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.
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References
Robb ID (1981) In: Lucassen-Reynders E (ed) Anionic surfactants: physical chemistry of surfactant action. Dekker, New York, pp 109–142
Goddard ED (1993) In: Goddard ED, Ananthapadmanabhan KP (eds) Interactions of surfactants with polymers and proteins. CRC, Boca Raton, pp 171–201
Rodenhiser AP, Kwak JCT (1998) In: Kwak JCT (ed) Polymer-surfactant systems, vol 77. Dekker, New York, pp 1–20
Hayakawa K, Kwak JCT (1991) In: Rubingh DN, Holland PM (eds) Cationic surfactants, physical chemistry. Dekker, New York, pp 189–248
Wei YC, Hudson SM (1995) J Macromol Sci Rev Macromol Chem Phys C 35:15
Piculell L, Lindman B, Karlström G (1998) In: Kwak JCT (ed) Polymer-surfactant systems, vol 77. Dekker, New York, pp 65–141
Ananthapadmanabhan KP (1993) In: Goddard ED, Ananthapadmanabhan KP (eds) Interactions of surfactants with polymers and proteins. CRC, Boca Raton, pp 5–58
Saito S, Yukawa M (1969) J Colloid Interface Sci 30:211
Saito S, Yukawa M (1969) Kolloid Z Z Polym 234:1015
Saito S (1970) J Polym Sci A 18:263
Saito S, Kitamura K (1971) J Colloid Interface Sci 35:346
Saito S, Taniguchi T, Kitamura K (1971) J Colloid Interface Sci 37:154
Harada S, Komatsu T, Nakagawa T (1974) Nippon Kagaku Kaishi 662
Harada S, Komatsu T, Nakagawa T (1974) Rep Prog Polym Phys Jpn 17:101
Harada S, Komatsu T, Nakagawa T (1976) Rep Prog Polym Phys Jpn 19:17
Binana-Limbele W, Zana R (1987) Macromolecules 20:1331
Zana R (1998) In: Kwak JCT (ed) Polymer-surfactant systems. Dekker, New York, pp 409–454
Goddard ED (1993) In: Goddard ED, Ananthapadmanabhan KP (eds) Interactions of surfactants with polymers and proteins. CRC, Boca Raton, pp 123–169
Kavanau JL (1964) Water and solute-water interactions. Holden-Day, San Francisco
Bockris JOM, Reddy AKN (1971) Modern electrochemistry, vol 1. Plenum, New York
Ridell A, Evertsson H, Nilsson S (2002) J Colloid Interface Sci 247:381
Saito S (1969) J Polym Sci A 17:1789
Saito S, Anghel DF (1998) In: Kwak JCT (ed) Polymer-surfactant systems, vol 77. Dekker, New York, pp 357–408
Anghel DF, Saito S, Baran A, Iovescu A (1998) Langmuir 14:5342
Mukerjee P, Mysels KJ (1971) Critical micelle concentration of aqueous surfactant systems, NSRDS-NBS 36. National Bureau of Standards, Washington, DC
Vogel AI (1956) A textbook of practical organic chemistry including qualitative organic analysis, 3rd edn. Longmans, London
Raicu V, Baran A, Iovescu A, Anghel DF, Saito S (1997) Colloid Polym Sci 275:372
Raicu V, Baran A, Anghel DF, Saito S, Iovescu A, Radoi C (1998) Prog Colloid Polym Sci 109:136
Anghel DF, Saito S, Iovescu A, Baran A (1994) Colloids Surf A 90:89
Katsuura H, Kawamura H, Manabe M, Maeda H (2001) Colloid Polym Sci 279:858
Katsuura H, Kawamura H, Manabe M, Kawasaki H, Maeda H (2002) Colloid Polym Sci 280:30
Saito S (1955) Kolloid Z 143:66
Rodenas E, Sierra ML (1996) Langmuir 12:1600
Fendler JH, Fendler EJ (1975) Catalysis in micellar and macromolecular systems. Academic, New York
Hansson P, Almgren M (1994) Langmuir 10:2115
Fundin J, Hansson P, Brown W, Lidegran I (1997) Macromolecules 30:1118
Lindman B, Thalberg K (1993) In: Goddard ED, Ananthapadmanabhan KP (eds) Interactions of surfactants with polymers and proteins. CRC, Boca Raton, pp 203–276
Lin SY, Lin YY, Chen EM, Hsu CT, Kwan CC (1999) Langmuir 15:4370
Finch JA, Smith GW (1973) J Colloid Interface Sci 45:81
Gaillon L, Leliève J, Gaboriaud R (1999) J Colloid Interface Sci 213:287–297
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Anghel, D.F., Saito, S., Iovescu, A., Bãran, A., Stîngã, G., Neamtu, C. (2003). Counterion effect of cationic surfactants on the interaction with poly(acrylic acid). In: Anghel, D.F. (eds) Aqueous Polymer — Cosolute Systems. Progress in Colloid and Polymer Science, vol 122. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-36114-6_3
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DOI: https://doi.org/10.1007/3-540-36114-6_3
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