Polymer, Vol.41, No.24, 8587-8596, 2000
Evidence of ternary interaction parameters for polymer solutions in mixed solvents from headspace-gas chromatography
Partial vapor pressures of the volatiles have been measured for four solvent/precipitant/polymer systems at different temperatures. The high molecular weight compounds were polysulfone or polyethersulfone and the mixed solvent was either DMF/acetone or DMF/water. Systems containing the very powerful precipitant water exhibit a special phenomenon: Upon the addition of polymer to a mixed solvent of constant composition the partial vapor pressure of water increases by a factor of more than two before it falls to zero as the volume fraction of the polymer approaches unity. This particular situation cannot be modeled using binary interaction parameters only, in contrast to the results obtained with acetone as the precipitant. The present findings are used to discuss the necessity of ternary interaction parameters and possibilities for their calculation from known binary interaction parameters.
Keywords:ternary interaction parameters;headspace-gas chromatography;polyethersulfone and polysulfone