Phase Diagram of Poly(4-vinylphenol)−<i>N</i>,<i>N</i>-Dimethyloctadecylamine Mixture

Akiba, Isamu; Akiyama, Saburo

doi:10.1021/ma982002y

Cited by 23 publications

(28 citation statements)

References 19 publications

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“…66 Hydrogen bonding allows non-charged self-assembled structures, as has been shown using e.g. poly(4-vinylpyridine)/alkylphenols by Ikkala ten Brinke et al, [67][68][69] poly(ethyleneoxide)/dodecylbenzene sulfonic acid by Chen et al, 70 and poly(vinylphenol)/aminic amphiphiles by Akiyama et al 71 Due to its weakness, hydrogen bonding allows additional freedom to control the strength of bonding e.g. by temperature.…”

Section: Hierarchical Self-assembly In Block-copolymer/ Amphiphile Comentioning

confidence: 99%

Hierarchical self-assembly in polymeric complexes: Towards functional materials

2004

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Combination of self-assembly at different length scales leads to structural hierarchies. It offers rich possibilities to construct nanostructured matter, nanoscale parts, and switching (responsive) properties based on the phase transitions of the self-assembled structures. Complexation of oligomeric amphiphiles to polymers using ionic interactions, coordination, or hydrogen bonding leads to polymeric comb-shaped supramolecules (complexes), which self-assemble at a length scale of a few nm. Self-assembly at an order of magnitude larger length scale is provided by block copolymers, and combination of the latter two concepts leads to structural hierarchies. They provide e.g. templates for mesoporous materials and nano-objects, and allow switching conductivity and switching optical properties. Structural hierarchies are also observed by complexing moderately monodisperse polymeric rods with amphiphiles. Finally, self-assembly at even a larger length scale upon using colloidal particles may be combined to the above structures, as encouraged by recent observations.

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Section: Hierarchical Self-assembly In Block-copolymer/ Amphiphile Comentioning

confidence: 99%

Hierarchical self-assembly in polymeric complexes: Towards functional materials

2004

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“…A study of the phase behavior of a poly(4-vinylphenol)-N,N-dimethyloctadecylamine system by Akiba et al largely corroborated these findings. 20 To date, however, there are still relatively few examples in the literature of systematic studies of the phase behavior of such polymer-ligand systems where the solvency of unbound ligand plays a crucial role. Furthermore, the case of mesogenic ligands remains quite unexplored in comparison to that of flexible aliphatic ligands, such as pentadecylphenol (PDP) or dodecylbenzenesulfonic acid (DBSA), which have been more frequently considered.…”

Section: Introductionmentioning

confidence: 99%

Smectic Demixing in the Phase Behavior and Self-Assembly of a Hydrogen-Bonded Polymer with Mesogenic Side Chains

Gopinadhan¹,

Beach²,

Anastas³

2010

Macromolecules

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We present a detailed study of the structure and properties of a supramolecular complex formed via hydrogen bond association between poly(acrylic acid) chains and an imidazole-terminated biphenyl mesogen. The system exhibits a rich phase behavior as a function of temperature and stoichiometry, expressed as the molar ratio S between the number of mesogens and binding sites present. Smectic mesophases are formed for all S ≥ 0.033, a surprisingly small number. The dependence of the characteristic length scale of the mesophase on stoichiometry does not follow the expected 1-D swelling law. At low stoichiometries, S ≤ 0.2, the system exhibits little or no change in structure up to temperatures as high as 200 °C, beyond which changes become temperature irreversible. In contrast, at higher S, the system features complex thermally driven transitions among tilted monolayer and bilayer arrangements and complete, reversible isotropization of the system at elevated temperatures. Over a limited range of temperatures and compositions, a supramolecular length scale emerges that is well beyond the upper limit imposed by a bilayer construct and thus cannot be accounted for within the conventional paradigm. Binding isotherms reveal that the polymer has a limited capacity for the ligand with saturation occurring for S ≥ 0.33. These results suggest that the common assumption of homogeneously distributed tightly bound ligands with layer-like phase separation from the polymer backbone do not apply in this system over all compositions. The anomalous phase display is consistent with demixing between polymer rich and polymer poor domains due to the presence of excess unassociated mesogen, which can act as a solvent for the system.

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“…In addition, the repulsion between PVP and the pentadecyl groups of PDP still remains in the hightemperature region because PVP is immiscible with hydrocarbon compounds even at high temperatures. [7] Thus, it allows more compact coiling of the P4VP chains and the P4VP(DBSA) 1.0 phase collapses into pits. Meanwhile, the PS-PDP component segregates to the surface to form a continuous film in order to minimize the polymer/air interfacial free energy (Figure 4c).…”

Section: Resultsmentioning

confidence: 99%

“…[5] They allow the formation of non-charged selfassembled structures, as have been shown using, e.g., poly(ethylene oxide)/dodecylbenzenesulfonic acid by Chen et al, [6] and poly(vinyl phenol)/aminic amphiphiles by Akiba and Akiyama. [7] Ikkala and co-workers and Brinke and co-workers have demonstrated the preparation of hierarchical polymeric materials through the complexation of end-functionalized oligomers and diblock copolymers in bulk by hydrogen bonds. [8][9][10][11][12] They have also studied both proton transfer interactions and hydrogen bonds in selforganized supramolecular polymers.…”

Section: Introductionmentioning

confidence: 99%

Surface Morphology Evolution of a Thin Polymeric Supramolecular Film by Tuning Interactions

Zhang

Gao

et al. 2006

Macromol. Rapid Commun.

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Summary: A polymeric supramolecule consisting of symmetric polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP), dodecylbenzenesulfonic acid (DBSA), and 3‐pentadecylphenol (PDP) was formed by proton transfer and hydrogen bonding. The surface morphology of a thin film of the polymeric supramolecule has been investigated. The spherical PS microdomains embedded in a P4VP(DBSA)1.0(PDP)1.0 matrix are observed for the as‐cast film because the weight fraction, fcomb, of the P4VP(DBSA)1.0(PDP)1.0 blocks is much higher than that of PS as a result of the non‐covalent interactions of P4VP and DBSA and DBSA and PDP. Upon annealing the PS‐b‐P4VP(1:1)(DBSA)1.0(PDP)1.0 film at high temperatures, the hydrogen bonding between the DBSA and PDP diminishes, which leads to a change of overall morphology from an ordered sphere to a pitted structure.AFM topographic image of a PS‐b‐P4VP(1:1)(DBSA)1.0(PDP)1.0 thin film.magnified imageAFM topographic image of a PS‐b‐P4VP(1:1)(DBSA)1.0(PDP)1.0 thin film.

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Phase Diagram of Poly(4-vinylphenol)−N,N-Dimethyloctadecylamine Mixture

Cited by 23 publications

References 19 publications

Hierarchical self-assembly in polymeric complexes: Towards functional materials

Hierarchical self-assembly in polymeric complexes: Towards functional materials

Smectic Demixing in the Phase Behavior and Self-Assembly of a Hydrogen-Bonded Polymer with Mesogenic Side Chains

Surface Morphology Evolution of a Thin Polymeric Supramolecular Film by Tuning Interactions

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