Size-exclusion chromatography of poly(ethylene 2,6-naphthalate)

A solvent mixture of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and dichloroacetic acid (DCAA) is used to dissolve difficultly soluble poly(ethylene 2,6-naphthalate) (PEN). Solutions can be diluted and analyzed in a common size-exclusion chromatography (SEC) eluent, HFIP. The HFIP/DCAA mixture is better at dissolving PEN than either solvent individually and it is easier and safer to work with than phenolic and strongly acidic eluents. Dissolution temperatures between 50 and 60 °C are sufficiently low to minimize hydrolytic degradation of the polyester. PEN does not dissolve in the solvent mixture if the water concentration is greater than 0.76 wt%, and preferably the water content should be less than 0.13 wt% to eliminate minor prepeak artifacts. The procedure is suitable for PEN that is less than 48% crystalline, including prepolymers, oriented films and some solid-state polymerized materials. Highly crystalline polymers can be melt-quenched into a more amorphous state to render them soluble. The dilute solution conformational properties of PEN are compared to PET in HFIP, and molar mass–intrinsic viscosity scaling constants and unperturbed dimensions are calculated from SEC data.

► A mixture of HFIP and dichloroacetic acid dissolves poly(ethylene naphthalate).
► The dissolved polymer can be analyzed by SEC in HFIP.
► Dissolution and chromatographic conditions minimize hydrolytic degradation.
► Conformational parameters and unperturbed dimensions are calculated.