Chemical composition separation of a propylene-ethylene random copolymer by high temperature solvent gradient interaction chromatography

•Chemical composition separations of a propylene-ethylene random copolymer and its TREF fractions were studied by high temperature SGIC.•HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution.•The retention volume of the component eluted in the gradient elution increased linearly with increasing ethylene content of the TREF fractions.•SGIC separation of the propylene-ethylene random copolymer is governed by adsorption-desorption processes of the ethylene units in the polymer chains.•2D HPLC shows that the 40 °C TREF fraction was rather broad in both molar mass and chemical composition distributions.

A propylene-ethylene random copolymer was fractionated by preparative temperature rising elution fractionation (TREF). The structural heterogeneity of the bulk sample and its TREF fractions was studied by high temperature liquid chromatography with a solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene. HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution. These components can only be detected after being separated and enriched by TREF followed by HPLC analysis. Chemical composition separations were achieved for TREF fractions with average ethylene contents between 2.1 and 22.0 mol%, showing that copolymers with higher ethylene contents were adsorbed stronger in the Hypercarb column and eluted later. All TREF fractions, except the 40 °C fraction, were relatively homogeneous in both molar mass and chemical composition. The 40 °C fraction was rather broad in both molar mass and chemical composition distributions. 2D HPLC showed that the molar masses of the components containing more ethylene units were getting lower for the 40 °C fraction. HPLC revealed and confirmed that co-crystallization influences the separation in TREF of the studied propylene-ethylene copolymer.