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Rheological properties of binary associating polymers

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Abstract

Dynamics of associating polymer solutions above the reversible gelation point are studied. Each macromolecule consists of a soluble backbone (B) and a small fraction of specific strongly interacting groups (A or C stickers) attached to B. A mixture of B–A and B–C associating polymers with 1:1 stoichiometric ratio is considered. As a result of AC association, the polymers reversibly gelate above the overlap concentration. It is shown that (1) the network strands are linear complexes (double chains) of B–A and B–C; (2) “diffusion” of the network junction points is characterized by an apparent activation energy, which can be significantly higher than the energy of one AC bond; (3) most importantly, the randomness of sticker distribution along the chain can significantly slow down the network relaxation leading to a markedly non-Maxwellian viscoelastic behavior. The theory elucidates the most essential features of rheological behavior of polysaccharide associating systems (with A = adamantyl moiety, C = β-cyclodextrin, B = either chitosan or hyaluronan) including similar behavior of G ′ and G ″ in a wide frequency range, strong temperature dependence of the characteristic frequency ω x , and an extremely strong effect of added free stickers (fC) on the dynamics.

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Authors and Affiliations

  1. Institut Charles Sadron, 6 rue Boussingault, 67083, Strasbourg Cedex, France

    Alexander Semenov

  2. Centre de Recherches sur les Macromolecules Vegetales (CNRS), University Joseph Fourier de Grenoble, BP 53, 38041, Grenoble Cedex, France

    Aurélia Charlot, Rachel Auzély-Velty & Marguerite Rinaudo

Authors
  1. Alexander Semenov
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  2. Aurélia Charlot
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  3. Rachel Auzély-Velty
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  4. Marguerite Rinaudo
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Correspondence to Alexander Semenov.

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Semenov, A., Charlot, A., Auzély-Velty, R. et al. Rheological properties of binary associating polymers. Rheol Acta 46, 541–568 (2007). https://doi.org/10.1007/s00397-006-0149-4

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  • DOI: https://doi.org/10.1007/s00397-006-0149-4

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