolecular nanostructured materials are constructed with peculiar conductivity behavior. The structures are, as such, not macroscopically aligned and therefore the conductivity is isotropic throughout the macroscopic sample. Two types of supramolecular materials are studied under an oscillatory shear flow in order to find routes towards macroscopically oriented hierarchical structures. The first type consists of 20 - 50 Å lamellar structure due to self-organization of comb-shaped supramolecules. The second structure is a hierarchically self-organized, i.e. lamellar-within-lamellar structure, where there are structures at two length scales, i.e. at 20 - 50 Å and 200 - 1000 Å. Shear flow conditions allowing optimal macroscopic order were identified. Finally, macroscopically aligned protonically conducting material is presented, which shows globally tridirectional conductivity with anisotropic hopping conductivity. Asymmetric structures i.e. lamellae-within-cylinders are also briefly studied and a method is found to achieve mesoporous materials with polymer brushes at the walls of emptied cylinders. The brushes can be used to tailor the functionalities of the pores. The results of this work show that materials, which are relatively simple to produce, allow tailored macroscopic properties due to their aligned self-organized nanoscale structures.reviewe

Polymeric Nanofibers Prepared from Self-Organized Supramolecules

A facile concept to prepare nano-objects based on self-organizing polymeric supramolecules (also called supramolecular block copolymers) is demonstrated using one particular shape, i.e., nanorods or nanofibers. Cylindrical aggregates consisting of a polystyrene (PS) core and a thin corona of poly(4-vinylpyridine) (P4VP) chains are prepared from P4VP(pentadecylphenol)-block-PS comb-coil supramolecules. Diblock copolymers P4VP-block-PS are stoichiometrically (with respect to the number of pyridine groups) hydrogen-bonded with pentadecylphenol (PDP) amphiphiles to yield P4VP(PDP)-block-PS comb-coil supramolecules. By the selection of appropriate relative block lengths for P4VP(PDP) and PS, a micro-phase-separated cylindrical morphology of PS cylinders inside a P4VP(PDP) matrix is obtained. Subsequent removal of the amphiphiles, accounting for ca. 75% of the matrix material, results in cylinders with a core of PS and a corona of easily adjustable thickness of P4VP. The advantages of the present concept compared to the existing procedures are discussed.