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论文类型：期刊论文

发表时间：2016-12-21

发表刊物：POLYMER CHEMISTRY

收录刊物：SCIE、EI、Scopus

卷号：7

期号：47

页面范围：7295-7303

ISSN号：1759-9954

摘要：Ultramicroporous semi-cycloaliphatic polyimides (sPIs) have been synthesized via solution polycondensation from bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride with 1,3,5,7-tetrakis(4-aminophenyl) adamantane and tetrakis(4-aminophenyl) methane, respectively. The well-controlled kinetic conditions result in a monodispersed pore size of 0.6 nm, located in the ultra-microporous region. Moreover, the introduction of cycloaliphatic moieties decreases the concentration of benzene rings, disrupts the p electron delocalization across the conjugated polyimide backbone and thereby effectively reduces the charge-transfer (CT) interactions between the neighboring polyimide segments. Thus, the improved porous environment gives rise to remarkably large adsorption capacities for both gases and organic vapors. For example, sPIs can uptake 23.75 wt% CO2 (273 K, 1 bar), 2.50 wt% H-2 (77 K, 1 bar), 176.0 wt% benzene and 85.1 wt% cyclohexane (298 K, P/P0 = 0.9), which are among the highest values for microporous organic polymers reported to date. In addition, it is interesting to observe that the adsorbed ratio of benzene to cyclohexane in the sPIs was tunable using various concentrations of cycloaliphatic and phenyl groups in the polyimide networks.