Gelation via cationic chelation/crosslinking of acrylic‐acid‐based polymers

The gelation characteristics of acrylic‐acid‐based polymers in the presence of a range of cationic species, namely Ca²⁺, Mg²⁺ and Al³⁺, were investigated using in situ rheological measurements during photo‐polymerisation. Fourier transform mechanical spectroscopy was used to identify the gel point, using the Winter–Chambon criteria which allow the gel point to be pinpointed by establishing the sample spanning network and quantitatively determining stiffness, relaxation exponent, gel stiffness and fractal dimensions. The results showed that the gelation processes were greatly influenced by the type of cationic species that was used in the syntheses. At the gel point, more open network clusters were formed when Al³⁺ cations were used instead of Ca²⁺ cations or Mg²⁺ cations, all relating to chloride salts. Although the concentrations of the chelating/crosslinking aluminium species affected the kinetics of the gelation, the critical gel characteristics were hardly affected. Also the solubility of the chosen aluminium salt was shown to dictate the crosslinking rates and the properties of the critical gels. The extents of the reactions and the types of network formed at the gel point and beyond indicated that reactions between the Al³⁺ ions and COOH sites, from growing poly(acrylic acid) molecular chains, differ from those exhibited by Mg²⁺ and Ca²⁺ ions. All of the chelation/crosslinking reactions met the criteria of low mutation number (N_mu), such that in all cases N_mu ? 1. © 2019 Society of Chemical Industry