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

Abstract

Supramolecular complexes of polystyreneblock-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.

Controlling the shape of Janus nanostructures through supramolecular modification of ABC terpolymer bulk morphologies

“…Compared to the prominent sphere, cylinder and lamella phases, the perforated lamella is rarely observed. It has been reported for diblock copolymers [13], terpolymer coreshell systems [56][57][58] and block copolymer blends [59]. In ABC triblock terpolymer systems, the block arrangement commonly corresponds to a core-shell structure, where the middle block completely engulfs one of the end blocks leaving no interface between the A/C end blocks.…”

“…Aside from synthetically controlled parameters such as block weight fractions and block chemistries, supramolecular complexation of small-molecule additives selectively to one block is a versatile concept to generate functional morphologies, unusual geometries, and even introduce structural hierarchies [11][12][13]. Much effort has been invested to identify the impact of smallmolecule complexation on the bulk behavior of diblock copolymers, where polystyrene-blockpoly(4-vinylpyridine) (PS-b-P4VP) has been the most prominent example.…”

Nickel Network Derived from a Block Copolymer Template for MnO2 Electrodes as Dimensionally Stabilized Lithium‐Ion Battery Anodes

“…First introduced by Vukovic et al., this approach offers considerable advantages over previously described polymer template‐directed synthesis of metal foams . The most striking advantage is the refined way of simply tuning the morphology of the overall template, PS‐ b ‐P4VP, by varying the addition of x (ratio between PDP molecules and P4VP monomer units) of a low‐weight amphiphilic compound . After annealing of the polymer films (Figure a), the formation of an open network structure facilitates removal of the amphiphile.…”

Highly Ordered Structure Formation in RAFT-Synthesized PtBOS-b-P4VP Diblock Copolymers

“…The synthesis of block copolymers and their ability to form a variety of nanoscale structures via self‐assembly has been the subject of extensive research . The structures formed depend on the degree of polymerization, , the block volume fractions, , and the interaction parameter, .For linear diblock copolymers the self‐assembled structures include spherical, cylindrical, lamellar, and bicontinuous gyroid morphologies . The latter appears in a relatively small range of the copolymer composition in the diblock copolymer phase diagram, mostly in the weak segregation regime (10 < < 40) …”