Impact of intrinsic backbone chain stiffness on the morphologies of bottle-brush diblock copolymers

Chremos, Alexandros; Theodorakis, Panagiotis E.

doi:10.1016/j.polymer.2016.05.034

Cited by 16 publications

(13 citation statements)

References 41 publications

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“…For example, branching of matrix blocks B stabilizes superstructures with spherical domains A , even if A is a majority block. These theoretical predictions are in good qualitative agreement with MD studies. , The morphological diagram of states for macromolecules with equal topological ratios of the blocks coincides with that for copolymers with linear blocks, and the lamella period H ∼ N 2/3 does not depend on copolymer composition. These predictions open novel perspectives in design of nanostructured materials.…”

supporting

confidence: 78%

Theory of Microphase Segregation in the Melts of Copolymers with Dendritically Branched, Bottlebrush, or Cycled Blocks

2019

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Theory of microphase segregation in the melt of diblock copolymers comprising two strongly incompatible blocks of similar or different topologies is developed. The spectrum of considered architectures include copolymers with arbitrary combinations of bottlebrush-like, dendritic, cycled blocks, and so on. Our theory provides quantitative predictions of how the morphology of the microphase segregated structures can be controlled not only by the volume fractions of the incompatible blocks, but also by their architecture. These predictions open perspectives for developing new materials, for example, photonic crystals, with independently adjustable volume fractions and morphology of the domains.

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confidence: 78%

Theory of Microphase Segregation in the Melts of Copolymers with Dendritically Branched, Bottlebrush, or Cycled Blocks

2019

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“…42−44 For linear BCPs, the microdomain morphology is dictated by χ, N, and the volume fraction between two blocks, while for bottlebrush copolymers, the molecular architecture plays a dominant role, and the morphologies can be tuned by the intrinsic backbone chain stiffness. 74 Bottlebrush copolymers can also be conveniently synthesized by a one-pot ring-opening metathesis polymerization (ROMP) of norbornyl endfunctionalized macromonomers with distinct chemical structures. 24,45 The synthesis, self-assembly, and application of densely grafted bottlebrush copolymers have recently become increasingly popular.…”

Section: ■ Introductionmentioning

confidence: 99%

“…With bulky side chains, the molecular backbone is more extended with a much larger persistence length, minimizing entanglements and favoring rapid self-assembly. − For self-assembly in thin films, microdomains oriented normal to the substrate surface are needed for high-fidelity pattern transfer. For high-χ linear BCPs, controlling the interfacial energy coupled with confinement effects arising from commensurability between the film thickness and period of the microdomain morphology is needed to orient the microdomains normal to the substrate. , However, with the entropic gain from the chain architecture, the BBCP domains could orient normal to the surface even if one block has a strong preferential interaction with the substrate. − For linear BCPs, the microdomain morphology is dictated by χ, N , and the volume fraction between two blocks, while for bottlebrush copolymers, the molecular architecture plays a dominant role, and the morphologies can be tuned by the intrinsic backbone chain stiffness . Bottlebrush copolymers can also be conveniently synthesized by a one-pot ring-opening metathesis polymerization (ROMP) of norbornyl end-functionalized macromonomers with distinct chemical structures. , …”

Section: Introductionmentioning

confidence: 99%

Hydrolysis-Induced Self-Assembly of High-χ–Low-N Bottlebrush Copolymers

Rzayev

et al. 2021

Macromolecules

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Densely grafted bottlebrush statistical copolymers (BSCPs) and bottlebrush block copolymers (BBCPs) were synthesized with polystyrene (PS) and poly(solketal methacrylate) (PSM) side chains grafted to a polynorbornene backbone. The PSM chains could be hydrolyzed into poly(glycerol monomethacrylate) (PGM), significantly increasing the segmental interaction parameter (χ). Self-assembly of the polymers was studied with small-angle X-ray scattering before and after hydrolysis. The well-known rapid self-assembly of BBCPs by thermal annealing was retarded after hydrolysis, due to a large χ between the segments of the brushes. Utilizing the well-ordered lamellar morphology before hydrolysis, we developed a solid-state hydrolysis method to achieve high-χ BBCPs with long-range order. Analysis of the Porod scattering invariant showed that for high-χ BBCPs, the density of each phase deviated from the density of linear homopolymer melts due to multiple restrictions placed on the configuration of the brushes.

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“…Bottlebrush polymers have attracted considerable attention in the last few years due to their unique molecular structural features, and these materials have inspired the design of novel applications as rheological property modifiers, 1 pressure sensors, 2 photonic bandgap materials, [3][4][5] pH-sensitive probes, 6 supersoft elastomers, 7,8 nanostructured morphologies, [9][10][11][12][13] and drug delivery agents. 14 Despite advances in polymer synthesis techniques for creating branched molecules with precise control of molecular architecture, [15][16][17][18][19] as well as, experimental 7,12,[19][20][21][22][23][24][25][26][27] and simulation, 11,13,[28][29][30] methods to establish structure property relationships between the bottlebrush polymer architecture, a general understanding of the physical properties of these materials remains largely unexplored. Part of the scientific challenge here is that direct experimental measurements of conformational properties in the melt state are difficult and experimental observations of these properties are often performed in solution rather than in the melt state.…”

Section: Introductionmentioning

confidence: 99%

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

Chremos

Douglas

2018

The Journal of Chemical Physics

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Thermodynamic, conformational, and structural properties of bottlebrush polymer melts are investigated with molecular dynamics simulations and compared to linear, regular star, and unknotted ring polymer melts to gauge the influence of molecular topology on polymer melt properties. We focus on the variation of the backbone chain length, the grafting density along the backbone, and the length of the side chains at different temperatures above the melt glass transition temperature. Based on these comparisons, we find that the segmental density, isothermal compressibility, and isobaric thermal expansion of bottlebrush melts are quantitatively similar to unknotted ring polymer melts and star polymer melts having a moderate number ( f = 5 to 6) of arms. These similarities extend to the mass scaling of the chain radius of gyration. Our results together indicate that the configurational properties of bottlebrush polymers in their melt state are more similar to randomly branched polymers than linear polymer chains. We also find that the average shape of bottlebrush polymers having short backbone chains with respect to the side chain length is also rather similar to the unknotted ring and moderately branched star polymers in their melt state. As a general trend, the molecular shape of bottlebrush polymers becomes more spherically symmetric when the length of the side chains has a commensurate length as the backbone chain. Finally, we calculate the partial static structure factor of the backbone segments and we find the emergence of a peak at the length scales that characterizes the average distance between the backbone chains. This peak is absent when we calculate the full static structure factor. We characterize the scaling of this peak with parameters characterizing the bottlebrush molecular architecture to aid in the experimental characterization of these molecules by neutron scattering.

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Impact of intrinsic backbone chain stiffness on the morphologies of bottle-brush diblock copolymers

Cited by 16 publications

References 41 publications

Theory of Microphase Segregation in the Melts of Copolymers with Dendritically Branched, Bottlebrush, or Cycled Blocks

Theory of Microphase Segregation in the Melts of Copolymers with Dendritically Branched, Bottlebrush, or Cycled Blocks

Hydrolysis-Induced Self-Assembly of High-χ–Low-N Bottlebrush Copolymers

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

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