Phase Behavior of Solutions of Polymers with Multiply Aggregating Groups

Kudlay, Alexander; Erukhimovich, I. Ya.

doi:10.1002/1521-3919(20010601)10:5<542::aid-mats542>3.0.co;2-s

Cited by 10 publications

(15 citation statements)

References 16 publications

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“…The phase behavior of uncharged, partially associated polymers has been thoroughly analysed in ref. [14,17,18] As has been shown in these papers, the presence of stickers leads to an effective attraction between monomeric units and an effective increase of theparameter.…”

Section: The Effect Of Multiplet Formationmentioning

confidence: 99%

“…[14] Neglecting all the interactions in the system except the association of unimers into dimers and tetramers, one can write the generating function ðz 1 ; z 2 Þ of all clusters present in the system as follows:…”

Section: Appendixmentioning

confidence: 99%

“…[14] for the aggregation free energy of the system of particles capable of thermoreversible formation of m-mers.…”

Section: Appendixmentioning

confidence: 99%

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The Influence of Ion Pair Formation on the Phase Behavior of Polyelectrolyte Solutions

Kramarenko¹,

Erukhimovich

Хохлов

2002

Macromol. Theory Simul.

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In this paper we calculate the phase diagrams of polyelectrolyte solutions taking into account the possibility of ion pair formation between counterions and ions on polymer chains with their subsequent aggregation in multiplets. Multiplets play a role of reversible physical crosslinks between different polymer chains. Furthermore, we assume that the dielectric constant, and hence the binding energy of ion pairs and multiplets, depends on the volume fraction of polymer in the solution. We have shown that ion pairing and multiplet formation leads to instability of the homogeneous phase, so that at some conditions the phase separation can proceed even in good solvent. Another qualitatively new feature of the behavior of polyelectrolyte solutions is the emergence of a triple point on the phase diagram. The effect of the solvent polarity and the polarity of the dry polymer on the general form of the phase diagram is studied in detail.

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Section: The Effect Of Multiplet Formationmentioning

confidence: 99%

Section: Appendixmentioning

confidence: 99%

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The Influence of Ion Pair Formation on the Phase Behavior of Polyelectrolyte Solutions

Kramarenko¹,

Erukhimovich

Хохлов

2002

Macromol. Theory Simul.

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“…The first process described by so-called critical incorporation concentration (CIC) 18 was shown to be non-cooperative, while micellization in initially non-aggregated system is highly cooperative and can result in jump-like changes in the system behavior. Whereas phase behavior of solutions of HM linear polymers with associating groups [21][22][23][24][25] and conformations of single polysoap molecules [26][27][28][29] have been studied in detail, there is no theoretical model considering swelling of polymer networks with hydrophobic side chains in surfactant solutions. In the present article, we develop a theoretical approach to describe hydrophobic association inside these networks and to study their interaction with surfactants.…”

Section: Introductionmentioning

confidence: 99%

Polymer gels with associating side chains and their interaction with surfactants

Gordievskaya

Rumyantsev

Kramarenko

2016

The Journal of Chemical Physics

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Conformational behaviour of hydrophobically modified (HM) polymer gels in solutions of nonionic surfactants is studied theoretically. A HM gel contains hydrophobic side chains (stickers) grafted to its subchains. Hydrophobic stickers are capable to aggregate into joint micelles with surfactant molecules. Micelles containing more than one sticker serve as additional physical cross-links of the network, and their formation causes gel shrinking. In the proposed theoretical model, the interior of the gel/surfactant complex is treated as an array of densely packed spherical polymer brushes consisting of gel subchains tethered to the surface of the spherical sticker/surfactant micelles. Effect of stickers length and grafting density, surfactant concentration and hydrophobicity on gel swelling as well as on hydrophobic association inside it is analyzed. It is shown that increasing surfactant concentration can result in a gel collapse, which is caused by surfactant-induced hydrophobic aggregation of stickers, and a successive gel reswelling. The latter should be attributed to a growing fraction of surfactants in joint aggregates and, hence, increasing number of micelles containing only one sticker and not participating in gel physical cross-linking. In polyelectrolyte (PE) gels hydrophobic aggregation is opposed by osmotic pressure of mobile counterions, so that at some critical ionization degree hydrophobic association is completely suppressed. Hydrophobic modification of polymers is shown to open new ways for controlling gel responsiveness. In particular, it is discussed that incorporation of photosensitive groups into gel subchains and/or surfactant tail could give a possibility to vary the gel volume by light. Since hydrophobic aggregation regularities in gels and solutions are common, we hope our findings will be useful for design of polymer based self-healing materials as well.

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“…Therefore it is natural to think in terms of the enumeration of graphs, as extensively reviewed by Kuchanov, et al [7]. The ideas can then be applied to a variety of systems, such as associating telechelics [8], polycondensation [9], polymers with multiply aggregating groups [10] and general thermally reversible aggregation, clustering or association [11][12][13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Field-theoretical approach to a dense polymer with an ideal binary mixture of clustering centers

Fantoni

Müller-Nedebock

2011

Phys. Rev. E

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We propose a field-theoretical approach to a polymer system immersed in an ideal mixture of clustering centers. The system contains several species of these clustering centers with different functionality, each of which connects a fixed number segments of the chain to each other. The field-theory is solved using the saddle point approximation and evaluated for dense polymer melts using the Random Phase Approximation. We find a short-ranged effective inter-segment interaction with strength dependent on the average segment density and discuss the structure factor within this approximation. We also determine the fractions of linkers of the different functionalities.

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Phase Behavior of Solutions of Polymers with Multiply Aggregating Groups

Cited by 10 publications

References 16 publications

The Influence of Ion Pair Formation on the Phase Behavior of Polyelectrolyte Solutions

The Influence of Ion Pair Formation on the Phase Behavior of Polyelectrolyte Solutions

Polymer gels with associating side chains and their interaction with surfactants

Field-theoretical approach to a dense polymer with an ideal binary mixture of clustering centers

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