Adsorption of Polycomplexes at Solution/Air Interface

The effect of complex formation of polyacids (polyacrylic (PAAc) and polymethacrylic (PMAAc)) with polyacrylamide (PAA) on their surface properties at solution/air interface has been studied by surface tension, electric conductivity and potentiometric measurements at 293±0.2 K. The relaxation time and surface activity of polycomplexes were calculated from kinetic data on the surface tension. It was found that during complex formation the relaxation time of a surface layer has a maximum and the surface activity of macromolecules is increased. Also the standard free energy of adsorption for PAA and polyacid-PAA polycomplexes were calculated. They are equal DadsG° 293 = - 19.1±0.1 kJ/base-mol. for PAA, DadsG° 293 = -21.2±0.1 kJ/basemol. for PMAAc-PAA polycomplex and DadsG° 293 = -23.0±0.1 kJ/base-mol. for PAAc-PAA polycomplex (calculation per base-mole of PAA monomer link). It is shown that the surface activity and ability to decrease of the water surface tension is less for PMAAc-PAA than for PAAc-PAA. Such anomalous behaviour of PMAAc-PAA polycomplex probably is caused by an excessive strengthening of inner- and intermolecular hydrophobic interactions in macromolecules of PMAAc- PAA polycomplexes due to the presence of α-methyl groups in PMAAc macromolecules. Because of the rebuilding of macromolecule segments of complex by polarity at the interface is becoming a difficult one.