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Dioxolane-Based Perfluoropolymers with Superior Membrane Gas Separation Properties
Macromolecules ( IF 5.1 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1021/acs.macromol.8b00273
Milad Yavari 1 , Minfeng Fang 2 , Hien Nguyen 1 , Timothy C. Merkel 3 , Haiqing Lin 1 , Yoshiyuki Okamoto 2
Affiliation  

Glassy perfluoropolymers have become an exciting materials platform for membrane gas separation as they define the upper bounds for some gas separations, such as He/H2, He/CH4, and N2/CH4. However, due to the difficulty in synthesis, only a few glassy perfluoropolymers are commercially available, including Teflon AF and Hyflon AD derived from dioxoles and Cytop derived from dihydrofuran. In this study, two perfluoropolymers based on dioxolanes, poly(perfluoro-2-methylene-1,3-dioxolane) (poly(PFMD)) and poly(perfluoro-2-methylene-4-methyl-1,3-dioxolane) (poly(PFMMD)), were synthesized by radical polymerization and characterized thoroughly for physical properties such as glass transition temperature (Tg), d-spacing between polymer chains, and fractional free volume (FFV). The gas permeability and solubility were determined at 35 °C for a series of pure gases in these perfluorodioxolanes and compared with the commercial perfluoropolymers. Poly(PFMD) and poly(PFMMD) exhibit separation properties of He/H2, He/CH4, H2/CH4, H2/CO2, and N2/CH4 near or above the upper bounds in Robeson’s plots, and superior to the commercial perfluoropolymers, despite their similar Tg and FFV. The underlying reasons for the superior gas separation properties in these dioxolane-based perfluoropolymers are discussed.

中文翻译:

具有优异的膜气分离性能的基于二氧戊环的全氟聚合物

玻璃态全氟聚合物已经成为膜气体分离的令人兴奋的材料平台,因为它们定义了某些气体分离的上限,例如He / H 2,He / CH 4和N 2 / CH 4。然而,由于合成上的困难,只有几种玻璃状全氟聚合物是可商购的,包括衍生自二氧杂环戊二烯的Teflon AF和Hyflon AD以及衍生自二氢呋喃的Cytop。在这项研究中,基于二氧戊环的两种全氟聚合物,聚(全氟-2-亚甲基-1,3-二氧戊环)(poly(PFMD))和聚(全氟-2-亚甲基-4-甲基-1,3-二氧戊环)(聚(PFMMD)),是通过自由基聚合反应合成的,并针对诸如玻璃化转变温度(T g),聚合物链之间的d-间距和分数自由体积(FFV)。在这些全氟二氧戊环中的一系列纯净气体在35 ° C下测定了气体渗透性和溶解度,并与市售全氟聚合物进行了比较。聚(PFMD)和聚(PFMMD)在Robeson图的上限附近或上方显示He / H 2,He / CH 4,H 2 / CH 4,H 2 / CO 2和N 2 / CH 4的分离特性,尽管它们的T g相近,但仍优于市售的全氟聚合物和FFV。讨论了在这些基于二氧戊环的全氟聚合物中优异的气体分离性能的根本原因。
更新日期:2018-03-19
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