Improving chromatographic separation of polyolefins on porous graphitic carbon stationary phases: effects of adsorption promoting solvent and column length.

The chromatographic separation of complex polyolefins on porous graphitic carbon stationary phases is strongly influenced by the composition of the mobile phase. Of particular interest is the effect of the chemical structure of the adsorption promoting solvent as this component of the mobile phase determines the adsorption-desorption behavior of the polyolefin molecules. In a systematic study, alkyl alcohols and linear alkanes are used as adsorption promoting solvents and the effect of the molecules' carbon chain length on chromatographic resolution is investigated. As representative examples, solvent gradient interaction chromatography experiments on polypropylene stereoisomers and ethylene- co -1-octene copolymers are presented. In a further study, the effect of increasing chromatographic column length on the solvent gradient separation of ethylene- co -1-octene copolymers is investigated. In summary, it is shown that the polypropylene stereoisomers are retained in 1-octanol as well as in n -decane and n -dodecane, allowing for identification of the individual stereoisomers in complex blends. For ethylene- co -1-octene copolymers it is shown that separation improves with increasing carbon chain length of the adsorption promoting solvent. Maximum resolution is obtained when a column length of 300 mm is used with 1-dodecanol as the adsorption promoting solvent.