Preparation and self-assembly of two-length-scale A-b-(B-b-A)n-b-B multiblock copolymers

Faber, Martin; Voet, Vincent S. D.; Brinke, G. ten; Loos, Katja

doi:10.1039/c2sm07211d

Cited by 25 publications

(24 citation statements)

References 56 publications

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“…Whereas linear diblock copolymers are known to form only four different stable structures upon self‐assembly (namely spheres, cylinders, lamellae, and gyroids), careful design of the macromolecular architecture or including additional blocks can enrich the phase behavior significantly . For instance, binary AB multiblock copolymers and A(AB) 3 miktoarm star polymers 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 .…”

Section: Methodsmentioning

confidence: 99%

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: Methodsmentioning

confidence: 99%

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

et al. 2016

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“…This phenomenon became an attractive area of research both experimentally [1][2][3][4][5][6][7][8][9][10][11][12] and theoretically, [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] during the last decades. First, the two-length-scale structures, which might be called lamellar-in-lamellar structures (see Fig.…”

Section: Introductionmentioning

confidence: 99%

Perpendicular lamellar-in-lamellar and other planar morphologies in A-b-(B-b-A)2-b-C and (B-b-A)2-b-C ternary multiblock copolymer melts

Марков

Kriksin

Erukhimovich

et al. 2013

The Journal of Chemical Physics

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Ordered planar morphologies in A-b-(B-b-A)2-b-C and (B-b-A)2-b-C terpolymer melts are studied within the framework of the self-consistent field theory for volume fractions of components A, B, and C in the ratio 1:1:2 and the Flory-Huggins interaction parameters satisfying χ(AB) = 2χ(AC). The stable phases turn out to be the disordered, hexagonal, parallel lamellar-in-lamellar L∥ (including the simple lamellar) as well as non-shifted and shifted (L⊥ and SL⊥) perpendicular lamellar-in-lamellar morphologies. Depending on the value of the ratio r = Θ(AB)/Θ(BC), where Θ is a characteristic temperature of the units involved, different sequences of phase transitions are shown to occur. The hexagonal phase is characteristic for r ≅ 1. The L⊥ and SL⊥ morphologies occur at weak and intermediate segregations whereas the L∥ morphology appears for stronger degrees of segregation. For (B-b-A)2-b-C a reduction in r favors the shifted SL⊥ phase over the non-shifted L⊥ one, whereas for A-b-(B-b-A)2-b-C we find re-entrant phase transitions SL⊥ - L⊥. The physics determining the particular phase behavior is discussed.

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“…In collaboration with the University of Groningen where a specialized anionic polymerization setup is available, influences from small impurities on the polymerization was examined. In this paper the results gained with the use of regular Schlenk lines (vacuum/N 2 , Hasselt technique) are compared to these reached in Groningen on the specialized setup [22,23], which allows to avoid the use of syringes and thus water and/or oxygen intake as much as possible. (iii) Finally, also the synthesis of block copolymers by addition of a second monomer to the living PPV polymers is described.…”

Section: Introductionmentioning

confidence: 99%

Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequential addition of monomers

Cosemans¹,

Vandenbergh²,

Voet³

et al. 2013

Polymer

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Preparation and self-assembly of two-length-scale A-b-(B-b-A)n-b-B multiblock copolymers

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Cited by 25 publications

References 56 publications

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers

Perpendicular lamellar-in-lamellar and other planar morphologies in A-b-(B-b-A)2-b-C and (B-b-A)2-b-C ternary multiblock copolymer melts

Anionic PPV polymerization from the sulfinyl precursor route: Block copolymer formation from sequential addition of monomers

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