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Stiff-Chain Polyelectrolytes

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Book cover Polyelectrolytes with Defined Molecular Architecture II

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

Abstract

Rod-like polyelectrolytes represent ideal model systems for a comprehensive comparison of theory and experiment because their conformation is independent of the ionic strength in the system. Hence, the correlation of the counterions to the highly charged macroion can be studied without the interference of conformational effects. In this chapter the synthesis and the solution behavior of rigid, rod-like cationic polyelectrolytes having poly(p-phenylene) (PPP) backbones is reviewed. These polymers can be characterized precisely and possess degrees of polymerization of up to P n ≈ 70. The analysis of the uncharged precursor polymer demonstrated that the PPP backbone has a high persistence length (ca. 22 nm) and hence may be regarded in an excellent approximation as rod-like macromolecules. The solution properties of the PPP-polyelectrolytes were analyzed using electric birefringence , small-angle X-ray scattering (SAXS) and osmometry. Measurements of the electric birefringence demonstrate that these systems form molecularly disperse systems in aqueous solution. The dependence of electric birefringence on the concentration of added salt indicates that an increase of ionic strength leads to stronger binding of counterions to the polyion. Data obtained from osmometry and small-angle X-ray scattering can directly be compared to the prediction of the Poisson-Boltzmann theory and simulations of the restricted primitive model. Semi-quantitative agreement is achieved.

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Abbreviations

a :

radius of macroion

f :

scattering factor (SAXS)

f’ :

real part of scattering factor f

f″ :

imaginary part of scattering factor f

I(q) :

scattering intensity of solution

I 0 (q) :

scattering intensity of isolated molecule

L :

length of rod-like molecule

n(r) :

radial distribution of counterions around rod

q :

magnitude of scattering vector

R M :

Manning radius (Eq. (5))

R 0 :

cell radius

RPM :

restricted primitive model

S(q) :

structure factor describing interaction between solute molecules

α:

cosin of angle between long axis of rod-like molecule and scattering vector q

β :

integration constant of cell model (Eq. (4))

ϕ :

osmotic coefficient

ϕ ∞ :

osmotic coefficient in Manning limit

κ :

screening constant

λ B :

Bjerrum length (Eq. (2))

Π :

osmotic pressure

ξ :

charge parameter (Eq. (1))

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Acknowledgment

The authors are indebted to the Deutsche Forschungsgemeinschaft for generous support within the Schwerpunkt “Polyelektrolyte”. C. Holm acknowledges M. Deserno for intensive collaboration on the presented material.

Author information

Authors and Affiliations

  1. Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 , Mainz, Germany

    C. Holm

  2. Institute for Macromolecular Chemistry, Technical University of Darmstadt, Petersenstrasse 22, 64287 , Darmstadt, Germany

    M. Rehahn

  3. Institut für Physikalische Chemie, Technische Universität Clausthal, Arnold-Sommerfeld-Str. 4, 38678, Clausthal-Zellerfeld, Germany

    W. Oppermann

  4. Polymer Institute, University of Karlsruhe, Kaiserstrasse 12, 76128 , Karlsruhe, Germany

    M. Ballauff

Authors
  1. C. Holm
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  2. M. Rehahn
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  3. W. Oppermann
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  4. M. Ballauff
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Corresponding author

Correspondence to M. Ballauff .

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Manfred Schmidt

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Holm, C., Rehahn, M., Oppermann, W., Ballauff, M. Stiff-Chain 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/b11347

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  • DOI: https://doi.org/10.1007/b11347

  • 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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