Polyelectrolyte complexes obtained by radical polymerization in the presence of chitosan

The radical polymerization of acrylic acid and sodium 4-styrenesulfonate in the presence of chitosan as a template gives insoluble products, identified as the polyelectrolyte complexes chitosan-poly(acrylic acid) and chitosan-poly(4-styrenesulfonate). Kinetic results do not permit to propose any mechanism in the first case, while suggest a ''pickup'' one in the second. The polyelectrolyte complexes have been characterized by FT-IR spectroscopy, X-ray diffractometry, optical and scanning electron microscopies, differential scanning calorimetry and thermogravimetric analysis. The results obtained indicate an ordered structure for the first complex, while the second one appears similar to that obtained by reacting the parent polymers. Therefore, the template polymerization technique appears advantageous only for the synthesis of the chitosan-poly(acrylic acid) complex. The thermal analysis shows that the complexes undergo two successive modifications on heating. FT-IR analysis demonstrates that the first process is an esterification between the hydroxyls of chitosan and the acidic groups of both daughter polymers; the second one appears to be an amidation of the chitosan ammonium groups only with the sulfonate groups.