Separation of short-chain branched polyolefins by high-temperature gradient adsorption liquid chromatography

A new separation principle was recently introduced into the analytical characterization of polyolefins by researchers from the German Institute for Polymers in Darmstadt. It was demonstrated that polyolefins can be selectively separated via high-performance liquid chromatography on the basis of their adsorption/desorption behaviours at temperatures as high as 160 °C. A Hypercarb® column packed with porous graphite gave the best results. The mobile phase consisted of a mixture of 1-decanol and 1,2,4-trichlorobenzene. In this work, the same chromatographic system is applied to the separation of ethylene/alkene and ethylene/norbornene copolymers. It was found that the elution volumes of the samples correlate linearly with the average chemical composition of samples. The elution volume is indirectly proportional to the concentration of branches in the ethylene/alkene copolymer. Branching shortens the length of continuous methylene sequences of the polymer backbone, thus decreasing the probability of orientation of a methylene sequence in a flat conformation on the graphite surface, which enables the most intensive van der Waals interactions between the methylene backbone and the carbon surface. An opposite trend in the elution order has been found for ethylene/norbornene copolymers. The elution volume of the ethylene/norbornene copolymers increased with the concentration of norbornene. It indicates pronounced attractive interactions between graphite and the cyclic comonomer.