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Марков, В. А.; Субботин, А. А.; Brinke, G. ten

doi:10.1103/physreve.84.041807

Cited by 7 publications

(8 citation statements)

References 43 publications

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“…By using a single, symmetric P4VP‐ b ‐PAPI (P4PA) diblock copolymer, several unique morphologies were observed in [poly(4‐vinylpyridine)‐ block ‐poly( N ‐acryloylpiperidine)](3‐nonadecylphenol) x complexes as a function of the comb density x . Besides that, both the double parallel ( x= 0.5) and perpendicular alignment ( x= 1.0) of the internal layers with respect to the large lamellar BCP structure were in excellent agreement with our previous theoretical work . Interestingly though, the parallel morphology demonstrated multiple internal layers.…”

Section: Methodssupporting

confidence: 84%

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

et al. 2016

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The formation of unusual multilayered parallel lamellae-in-lamellae in symmetric supramolecular doublecomb diblock copolymers is presented. While keeping the concentration of surfactant fixed, the number of internal layers was found to increase with molecular weight M up to 34 for the largest block copolymer. The number of internal structures n was established to scale as M 0.67 and therefore enables easy design of such structures with great precision.Whereas linear diblock copolymers are known to form only four different stable structures upon self-assembly (namely spheres, cylinders, lamellae, and gyroids), [1][2][3] careful design of the macromolecular architecture or including additional blocks can enrich the phase behavior significantly.[4] For instance, binary AB multiblock copolymers [5] and A(AB) 3 miktoarm star polymers [6] were recently demonstrated to give parallel lamellae-in-lamellae or extremely asymmetric lamellae. Incorporation of a third component in ABC triblock terpolymers gives rise to an even higher morphological complexity.[7] However, preparation of more complex polymeric architectures does not automatically imply formation of more complex structures, since reduced mobility and confinement of the junction points can hamper proper phase separation.For real-life technological applications, a synthetically less-challenging approach is required. A supramolecular route [8][9][10] enables researchers to produce comb-shaped copolymers by simply combining regular linear block copolymers (BCPs) and small amphiphilic molecules, thereby avoiding such complex preparation methods. [11,12] Supramolecular complexes based on poly(4-vinylpyridine) and 3-pentadecylphenol (P4VP(3-PDP) x , with x representing the number of 3-PDP molecules per monomer) are among the most studied comb-shaped systems. Since by now their phase behavior is very well understood [13,14] and materials are widely commercially available, several unique functional materials originating from such complexes have been reported. Examples include temperature-responsive photonic crystals, [15] CdSe/PbS nanoparticle assemblies, [16] and highly ordered Au nanocomposites in thin films [17][18][19] or solution. [20] In polystyrene-containing P4VP(3-PDP) x -b-PS comb-coil diblock copolymers, the supramolecular nature of the complex also provides an easy route for creating ordered porous structures by simple dissolution of 3-PDP. Such templates have for instance been refilled with metal or carbon for the preparation of actuating materials [21] or nanoporous cathodes, [22] respectively. From a fundamental point of view these combcoil systems are surprisingly interesting as well, as simultaneous self-assembly of both the comb (3-PDP/P4VP) and diblock (P4VP(3-PDP) x -b-PS) led to hierarchical structure formation. [23] By changing the concentration of the alkylphenol or the composition of the parent PS-b-P4VP copolymer, self-assembly gave access to multiple classical morphologies with an additional internal structure.[24] Only highly sophistic...

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Section: Methodssupporting

confidence: 84%

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

et al. 2016

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“…Although the previously found perpendicular orientation [23] of the small 3-NDP lamellae with respect to the large P4PA lamellae was in excellent agreement with our theoretical, but highly simplified, all-covalent analysis, [26] it is exciting to see that despite the low concentration of P4PA (about 25 wt%), such a complex was still able to assemble into an ordered morphology at room temperature. By preparation of additional stoichiometric P4PA(3-NDP) 1.0 complexes using these five symmetric P4PA diblock copolymers and studying those by several temperature-resolved techniques, we will present a more detailed description of the mechanism that drives the selfassembly of these intriguing supramolecules.…”

Section: Diblock Copolymerssupporting

confidence: 56%

The Origin of Hierarchical Structure Formation in Highly Grafted Symmetric Supramolecular Double‐Comb Diblock Copolymers

Hofman

Reza

Ruokolainen

et al. 2017

Macromol. Rapid Commun.

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Involving supramolecular chemistry in self‐assembling block copolymer systems enables design of complex macromolecular architectures that, in turn, could lead to complex phase behavior. It is an elegant route, as complicated and sensitive synthesis techniques can be avoided. Highly grafted double‐comb diblock copolymers based on symmetric double hydrogen bond accepting poly(4‐vinylpyridine)‐block‐poly(N‐acryloylpiperidine) diblock copolymers and donating 3‐nonadecylphenol amphiphiles are realized and studied systematically by changing the molecular weight of the copolymer. Double perpendicular lamellae‐in‐lamellae are formed in all complexes, independent of the copolymer molecular weight. Temperature‐resolved measurements demonstrate that the supramolecular nature and ability to crystallize are responsible for the formation of such multiblock‐like structures. Because of these driving forces and severe plasticization of the complexes in the liquid crystalline state, this supramolecular approach can be useful for steering self‐assembly of both low‐ and high‐molecular‐weight block copolymer systems.

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“…Self-Assembly of the Individual Components. For constructing the by Markov et al 23 theoretically investigated double-comb diblock copolymer system, we chose to use a double supramolecular approach, since this brings several advantages over a double covalent route. First of all, in order to look into the influence of the comb density on its self-assembly, only one diblock copolymer needs to be synthesized.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…For further extension of the complexity of these materials, one can think of introducing side chains on the second block as well, resulting in what we will refer to as a double-comb diblock copolymer. According to the theoretical work of Markov et al self-assembly of such block copolymers could result in intriguing hierarchical morphologies upon microphase separation of all components. Several experimental examples of such materials have been reported in literature, but so far this approach was mostly used to achieve high molecular weight block copolymers, − without paying attention to the internal self-assembly of the comb blocks, or only one of the two small structures could be observed in real space. , To date, the only example in which both small length scales were observed simultaneously by TEM, is our system based on a double supramolecular approach .…”

Section: Introductionmentioning

confidence: 99%

Hierarchical Self-Assembly of Symmetric Supramolecular Double-Comb Diblock Copolymers: a Comb Density Study

Hofman¹,

Reza

Ruokolainen

et al. 2014

Macromolecules

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A double-comb diblock copolymer was constructed experimentally using a double supramolecular approach. Addition of 3-nonadecylphenol (3-NDP) amphiphiles to a symmetric, double hydrogen bond accepting poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) (P4VP-b-PAPI) diblock copolymer resulted in microphase separation on both the block copolymer and polymer− amphiphile level. Variation of the comb density x in these [P4VP-b-PAPI](3-NDP) x supramolecular complexes gave rise to several unique hierarchical nanostructures. For high comb densities (x = 0.8−1.2) double perpendicular lamellae-in-lamellae were observed, while lowering the density to x = 0.5 resulted in a double parallel lamellar morphology as demonstrated by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Further decreasing the concentration of 3-NDP (x = 0.3) caused the complex to self-assemble into cylinders-in-lamellae, while for x = 0.1 3-NDP only serves as a plasticizing agent. The phase transitions identified as a function of x are all in excellent agreement with our previously performed theoretical analysis.

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Self-assembly of (A-comb-C)-b-(B-comb-

Cited by 7 publications

References 43 publications

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

The Origin of Hierarchical Structure Formation in Highly Grafted Symmetric Supramolecular Double‐Comb Diblock Copolymers

Hierarchical Self-Assembly of Symmetric Supramolecular Double-Comb Diblock Copolymers: a Comb Density Study

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