Polyelectrolyte complex formation between poly(diallyldimethyl-ammonium chloride) and copolymers of acrylamide and sodium-acrylate

The interaction between oppositely charged polyelectrolytes, in this study poly(diallyldimethylammonium chloride) (PDADMAC) and copolymers of acrylamide and sodium-acrylate differing in their chain length and charge density parameter (xi) was investigated in relation to the molar charge ratio of anionic to cationic charges (n(-)/n(+)). The molecular weights of the polyelectrolytes used were 2.9.10(5) g/mol for PDADMAC and for the Polyacrylamide copolymers 14.10(6) g/mol as well as 5.10(5) g/mol obtained by ultrasonic degradation of the high molecular weight copolymers. The charge density parameters of the polyanions used (xi(PR)) varied between 0.14 and 0.64. Complexation between PDADMAC and high molecular weight polyanions leads mainly to macroscopic phase separation whereas the degraded polyanions and PDADMAC formed soluble complexes as well as stable dispersions, if charge excess was available. Precipitates and dispersions were characterized by several methods such as element analysis, thermogravimetry, pyrolysis-GC/MS, PEL titration, zeta-potential measurements, determination of turbidity, particle size measurements and determination of carbon content (TOC). All precipitated complexes include about 20% water and are of 1:1 stoichiometry concerning ionic binding. Investigations of dispersions confirm 1:1 stoichiometry of complex particles stabilized by excess polyelectrolyte and soluble complexes. It was also found that the particle size can be varied via the charge density parameter of the polyanions used in the range of negative charge excess.