Evolution of composition, molar mass, and conductivity during the free radical copolymerization of polyelectrolytes

Despite their importance in biological and technological contexts, copolymeric polyelectrolytes (or "copolyelectrolytes") continue to present challenges to theorists and experimentalists. The first results of a unified approach to the kinetics and mechanisms of copolyelectrolyte synthesis and the physical characteristics of the resulting polymers are presented. The free radical copolymerization of 4-vinylbenzenesulfonic acid sodium salt and acrylamide was monitored using automatic continuous online monitoring of polymerization reactions (ACOMP), from which the average bivariate composition and mass distributions were determined. Composition drift was related to the evolution of conductivity. In some cases bimodal populations of copolyelectrolyte and homopolymeric poly(acrylamide) resulted, i.e., blends of copolyelectrolyte and neutral homopolymer. The end-product scattering behavior depended on whether the end-product was bimodal or not, as demonstrated using automatic continuous mixing (ACM) in conjunction with light scattering and viscosity. Negative light-scattering third virial coefficients were found for bimodal end-products. This combined approach may allow connecting the synthesis kinetics to the resulting "trivariate" distribution of composition, molar mass, and linear charge density, which in turn controls the properties of end-product solutions, such as chain conformations, interparticle interactions, viscosity, interactions with colloids and other polymers, phase separation, etc. Unified results may allow testing and improvement of existing polyelectrolyte theories, development of new quantitative physicochemical models, provide advanced characterization methods, set the stage for studying more complex copolyelectrolytes, such as hydrophobically modified ones, and provide tools for ultimately controlling and tailoring the synthesis and properties of copolyelectrolytes.