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Conformation and Phase Diagrams of Flexible Polyelectrolytes

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Polyelectrolytes with Defined Molecular Architecture II

Part of the book series: Advances in Polymer Science ((POLYMER,volume 166))

Abstract

The present article addresses the dilute solution behavior of two different polyelectrolyte systems: Aqueous solutions of quaternized poly(2-vinylpyridines) and of polyacrylic acids. Firstly, it is demonstrated that the dimensions of the chains for all investigated polyelectrolytes are described by a model that explicitly considers (i) an excluded volume comprising contributions of the electrostatic interactions via the effective charge density, and (ii) the intrinsic excluded volume in terms of the Flory interaction parameter. The effect of the chain hydrophobicity and the type of counterions on the coil dimension of the chains and the effective charge density is discussed. The latter is compared with results obtained from osmotic pressure measurements and conductometry.

The second part of the review is devoted to an investigation of the phase behavior of the two systems. For quaternized poly-2-vinylpyridines phase transitions are induced by addition of inert salt, typically NaI and are denoted as “salting out” and “salting in” . The phase behavior is assumed not to be influenced by ion specific interactions other than the Flory excluded volume parameter. Contrary, in case of polyacrylic acid highly specific interactions, such as complexation, between the polyion and bivalent earth alkaline cations may cause a precipitation of the polyelectrolyte. The precipitation point depends on both, the concentration of the polyions and the counter ions. Investigation of the coil dimensions by means of combined static and dynamic light scattering reveals a coil collapse towards spherical particles. Possible transition states along this shrinking process are discussed.

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Abbreviations

DMF:

dimethylformamide

GPC:

gel permeation chromatography

LS:

light scattering

NaPA:

sodium salt of polyacrylic acid

NaPMA:

sodium salt of polymethacrylic acid

NaPSS:

sodium salt of polystyrene sulfonic acid

PEO:

polyethyleneoxide

PNIPAM:

poly(n-isopropylacrylamide)

PVP:

poly(2-vinylpyridine)

THF:

tetrahydrofuran

SAXS:

small angle x-ray scattering

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Author information

Authors and Affiliations

  1. Institut für Physikalische Chemie, Johannes Gutenberg-Universität, 55099 , Mainz, Germany

    N. Volk, D. Vollmer & M. Schmidt

  2. School of Physics, University of Edinburgh, Kings Building, Edinburgh, UK

    D. Vollmer

  3. Institut für Physikalische Chemie der Technischen Universität Clausthal, 38678 , Clausthal-Zellerfeld, Germany

    W. Oppermann

  4. Institut für Physikalische Chemie, Universität Paderborn, 33098, Paderborn, Germany

    K. Huber

Authors
  1. N. Volk
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  2. D. Vollmer
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  3. M. Schmidt
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  4. W. Oppermann
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  5. K. Huber
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Corresponding author

Correspondence to K. Huber .

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Manfred Schmidt

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Volk, N., Vollmer, D., Schmidt, M., Oppermann, W., Huber, K. Conformation and Phase Diagrams of Flexible Polyelectrolytes. In: Schmidt, M. (eds) Polyelectrolytes with Defined Molecular Architecture II. Advances in Polymer Science, vol 166. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b11348

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  • DOI: https://doi.org/10.1007/b11348

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-00556-8

  • Online ISBN: 978-3-540-36463-4

  • eBook Packages: Springer Book Archive

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