Shape Changes of Statistical Copolymacromonomers:  From Wormlike Cylinders to Horseshoe- and Meanderlike Structures

Stephan, Thomas; Muth, Sandra; Schmidt, Manfred

doi:10.1021/ma025711r

Cited by 116 publications

(136 citation statements)

References 18 publications

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“…For asymmetric side chain lengths (and flexible backbones) this length scale is related to the spontaneous curvature of the cylinder-shaped bottle brush polymer. Controlling this curvature is desirable for the anticipated application of such molecules in nanotechnology [5].…”

Section: Resultsmentioning

confidence: 99%

“…Clearly, this creates additional possibilities when one considers the desired [5] use of such shape persistent cylindrical macromolecules as building blocks in molecular assemblies. Thus, the problem of phase separation within a simple copolymer bottle brush has also found attention both by analytical theory [6] and computer simulation [7] , the possibility to create "Janus cylinders" (upper half of the cylinder containing the B monomers, lower half containing the A monomers) was suggested, and predictions how the phase transition point from the randomly mixed state (where both A and B monomers are homogeneously distributed in the cylinder volume) to the separated state depends on the chain length of the side chains N were given [6].…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular phase separation of copolymer “bottle brushes”: No sharp phase transition but a tunable length scale

2006

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A lattice model for a symmetrical copolymer "bottle brush" molecule, where two types (A,B) of flexible side chains are grafted with one chain end to a rigid backbone, is studied by a variant of the pruned-enriched Rosenbluth method (PERM), allowing for simultaneous growth of all side chains in the Monte Carlo sampling. Choosing repulsive binary interactions between unlike monomers and varying the solvent quality, it is found that phase separation into an A-rich part of the cylindrical molecule and a B-rich part can occur only locally. Long range order (in the direction of the backbone) does not occur, and hence the transition from the randomly mixed state of the bottle brush to the phase separated structure is strongly rounded, in contrast to corresponding mean field predictions. This lack of a phase transition can be understood from an analogy with spin models in one space dimension. We predict that the range of microphase separation along the bottle brush backbone can be controlled on the nanoscale by varying the solvent quality.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Intramolecular phase separation of copolymer “bottle brushes”: No sharp phase transition but a tunable length scale

2006

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“…[17] The synthesis of such molecules is rather involved, and so far, only one experimental paper has been published. In this paper, Schmidt and co-workers [37] discussed the preparation of statistical copolymacromonomers from poly(2-vinyl pyridine) and poly(methyl methacrylate) macromonomers. Depending on the solvent quality, they demonstrated the presence of different shapes of the copolymer brushes from wormlike to horseshoe or meander structures when spin-cast onto mica.…”

Section: Introductionmentioning

confidence: 99%

Conformational Aspects and Intramolecular Phase Separation of Alternating Copolymacromonomers: A Computer Simulation Study

Jong

Brinke

2004

Macro Theory & Simulations

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Summary: Using the bond fluctuation model (BFM), simulations have been performed on molecular bottle brushes with two chemically different types of side chains. In the first part of this work, rigidity of the backbone is imposed. The influence of solvent quality and side chain length on the intramolecular phase separation of side chain material, leading to Janus cylinders, has been investigated and compared to theoretical predictions. In the second part of this work, the restriction of rigidity for the backbone is relaxed. In a poor solvent, the side chain material collapses into a globular state. Several globules containing each one type of side chain material are connected together by backbone material. When imposing different solvent conditions for both types of side chains, a bending of the backbone is found as predicted by theory and observed in very recent experiments.Comparison between typical snapshots in θ solvent. The side chain length is 25 beads. Dark and light coloured side chains repel each other.imageComparison between typical snapshots in θ solvent. The side chain length is 25 beads. Dark and light coloured side chains repel each other.

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“…[25][26][27] Concerning the second problem, recently the existence of a local phase separation along the backbone of the bottle-brush giving rise to ''horseshoe'' and ''meander''-like structures of copolymer bottle-brushes was observed in experiments. [28] The problem of phase separation within a simple copolymer bottle-brush has also drawn attention both by analytical theory [29] and computer simulation. [30,31] In Ref., [29,30] authors gave the predictions of how the phase transition point from the randomly mixed state (where both A and B monomers are homogeneously distributed in the cylinder volume) to the separated state depends on the chain length N of the side chains and also suggested the possibility to create ''Janus cylinders'' (upper half of the cylinder containing the A monomers, lower half containing the B monomers).…”

mentioning

confidence: 99%

Simulation of Copolymer Bottle‐Brushes

Hsu

Paul

Binder

2007

Macromolecular Symposia

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Summary:The structure of bottle-brush polymers with a rigid backbone and flexible side chains is studied in three dimensions, varying the grafting density, the side chain length, and the solvent quality. Some preliminary results of theoretical scaling considerations for one-component bottle-brush polymers in a good solvent are compared with Monte Carlo simulations of a simple lattice model. For the simulations a variant of the pruned-enriched Rosenbluth method (PERM) allowing for simultaneous growth of all side chains in the Monte Carlo sampling is employed. For a symmetrical binary (A,B) bottle-brush polymer, where two types (A,B) of flexible side chains are grafted with one chain end to the backbone in an alternating way, varying repulsive binary interactions between unlike monomers and the solvent quality, it is found that phase separation into an A-rich part of the cylindrical molecule and a B-rich part can occur only locally. Long range order (in the direction of the backbone) does not occur, and hence the transition from the randomly mixed state of the bottle-brush to the phase-separated structure is strongly rounded, in contrast to the corresponding mean field predictions of a sharp transition to a ''Janus cylinder'' phase-separated structure. This lack of a phase transition can be understood from an analogy with spin models in one dimension. By estimating the correlation length for this phase separation along the backbone as a function of side chain length and solvent quality, we present strong evidence that no sharp phase transition occurs.

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Shape Changes of Statistical Copolymacromonomers: From Wormlike Cylinders to Horseshoe- and Meanderlike Structures

Cited by 116 publications

References 18 publications

Intramolecular phase separation of copolymer “bottle brushes”: No sharp phase transition but a tunable length scale

Intramolecular phase separation of copolymer “bottle brushes”: No sharp phase transition but a tunable length scale

Conformational Aspects and Intramolecular Phase Separation of Alternating Copolymacromonomers: A Computer Simulation Study

Simulation of Copolymer Bottle‐Brushes

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