Concentration dependence of rheological properties of telechelic associative polymer solutions

Uneyama, Takashi; Suzuki, Shinya; Watanabe, Hiroshi

doi:10.1103/physreve.86.031802

Cited by 66 publications

(140 citation statements)

References 39 publications

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“…20 At low frequencies the moduli are within a viscous regime, where G′ < G″. This viscous behavior typically exhibits a frequency dependence which scales as G′ ∝ ω 2 and G″ ∝ ω.…”

Section: ■ Rheological Propertiesmentioning

confidence: 97%

Computational Study of the Structure and Rheological Properties of Self-Associating Polymer Networks

Wilson¹,

Rabinovitch

Baljon³

2015

Macromolecules

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Utilizing a novel, hybrid molecular dynamics, Monte Carlo simulation, we report on microstructural changes in a polymer network that arise in response to oscillatory shear deformation. We model telechelic selfassociating polymers as a course-grained, bead−spring system. The stress response of the system is obtained from rheological experiments and is reported as a function of frequency and amplitude in both the linear and nonlinear regimes. The frequency-dependent material properties are then correlated with observed changes in the topological network structure. While only minimal structural variations are observed in the elastic regime, a substantial rearrangement occurs in the low frequency, large amplitude viscous regime. Aggregates tend to break apart, resulting in an increased density of free chains. Additionally, the network tends to break and form larger structural elements with an increase multiplicity of chains bridging between the same two aggregates. ■ INTRODUCTIONAssociating polymers have the unique ability to span a large spectrum of rheological properties, from fluid-like viscosity to near solid-like elastic dynamics. Telechelic polymers are one class of associating polymers. These triblock polymers consist of two differing chemical groups. The backbone has a high molecular weight and is constructed from multiple, repeating units. The two functionalized ends of the molecule, referred to as end groups, are members of a different chemical group and comprise a small fraction of the total molecular weight. In solution, end groups tend to aggregate by gathering into localized domains. At low enough temperatures and at concentrations above the micelle transition, a space spanning network is formed. The nodes of this network consist of aggregates of end groups, while links between aggregates are formed by one or more bridging polymer chains. End groups associate and dissociate from aggregates frequently; therefore, the topological structure within the network exhibits transient behavior.The general fluid thickening characteristics of telechelic polymers have long since had utility as a rheological modifier in industrial applications within coatings 1 such as paints, adhesives, plastics, and sealants. Over the past few decades, they have come into considerable interest in a multitude of fields. Most recently, composite materials, partially composed of telechelic polymers, have found their respective place in medical and biological applications. Examples include a temporary matrix for bone tissue regeneration 2 and an injectable drug delivery method 3,4 along with regenerative tissue engineering for wound dressing. 5 Within these applications a water-soluble polymer is desirable, constructed as a hydrophilic backbone terminated by hydrophobic groups. 6−9 Because of the fact that these materials are primarily water by weight, they can exhibit biocompatible and biodegradable properties. They can also be subject to external parameters such as temperature and pH. 10,11 The behavior of these materials is highly s...

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Section: ■ Rheological Propertiesmentioning

confidence: 97%

Computational Study of the Structure and Rheological Properties of Self-Associating Polymer Networks

Wilson¹,

Rabinovitch

Baljon³

2015

Macromolecules

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“…Several theoretical models have been proposed to describe the rheological response of telechelic polymers [77,78] and unentangled [41,[79][80][81][82] or entangled [83][84][85][86][87] supramolecular polymers. For unentangled polymers with supramolecular side-groups, the polymer type relevant to our work, the so-called sticky-Rouse model has been proposed [41,[79][80][81][82].…”

Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate based polymers for which the concentration of randomly distributed supramolecular side-groups are systematically varied. We perform a detailed investigation of the appplicability of Time Temperature Superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the "stickyRouse" model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the "sticky-Rouse" model, which includes more realistic assumptions with regards to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends and (iii) the chain motion upon dissociation of a sticker and re-association with a new co-ordination which involves a finite sized "hop" of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology. * k.j.l.mattsson@leeds.ac.uk 2

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“…as 6‐Cet, 15‐Cet, and 32‐Cet), follow the functional form for the concentration dependence of the relaxation time predicted by Equation (1) fairly well. The relationship fails, however to give a good fit for the τ shear ( c L ) reported by Uneyama et al for molecular weight M n = 36 kDa HEUR. It is not clear why the model fails for this last system and not the others.…”

Section: Resultsmentioning

confidence: 79%

“…The data of Annable et al are particularly amenable to the application of Equation (1) because the data points are sampled densely enough along the concentration axis to allow the slope dG 0 / dc L to be estimated with confidence. Sparser data sets on similar HEUR polymers have also been published . As a plausibility check for the consistency of Equation (1) with these results, we assume a shifted power‐law dependence of the plateau modulus, which according to Equation (1) implies τ shear ( c L ) ∝( c L ‐ c 0 )/ c L .…”

Section: Resultsmentioning

confidence: 82%

“…Another factor that may contribute to the difference between the behaviors of the systems studied by Uneyama et al and Barmar et al is polydispersity. The Uneyama material was relatively monodisperse (polydispersity index M w / M n = 1.35 compared with 1.8, 1.9, and 2.5 for the three samples analyzed in ref., in order of increasing molecular weight.) Monodisperse linkers are expected to produce more regular spacings between micelles, and spatial correlations are not accounted for in the model.…”

Section: Resultsmentioning

confidence: 86%

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On the Relationship Between Plateau Modulus and Shear Relaxation Time in Transient Networks

West

Kindt

2015

Macromol. Theory Simul.

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The linear rheology of unentangled Maxwellian transient networks formed from reversibly associating telechelic polymers can be characterized by a plateau modulus and a shear relaxation time. The concentration dependences of both these properties have been modeled using a variety of theories. An expression is introduced here that allows the concentration dependence of shear relaxation time to be determined (to within a constant, the microscopic chain lifetime) directly from the concentration dependence of the plateau modulus, subject to some approximations. This prediction is tested against experimental results for hydrophobic ethoxylated urethane (HEUR) and against results of simple‐model simulations. The nature of the approximations needed to derive this relationship and the scope of its applicability are discussed.

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Concentration dependence of rheological properties of telechelic associative polymer solutions

Cited by 66 publications

References 39 publications

Computational Study of the Structure and Rheological Properties of Self-Associating Polymer Networks

Computational Study of the Structure and Rheological Properties of Self-Associating Polymer Networks

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

On the Relationship Between Plateau Modulus and Shear Relaxation Time in Transient Networks

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