Ma Xiaohua, Lai Holden W H, Wang Yingge, Alhazmi Abdulrahman, Xia Yan, Pinnau Ingo
Functional Polymer Membranes Group, Advanced Membranes and Porous Materials Center, Division of Physical Science and Engineering, Chemical Engineering Program, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, KSA.
Department of Chemistry, Stanford University, Stanford, California 94305, United States.
ACS Macro Lett. 2020 May 19;9(5):680-685. doi: 10.1021/acsmacrolett.0c00135. Epub 2020 Apr 24.
We report the facile synthesis and study of two soluble microporous ladder polymers, CANAL-TBs, by combining catalytic arene-norbornene annulation (CANAL) and Tröger's base (TB) formation. The polymers were synthesized in two steps from commercially available chemicals in high yields. CANAL-TBs easily formed mechanically robust films, were thermally stable up to 440 °C, and exhibited very high Brunauer-Teller-Emmett surface areas of 900-1000 m g. The gas separation performance of the CANAL-TBs for the O/N pair is located between the 2008 and 2015 permeability/selectivity upper bounds. After 300 days of aging, CANAL-TBs still exhibited O permeability of 200-500 barrer with O/N selectivity of about 5. The polymer with more methyl substituents exhibited higher permeability and slightly larger intersegmental spacing as revealed by WAXS, presumably due to more frustrated chain packing. The facile synthesis, excellent mechanical properties, and promising air separation performance of the CANAL-TB polymers make them attractive membrane materials for various air separation applications, such as aircraft on-board nitrogen generation and oxygen enrichment for combustion.
我们报道了通过结合催化芳烃 - 降冰片烯环化反应（CANAL）和特罗格碱（TB）的形成，简便合成并研究了两种可溶性微孔梯形聚合物CANAL - TBs。这些聚合物由市售化学品分两步合成，产率很高。CANAL - TBs很容易形成机械坚固的薄膜，在高达440°C的温度下热稳定，并且具有900 - 1000 m²/g的非常高的布鲁诺尔 - 泰勒 - 埃米特表面积。CANAL - TBs对O₂/N₂气体对的分离性能介于2008年和2015年的渗透率/选择性上限之间。经过300天的老化后，CANAL - TBs仍表现出200 - 500巴每尔的O₂渗透率和约5的O₂/N₂选择性。如广角X射线散射（WAXS）所示，具有更多甲基取代基的聚合物表现出更高的渗透率和稍大的链段间距，这可能是由于链堆积更无序。CANAL - TB聚合物简便的合成方法、优异的机械性能和有前景的空气分离性能使其成为用于各种空气分离应用的有吸引力的膜材料，例如飞机机载制氮和燃烧用氧气富集。
