Bengtson Gisela, Neumann Silvio, Filiz Volkan
Helmholtz-Zentrum Geesthacht, Institute of Polymer Research, Max-Planck-Strasse 1, 21502 Geesthacht, Germany.
Membranes (Basel). 2017 Jun 5;7(2):28. doi: 10.3390/membranes7020028.
Until now, the leading polymer of intrinsic microporosity PIM-1 has become quite famous for its high membrane permeability for many gases in gas separation, linked, however, to a rather moderate selectivity. The combination with the hydrophilic and low permeable poly(ethylene glycol) (PEG) and poly(ethylene oxides) (PEO) should on the one hand reduce permeability, while on the other hand enhance selectivity, especially for the polar gas CO₂ by improving the hydrophilicity of the membranes. Four different paths to combine PIM-1 with PEG or poly(ethylene oxide) and poly(propylene oxide) (PPO) were studied: physically blending, quenching of polycondensation, synthesis of multiblock copolymers and synthesis of copolymers with PEO/PPO side chain. Blends and new, chemically linked polymers were successfully formed into free standing dense membranes and measured in single gas permeation of N₂, O₂, CO₂ and CH₄ by time lag method. As expected, permeability was lowered by any substantial addition of PEG/PEO/PPO regardless the manufacturing process and proportionally to the added amount. About 6 to 7 wt % of PEG/PEO/PPO added to PIM-1 halved permeability compared to PIM-1 membrane prepared under similar conditions. Consequently, selectivity from single gas measurements increased up to values of about 30 for CO₂/N₂ gas pair, a maximum of 18 for CO₂/CH₄ and 3.5 for O₂/N₂.
到目前为止,主要的固有微孔聚合物PIM-1因其在气体分离中对许多气体具有高膜渗透性而颇负盛名,然而,这与相对适中的选择性有关。与亲水性且低渗透性的聚乙二醇(PEG)和聚环氧乙烷(PEO)相结合,一方面应降低渗透性,另一方面应提高选择性,特别是对于极性气体CO₂,通过改善膜的亲水性来实现。研究了将PIM-1与PEG或聚环氧乙烷和聚环氧丙烷(PPO)相结合的四种不同途径:物理共混、缩聚淬灭、多嵌段共聚物的合成以及带有PEO/PPO侧链的共聚物的合成。共混物和新型化学连接聚合物成功制成独立的致密膜,并通过时间滞后法对N₂、O₂、CO₂和CH₄的单气体渗透进行了测量。正如预期的那样,无论制造工艺如何,添加任何大量的PEG/PEO/PPO都会降低渗透性,且与添加量成比例。与在类似条件下制备的PIM-1膜相比,向PIM-1中添加约6至7 wt%的PEG/PEO/PPO可使渗透性减半。因此,单气体测量的选择性对于CO₂/N₂气体对增加到约30,对于CO₂/CH₄最高为18,对于O₂/N₂为3.5。