Aggregates of Isotactic Poly(methacrylic acid) Chains in Aqueous CsCl Solutions: a Static and Dynamic Light...

Properties of isotactic polymethacrylic acid, iPMA, chains were studied at 25°C in aqueous solutions at various CsCl concentrations, c(s) (= 0.05-0.20 M), in dependence on degree of neutralization of the polyion's carboxyl groups, α(N), using static, SLS, and dynamic light scattering, DLS, measurements. It was demonstrated that iPMA chains with α(N) somewhat above the solubility limit of iPMA in aqueous solutions (in the present case at α(N) ≈ 0.27) are strongly aggregated. The size of the aggregates increases with increasing c(s), whereas the shape parameter, ρ, is approximately constant (ρ ≈ 0.6), irrespective of c(s). The low ρ value suggests that the aggregates have characteristics of microgel particles with a dense core surrounded by a less dense corona. The diffusion of iPMA chains was investigated also at higher α(N), up to α(N) = 1. The polyion slow mode arising from electrostatic interactions between charged chains was observed for α(N) exceeding the value 0.27 even at the highest c(s) (= 0.20 M). The diffusion coefficients for the show mode were nearly independent of α(N) and cs at the studied polymer concentration.