Influence of the Comonomer on the Dissociation of Some Alternating Maleic Acid Copolymers

Five alternating copolymers of maleic acid with N-vinylpyrrolidone, vinyl acetate, styrene, 2-vinylnaphthalene, and vinyl cyclohexane were used in order to study the influence of the comonomer on the polyelectrolyte behavior. The dissociation of the maleic acid copolymers was investigated by electrochemical methods in pure water and in the presence of supporting electrolytes. The conformational modifications during the dissociation were directly investigated by viscosimetry and fluorescence probing. The shape of the potentiometric and conductometric titration curves was influenced by the comonomer structure. In salt-free solution, only the first dissociation step was observed. The addition of univalent counterions permitted the evidencing of the second ionization step only for the copolymers with hydrophilic comonomers, but the addition of divalent counterions permitted the evidencing of the second ionization step for all five copolymers. The apparent dissociation constants increase with the increase of t...