Association of 4-n-Alkylbenzene Sulfonates with Hydrophobically Modified Poly (Diallyldimethylammonium) Chlorides

The association of poly (diallyldimethylammonium) chloride (PDDAC) hydrophobically modified with octyl, decyl, and dodecyl chlorides, with 4-n-alkylbenzene sulfonates, was studied in aqueous solution by ultrafiltration. Experimental data agree well with the Hill's equation for the association process. The association degree increases with the size of the sulfonate anion and decreases as the polyelectrolyte side chains length increases. This kind of polyelectrolyte is able to form hydrophobic microdomains lowering the availability of association sites due to a hypercoiling process. The association process was, in all cases, cooperative, having a maximum with the octyl derivative. The association degrees were significantly higher than those found with PDDAC itself. The standard free-energy contribution to the association process was between −19 and −20 kJ/mol of benzene sulfonate. These values are comparable with those recently found for a family of hydrophobic cationic polyelectrolytes at the water/chlorof...