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Counterion effect of cationic surfactants on the interaction with poly(acrylic acid)

  • Dan F. Anghel
  • Shuji Saito
  • Alina Iovescu
  • Adriana Bãran
  • Gabriela Stîngã
  • Constantin Neamtu
Conference paper
Part of the Progress in Colloid and Polymer Science book series (PROGCOLLOID, volume 122)

Abstract

In the interaction of poly(acrylic acid) (PAA) and some cationic surfactants, the effects of counterions on the critical aggregation concentration (Cac or T 1) and other critical points were studied by surface tension, conductance, pH and viscosity measurements in unbuffered systems. The surfactant cations were n-dodecylammonium, n-dodecyltrimethylammonium and n-decylammonium (DeA), the latter being mainly employed. The inorganic counterions were chloride, iodide and thiocyanate. These anions are in both far positions in the lyotropic series. The organic counterions were short-chain alkyl carboxylate ions (R-, i.e., acetate, propionate and butyrate). Whereas the critical micelle concentration (cmc) of DeA-Cl was higher than that of DeA-SCN, T 1 in presence of PAA was the opposite. No pH shift was observed below T 1. It was considered that when Cl- ion is taken as the reference, the strong water-structure-breaking SCN- ion may promote hydrophobic self-association of surfactant cations and induce low dissociation or ion-pairing. This counterion effect lowers the cmc and raises T 1. The cmc of DeA-acetate was the highest among the three DeA-Rs, but its T 1 was the lowest though the differences were slight. Therefore, the opposite relation between the cmc and T 1 holds for inorganic and the organic counterions as well. The cmcs of DeA-Cl and DeA-acetate were similar, but T 1 for the latter was much lower. By addition of DeA-Rs, the pH rose even below T 1. The carboxylate ion positions between F- and Cl- in the lyotropic series because of its strong electrical field, and the degree of dissociation of the surfactant as salt is related to T 1. In these T 1 features, in addition to the electrostatic effect, the hydrophobic factor and pH change are involved. Thus, SCN- and R-s emphasize significant roles of the counterion in the interaction with oppositely charged polymers. The T 1/cmc ratios for the three DeA-Rs were much lower than that for DeA-Cl, which was lower than that for DeA-SCN. For nonionic surfactants, the T 1/cmc was markedly higher than for the cationic surfactants.

Keywords

Poly(acrylic acid) Cationic surfactants Counterions Nonionic surfactants Complexes 

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Copyright information

© Springer-Verlag 2003

Authors and Affiliations

  • Dan F. Anghel
    • 1
  • Shuji Saito
    • 2
  • Alina Iovescu
    • 1
  • Adriana Bãran
    • 1
  • Gabriela Stîngã
    • 1
  • Constantin Neamtu
    • 3
  1. 1.Department of Colloids“I.G. Murgulescu” Institute of Physical ChemistryBucharestRomania
  2. 2.TakarazukaJapan
  3. 3.Department of PesticidesInstitute of Chemical ResearchBucharestRomania

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