The characterisation of polymer-solute and solvent-solute interactions

Abstract

Solvent-solute interactions have been characterised by investigating the effect a solvent or polymer has on the wavelength at maximum absorption of a solvatochromic dye. This allowed the solvent or polymer to be characterised in terms of hydrogen bond basicity, β1, hydrogen bond acidity, α1 and dipolarity π1. Inverse gas chromatography (IGC) has also been used to characterise the polymer-solute interactions; specific retention volumes Vg, for a set of solutes (or probes) were obtained on various polymeric phases, and the logVg values regressed against the solute descriptors in a multiple linear solvation equation, logVg = c + rR2 + sπH2 + aσαH2 + bσβH2 + 1 logL16 The solute descriptors denoted by subscript 2 are R2 the excess molar refraction, π2 the solute dipolarity/ polarisability; σβH2 and σαH2 are the solute hydrogen bond basicity and acidity respectively. L16 the partition coefficient of the solute on hexadecane at 298K and it is a measure of dispersion interaction. The constants r, s, a, b and 1 are the characteristic properties of the polymer complimentary to the solute descriptors. Solvatochromic parameters have been determined for pure solvents and polymers including polystyrene (PS), polyvinylmethylether (PVME), a blend of PS and PVME, polyethylene glycol, polyester polyols and polyether polyols. IGC has been used to characterize PS, PVME, a blend of PS and PVME, polyacrylic acid (PAA), polyethylene oxide (PEO), a complex formed from PEO and PAA, and polyethyleneglycol. Literature data on retention volumes have also been analysed by the application of the linear solvation equation

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