Molecular characterization of water-soluble,cationic polyelectrolytes

Poly{acrylamide-co-[2-(acryloyloxy)ethyltrimethylammonium chloride]} (1) , Poly{acrylamide-co-[2-(methacryloyloxy)ethyltrimethylammonium chloride]} (2) and Poly{acrylamide-co-[3-(acryloylamino)propyltrimethylammonium chloride]} (3) with cationic monomeric unit mole fractions of 8, 25, and 50 mol-%, and the corresponding homopolymers were characterized with respect to their molecular dimensions in 1 M sodium chloride solution at 25°C in the molecular weight range from 200000 to 16000000, using light-scattering and viscometric measurements. It was possible to establish correlations between molecular weight, intrinsic viscosity and radius of gyration. Whereas a steady increase in the exponents of the [η] vs. M- and 〈R²_G〉^0,5 vs. M-relationships can be observed with increasing charge density, there is an initial decrease in the values of the exponents for 2 and 3 , when 8 mol-% of the cationic monomer is inserted into poly-acrylamide. If the charge density is increased further, these values can also be seen to rise steadily. The findings are explained by the different structures in solution, which are formed by the copolymers and homopolymers investigated due to their chemical structure. The radii of gyration were calculated from the intrinsic viscosities with the aid of the Flory-Fox equation. However, neither the results obtained with the Flory-Fox constant Φ₀= 3,69. 10²⁴ mol^?1, nor those with the value of Φ₀= 2,10. 10²⁴ mol^?1 showed good agreement with the experimentally recorded data.