Subambient Temperature CO₂ and Light Gas Permeation Through Segmented Block Copolymers with Tailored Soft Phase

The permeation properties of a series of block copolymers based on poly(ethylene oxide)-ran-poly(propylene oxide) (PEO-ran-PPO) soft segments and monodisperse tetra-amide (T6T6T) hard segments have been studied. The polyether soft segment used in the current study differs from the commonly used pure poly(ethylene oxide) (PEO) soft segment by the fact that it contains 25 wt % randomly distributed poly(propylene oxide) (PPO). The presence of the methyl group of PPO suppresses crystallization of the soft segment and strongly improves the permeability of these materials, especially at subambient temperatures. In addition, the unique monodisperse character of the hard segment ensures a very well phase-separated morphology, resulting in a very pure soft phase. The soft segment length of these block copolymers was varied between 1000 and 10000 g/mol (62−89 wt %). High soft segment concentrations and flexibility were obtained resulting in high CO₂ permeabilities (up to 570 Barrer at 50 °C). Due to the random distribution of PPO in the predominantly PEO based soft segment crystallization of PEO was not observed at temperatures as low as −10 °C. CO₂ permeabilities exceeding 200 Barrer could be obtained at this low temperature. The CO₂/light gas selectivity in these materials is governed by the solubility selectivity and consequently only slightly lowered because of the introduction of PPO in the soft segment. Comparison with literature revealed that this block copolymer system has exceptionally high CO₂ permeabilities combined with reasonable CO₂/light gas selectivities. It is very interesting in CO₂ separation processes where subambient conditions are present (e.g., separation of CO₂ from natural gas), as at these low temperatures, one can take maximum advantage of the increased separation ability of the polymer materials while maintaining excellent transport characteristics.