Association Phenomena Involving Hydrophobically Modified Polymers. Electrostatic and Hydrophobic Contributions

Research output: ThesisDoctoral Thesis (compilation)


The electrostatic and hydrophobic interactions in aqueous solutions of hydrophobically-modified water-soluble non-ionic or ionic polymers, their mixtures with a second polymer, nonionic or of opposite charge, and their mixtures with surfactants of opposite charge have been investigated. The relative strength of the electrostatic and hydrophobic contributions has been modulated by a variation of the polymer charge density and the solution pH, and by a variation in the degree and strength of the hydrophobic modifications, respectively. The repercussions of such interactions on the thermodynamics and dynamics of the systems under study have been quantified experimentally with the aid of phase behavior, rheology, and light scattering techniques, and have been rationalized theoretically in the context of dynamic scaling theory. The association between two oppositely charged hydrophobically modified polyelectrolytes can lead to the formation of soluble or insoluble mixtures depending on the mixture composition, the total polymer concentration, and the charge density of the polyions. The simultaneous presence of ionic and hydrophobic groups in both polymers results in a broad miscibility region (instead of the precipitate expected if only electrostatics were in effect), where the viscosity is three to four orders of magnitude higher than that of the solutions of the individual polymers. The physical networks obtained through the formation of mixed aggregates are especially reinforced in the proximity of phase separation as revealed by the existence of two relaxation modes, a fast diffusive mode and a slow mode (attributed to enhanced hydrophobic associations) in the time correlation data obtained from light scattering measurements. The network dynamics are strongly affected by the presence of the hydrophobic moieties and by the mixture composition, thus making the hydrophobically modified polyelectrolyte mixtures exhibit rheological properties of complex scaling behavior. However, the binary mixtures of unmodified polyelectrolytes as well as the single polyelectrolyte solutions exhibit a viscosity scaling behavior in good agreement with recent predictions of the dynamic scaling theory of polyelectrolytes in the semidilute regime. The interactions between polymers and surfactants of opposite charge in aqueous solutions can lead to the formation of transient networks, the rheological properties of which have been modulated via the addition of cyclodextrins. Cyclodextrins can form inclusion complexes with the hydrophobic moieties of surfactants, and thus they disrupt the polymer-surfactant network as evidenced by their ability to reverse the high viscosities exhibited by such networks.


  • Marina Tsianou
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Physical Chemistry


  • scaling, light scattering, rheology, aqueous solution behavior, phase behavior, cyclodextrin, surfactant, polyacrylate, cellulose ether, polyelectrolyte, hydrophobically modified polymer, Polymer, water soluble polymer, viscosity, association, segregation, Physical chemistry, Fysikalisk kemi
Original languageEnglish
Awarding Institution
Supervisors/Assistant supervisor
  • [unknown], [unknown], Supervisor, External person
Award date1999 Dec 11
  • Lund University
Print ISBNs91-628-3904-7
Publication statusPublished - 1999
Publication categoryResearch

Bibliographic note

Defence details Date: 1999-12-11 Time: 10:15 Place: Lecture Hall C, Kemicentrum, Lund University External reviewer(s) Name: Malmsten, Martin Title: Doc Affiliation: Ytkemiska Institutet, Box 5607, 114 86 Stockholm --- Article: Complex Formation between Oppositely Charged Hydrophobically Modified Polyelectrolytes. Effect of Polymer Charge Density.Marina Tsianou, Krister Thuresson, Lennart Piculell, and Björn LindmanManuscript. Article: Light Scattering and Viscoelasticity in Aqueous Mixtures of Oppositely Charged and Hydrophobically Modified Polyelectrolytes.Marina Tsianou, Anna-Lena Kjøniksen, Krister Thuresson, and Bo NyströmMacromolecules 1999, 32, 2974-2982. Article: Viscosity Scaling in Polyelectrolytes and Mixed Polyelectrolyte Systems in Aqueous Solutions.Marina Tsianou, Krister Thuresson, and Björn LindmanMacromolecules, submitted for publication. Article: Phase Separation in Aqueous Mixtures of Hydrophobically Modified Cellulose Derivatives with their Non-modified Analogues.Krister Thuresson, Marina Tsianou, and Lennart PiculellManuscript. Article: Control of the Rheological Properties in Solutions of a Polyelectrolyte and an Oppositely Charged Surfactant by the Addition of Cyclodextrins.Marina Tsianou and Paschalis AlexandridisLangmuir 1999, 15, 8105-8112.