Molecular dynamics simulations of bottlebrush macromolecules in two dimensional polymeric melts under flow conditions

Carrillo, Jan‐Michael Y.; Sheiko, Sergei S.; Dobrynin, Andrey V.

doi:10.1039/c0sm01165g

Cited by 3 publications

(3 citation statements)

References 30 publications

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“…These methods can easily handle number of particles, ,,,, yet bottlebrush multichain systems are much more computationally expensive to simulate if the number of particles per chain remains . To this end, state-of-the-art particle-based simulations are limited to a modest number of particles per chain. ,,,,,− However, there remains a strong need for modeling large bottlebrush molecules to match synthetic polymers. There have been two general approaches to address this problem.…”

Section: Recent Advances In Bottlebrush Engineeringmentioning

confidence: 99%

Materials Design of Highly Branched Bottlebrush Polymers at the Intersection of Modeling, Synthesis, Processing, and Characterization

et al. 2022

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Highly branched “bottlebrush” polymers are a class of macromolecules characterized by side chains that are densely grafted from a backbone that is typically linear. Their unique and often-desirable properties stem from steric repulsion between side chains, which stiffens the molecular contour and increases interchain spacing. There has been a renaissance in both our fundamental understanding, practical synthesis, and application of these materials, due to synergistic advances in all branches of polymer science. In this perspective, we outline how a wide variety of new functional bottlebrush materials have emerged from the convergence of insights from the entire materials design process; the integration of synthesis, characterization, processing, and modeling has demonstrated the promise of these branched macromolecules as a versatile platform for molecular engineering. We discuss how this platform may be further developed to exhibit novel material properties in and out of equilibrium and put into practice due to the next generation of synthetic, analytical, processing, and computational tools in materials chemistry.

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Section: Recent Advances In Bottlebrush Engineeringmentioning

confidence: 99%

Materials Design of Highly Branched Bottlebrush Polymers at the Intersection of Modeling, Synthesis, Processing, and Characterization

et al. 2022

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“…This is particularly prevalent in the simulation literature, with a wide range of simulation models to try to capture the conformational properties of bottlebrush polymers. Efforts include Monte Carlo (MC) simulations (both lattice-based and off-lattice − ), bond fluctuation models, − cellular automaton models, molecular dynamics (MD) models, ,− and Brownian dynamics (BD) models . In addition, numerical theory such as self-consistent field theory , and polymer reference interaction site model (PRISM) theory have also been used to capture the conformational attributes of bottlebrush polymers.…”

Section: Introductionmentioning

confidence: 99%

Bridging Simulation Length Scales of Bottlebrush Polymers Using a Wormlike Cylinder Model

Dutta

Pan

Sing³

2019

Macromolecules

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Bottlebrush polymers, formed from a linear backbone polymer with a high density of grafted side chains, are functional macromolecules useful in molecular assembly and responsive materials due to their unique physical properties. Interactions between the side chains stiffen the molecular backbone and imbue it with a molecular dimension beyond simply the polymer length, drastically altering dynamic relaxation and intrapolymer interactions. Simulation prediction of these material properties remains a challenge, however, because they specifically depend on side chain degrees of freedom that are computationally expensive to model. In this work, we use the wormlike cylinder framework to systematically map molecular features from a single-molecule hybrid Brownian dynamics and Monte Carlo (BD/MC) simulation with explicit side chains to a simple touched-bead polymer model. We use static properties from the explicit side chain simulations such as end-to-end distance and radius of gyration to parameterize the wormlike cylinder model and consistently reproduce other single-chain properties such as hydrodynamic radius and intrinsic viscosity. This parameterization yields the stiffness parameter and equivalent diameter of a bottlebrush and is compared to prior scaling theories and simulation results. We find that the wormlike cylinder model, appropriately parameterized, provides an accurate description of these quantities over a wide range of side chain lengths and grafting densities. We demonstrate that a coarse-grained representation is able to consistently reproduce the bottlebrush structure and show that the wormlike cylinder model can be useful for large-scale coarse-grained simulations of bottlebrush suspensions.

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“…Most of the efforts to computationally model bottlebrush polymers have so far been focused on determining the relationship between molecular architecture and bottlebrush conformation; in particular, Monte Carlo (MC), , molecular dynamics (MD), ,,,,− and Brownian dynamics (BD) simulations have all been used to examine questions related to the effect of molecular parameters such as grafting density, side-chain length ( N sc ), and backbone length ( N bb ) on observables such as stiffness, molecular size (i.e., end-to-end distance, radius of gyration), and shape. When compared to experiments, such as via X-ray scattering or intrinsic viscosity, these simulations often perform well. , …”

Section: Introductionmentioning

confidence: 99%

Implicit Side-Chain Model and Experimental Characterization of Bottlebrush Block Copolymer Solution Assembly

et al. 2021

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Bottlebrush polymers are a class of macromolecules with linear backbones and densely grafted side chains, possessing unique physical properties due to strong steric interactions between the side chains. These interactions serve to both stiffen the molecular contour and impart a molecular width, leading to material properties distinct from linear counterparts. This is especially important for the case of diblock bottlebrush copolymers, where side-chain-induced stiffness leads to assembly on large length scales while simultaneously suppressing molecular entanglements that would otherwise hinder self-assembly. The resulting microphase-separated structure is thus ideal for photonic crystals, due to the formation of long-range order with features on length scales commensurate with the wavelength of visible light. Despite the usefulness of block copolymer bottlebrush materials, it remains challenging to model their self-assembly in solution due to the additional side-chain degrees of freedom, which are computationally expensive to resolve. In this paper, we develop a simulation model for bottlebrush block copolymer solution selfassembly that adapts a recently developed implicit side-chain model, accounting for the effect of side chains within a simplified, beadrod polymer model. We further extend this model by deriving an intermolecular interaction potential from scaling arguments and show that we can predict bottlebrush self-assembly over a range of block fractions and polymer concentrations. For all architectures studied, we observe an order−disorder transition to lamellar morphologies and regions of significant compositional fluctuations in the disordered phase. We compare computational predictions of self-assembly to experiments, using diblock bottlebrush copolymers synthesized with poly(norbornene) backbones and polystyrene side chains and poly(lactic acid) side chains on each block. We show that the simulation structure factors match well with experimental scattering and indicate the emergence of self-assembly at high concentrations.

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Molecular dynamics simulations of bottlebrush macromolecules in two dimensional polymeric melts under flow conditions

Cited by 3 publications

References 30 publications

Materials Design of Highly Branched Bottlebrush Polymers at the Intersection of Modeling, Synthesis, Processing, and Characterization

Materials Design of Highly Branched Bottlebrush Polymers at the Intersection of Modeling, Synthesis, Processing, and Characterization

Bridging Simulation Length Scales of Bottlebrush Polymers Using a Wormlike Cylinder Model

Implicit Side-Chain Model and Experimental Characterization of Bottlebrush Block Copolymer Solution Assembly

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