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Nitrogen-Containing Microporous Conjugated Polymers via Carbazole-Based Oxidative Coupling Polymerization: Preparation, Porosity, and Gas Uptake

机译:通过咔唑基氧化偶联聚合制得的含氮微孔共轭聚合物:制备,孔隙率和气体吸收

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摘要

Facile preparation of microporous conjugated polycarbazoles via carbazole-based oxidative coupling polymerization is reported. The process to form the polymer network has cost-effective advantages such as using a cheap catalyst, mild reaction conditions, and requiring a single monomer. Because no other functional groups such as halo groups, boric acid, and alkyne are required for coupling polymerization, properties derived from monomers are likely to be fully retained and structures of fi nal polymers are easier to characterize. A series of microporous conjugated polycarbazoles (CPOP-2-7) with permanent porosity are synthesized using versatile carbazolyl-bearing 2D and 3D conjugated core structures with non-planar rigid conformation as building units. The Brunauer-Emmett-Teller specifi c surface area values for these porous materials vary between 510 and 1430 m 2 g ?1. The dominant pore sizes of the polymers based on the different building blocks are located between 0.59 and 0.66 nm. Gas (H 2 and CO 2) adsorption isotherms show that CPOP-7 exhibits the best uptake capacity for hydrogen (1.51 wt% at 1.0 bar and 77 K) and carbon dioxide (13.2 wt% at 1.0 bar and 273 K) among the obtained polymers. Furthermore, its high CH 4 /N 2 and CO 2 /N 2 adsorption selectivity gives polymer CPOP-7 potential application in gas separation.
机译:据报道,通过咔唑基的氧化偶联聚合可以容易地制备微孔共轭聚咔唑。形成聚合物网络的方法具有成本效益高的优点,例如使用便宜的催化剂,温和的反应条件以及需要单一单体。由于偶联聚合不需要其他官能团,例如卤素,硼酸和炔烃,因此衍生自单体的特性很可能会完全保留,最终聚合物的结构更容易表征。以具有非平面刚性构象的多功能含咔唑基的2D和3D共轭核心结构为构建单元,合成了具有永久孔隙度的一系列微孔共轭聚咔唑(CPOP-2-7)。这些多孔材料的Brunauer-Emmett-Teller比表面积值在510和1430 m 2 g?1之间变化。基于不同结构单元的聚合物的主要孔尺寸位于0.59至0.66nm之间。气体(H 2和CO 2)的吸附等温线表明,在获得的氢中,CPOP-7表现出对氢气(1.0 bar和77 K下为1.51 wt%)和二氧化碳(1.0 bar和273 K下为13.2 wt%)的最佳吸收能力​​。聚合物。此外,其高的CH 4 / N 2和CO 2 / N 2吸附选择性使聚合物CPOP-7在气体分离中具有潜在的应用前景。

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