The thermo-responsive phase behaviour of the sodium salt of poly(acrylic acid) (PAA) was studied when its counter-ion was exchanged for a series of metal cations (PAA–metal cation complexes). The thermo-responsivity of such PAA–metal cation complexes appeared greatest for divalent metal cations capable of interacting weakly with PAA carboxylates. The thermo-responsivity was correlated with the adsorption behaviour of PAA towards such cations and the hydration structure of the complexes. The effect of metal cations on the thermo-responsivity followed the Irving–Williams order of stability. The condition of such complexes allowing the generation of thermo-responsivity was discussed.
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