100th Anniversary of Macromolecular Science Viewpoint: Block Copolymers with Tethered Acid Groups: Challenges and Opportunities

Kang, Sejong; Park, Moon Jeong

doi:10.1021/acsmacrolett.0c00629

Cited by 17 publications

(15 citation statements)

References 143 publications

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“…For example, ion association and polymer segmental dynamics in ion-doped polymers are both strongly affected by ion–ion and ion–polymer interactions . In addition to these interactions, ion transport properties in copolymeric systems depend also on the polymers’ microphase morphology, which itself is influenced by the ion–polymer interactions and polymeric/ionic compositions. − In the case of charged polymers, nanoscale ionic aggregates can form due to strong Coulomb interactions between ions in a relatively low polarity polymer matrix (such as in typical solvent-free ionomer melts) . Meanwhile, when charged polymers are used with solvents (e.g., in polyelectrolyte solutions), ionic aggregation is less strong, but how the solvent interacts with charged polymer chains becomes critical …”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Simulations of Ion-Containing Polymers Using Generic Coarse-Grained Models

2021

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Molecular dynamics simulations with generic bead–spring models have been instrumental in revealing the molecular-scale behavior that underlies structure–property relationships of various types of polymeric systems. The generic, coarse-grained modeling approach does not include atomistic detail and is not focused on quantitatively matching the properties of a particular chemical system, though typically several parameters are included that can be tuned to consider different types of chemistries. Besides allowing access to longer length and time scales due to computational efficiency, this type of approach is advantageous in that the physical insight gained is often relevant across the entire class of related materials. The connectivity and number of beads in a generic bead–spring models can be adjusted in an obvious manner to describe the most basic homopolymer features (e.g., to consider different chain lengths and linear versus branched architectures). In uncharged copolymers or solvent-containing systems, the chemical interactions between components are considered by adjusting the strength of the various pairwise interparticle potentials (usually without changing their form). However, ions can have stronger and longer-ranged interactions with each other, with solvents, and with monomers that can require additional complexity be added to appropriately describe relevant phenomena in ion-containing polymeric systems. Recent efforts are pushing the boundaries of the generic coarse-grained approach by including additional ion–ion or ion–polymer interactions to more closely capture and analyze such phenomena, while still avoiding detailed and specific empirical adjustments that would make the model only apply to a single chemical system. In this perspective, we highlight a variety of recent molecular dynamics work that applies generic coarse-grained models to study ion-containing polymeric materials. We also discuss possible future directions and challenges of the generic coarse-graining approach in this area.

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Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Simulations of Ion-Containing Polymers Using Generic Coarse-Grained Models

2021

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“…In the past few decades, various types of polymer electrolytes have been extensively investigated in their potential for energy storage and electrochemical devices. − Despite promising advances in this regard, the generally lower conductivity of such materials have hindered their adoption in practical technological contexts. As a possible means to maintain sufficiently high conductivity simultaneously with mechanical strength, attention has turned toward designing block copolymeric electrolytes (BCP) composed of combinations of conductive and mechanically strong blocks. − It has been suggested that by appropriately choosing blocks to facilitate ion transport and mechanical strength and by tuning the morphology and domain sizes, such block copolymeric materials could overcome the trade-off between mechanical strength and conductivity underlying many polymer electrolytes.…”

Section: Introductionmentioning

confidence: 99%

A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids

Zhang

Krajniak²,

Ganesan

2021

Macromolecules

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We present results of a multiscale simulation study involving coarse-graining and reverse-mapping steps probing at an atomistic resolution the influence of morphology on ion transport in block copolymer polymeric ionic liquids. We provide a detailed description of the multiscale simulation methodology and then describe the results in the context of four microphase-separated morphologies: two lamella systems, a cylinder, and a gyroid morphology. For the framework adopted in this study (in which the total number of ions was maintained fixed), morphology had little influence on the fraction of ions segregating to the interface and the coordination and hopping characteristics of such interfacially present ions. Such results manifested in anion mobilities being insensitive to the morphology once the dimensionality of the morphology was accounted for. Overall, our results are consistent with the hypothesis that the mobility of ions in such microphase-separated morphologies, after accounting for the dimensionality effects, can be roughly correlated to a linear superposition based on the fraction of bulk anions, which possess mobilities unperturbed from their values in the conducting homopolymers, and the interfacial anions, which exhibit much lower mobilities.

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“…When bearing charged groups in one block, the BCPs self-assembled in a complicated manner due to the complex interactions. There are some pioneering theoretical and experimental research works focusing on the self-assembly of charged BCPs or BCPEs. ,,, Goswami et al. reported the unusual bulk morphology of fluorinated polyisoprene- block -sulfonated polystyrene (FPI- b -PSS) consisting of a hexagonal FPI cylinder dispersed in a continuous phase of the minority PSS component.…”

Section: Introductionmentioning

confidence: 99%

“…There are some pioneering theoretical and experimental research works focusing on the self-assembly of charged BCPs or BCPEs. 9,10,20,21 component. This phenomenon was ascribed to the charge percolation driven by Coulombic interactions.…”

Section: Introductionmentioning

confidence: 99%

Electrostatic Control of the Three-Dimensional Confined Assembly of Charged Block Copolymers in Emulsion Droplets

et al. 2021

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Understanding the microphase separation of charged block copolymers (BCPs) is very important for the development of functional materials with tunable structures. Although the morphological behavior of charged BCPs in bulk and in solution has been explored, the three-dimensional (3D) confined self-assembly of charged BCPs is still unknown. Here, we report the confined assembly of positively charged polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in emulsion droplets. The fraction of charged segments can be well tailored by the quaternization of the 4VP unit with methyl iodide. A series of BCP particles, including pupa-like, onion-like, bumpy, sphere-in-sphere particles, large compound vesicles, and others, could be obtained by tuning the charge fraction and block ratio of BCPs. The introduction of charge affected the hydrophilicity and chain conformation of BCPs, leading to the change in the morphology of assemblies. Moreover, the addition of inorganic salts showed an obvious effect on the assembly of charged PS-b-P4VP, whose morphology was dependent on the hydration nature of the counterions. This work not only presents a fundamental understanding of the self-assembly of charged BCP under 3D confinement but also inspires the design and preparation of functional nanoparticles with tunable morphologies.

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100th Anniversary of Macromolecular Science Viewpoint: Block Copolymers with Tethered Acid Groups: Challenges and Opportunities

Cited by 17 publications

References 143 publications

Molecular Dynamics Simulations of Ion-Containing Polymers Using Generic Coarse-Grained Models

Molecular Dynamics Simulations of Ion-Containing Polymers Using Generic Coarse-Grained Models

A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids

Electrostatic Control of the Three-Dimensional Confined Assembly of Charged Block Copolymers in Emulsion Droplets

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