Davletbaeva Ilsiya M, Zaripov Ilnaz I, Mazilnikov Alexander I, Davletbaev Ruslan S, Sharifullin Raphael R, Atlaskin Artem A, Sazanova Tatyana S, Vorotyntsev Ilya V
Department of Synthetic rubber, Kazan National Research Technological University, 68 K. Marx str., 420015 Kazan, Russia.
Department for Materials Science, Welding and Industrial Safety, Kazan National Research Technical University, n.a. A.N. Tupolev, 10 K. Marx str., 420111 Kazan, Russia.
Membranes (Basel). 2019 Mar 20;9(3):42. doi: 10.3390/membranes9030042.
Nowadays, block copolymers hold great promise for the design of novel membranes to be applied for the membrane gas separation. In this regard, microporous block copolymers based on a macroinitiator with an anionic nature, such as potassium-substituted block copolymers of propylene oxide and ethylene oxide (PPEG) and 2,4-toluene diisocyanate (TDI), were obtained and investigated as effective gas separation membranes. The key element of the macromolecular structure that determines the supramolecular organization of the studied polymers is the coplanar blocks of polyisocyanates with an acetal nature (O-polyisocyanate). In the present research, the influence of the content of peripheral polyoxyethylene (POE) blocks in PPEG on the supramolecular structure processes and gas transport characteristics of the obtained polymers based on PPEG and TDI was investigated. According to the study of polymers if the POE block content is 15 wt %, the polyoxypropylene segments are located in the internal cavity of voids formed by O-polyisocyanate blocks. When the POE block content is 30 wt %, the flexible chain component forms its own microphase outside the segregation zone of the rigid O-polyisocyanate blocks. The permeability for polar molecules, such as ammonia or hydrogen sulfide, significantly exceeds the permeability values obtained for non-polar molecules He, N₂ and СН₄. A relatively high permeability is also observed for carbon dioxide. At the same time, the content of POE blocks has a small effect on the permeability for all studied gases. The diffusion coefficient increases with an increase in the POE block content in PPEG for all studied gases.
如今，嵌段共聚物在设计用于膜气体分离的新型膜方面具有巨大潜力。在这方面，基于具有阴离子性质的大分子引发剂制备并研究了微孔嵌段共聚物，例如环氧丙烷和环氧乙烷的钾取代嵌段共聚物（PPEG）与2,4-甲苯二异氰酸酯（TDI），将其作为有效的气体分离膜。决定所研究聚合物超分子结构的大分子结构的关键要素是具有缩醛性质的聚异氰酸酯的共平面嵌段（O-聚异氰酸酯）。在本研究中，研究了PPEG中周边聚氧乙烯（POE）嵌段的含量对基于PPEG和TDI的所得聚合物的超分子结构过程和气体传输特性的影响。根据对聚合物的研究，如果POE嵌段含量为15 wt％，聚氧化丙烯链段位于由O-聚异氰酸酯嵌段形成的空隙的内腔中。当POE嵌段含量为30 wt％时，柔性链组分在刚性O-聚异氰酸酯嵌段的偏析区之外形成其自身的微相。对于极性分子，如氨或硫化氢，其渗透率明显超过非极性分子He、N₂和CH₄的渗透率值。对于二氧化碳也观察到相对较高的渗透率。同时，POE嵌段的含量对所有研究气体的渗透率影响较小。对于所有研究的气体，扩散系数随着PPEG中POE嵌段含量的增加而增加。
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