四苯基乙烯基共轭微孔聚合物的制备及其气体吸附  

Conjugated Microporous Polymers Based on Tetraphenylethylene for Gas Adsorption

作　　者：赵洋[1] 王笑颜[1] 张崇[1] 蒋加兴[1] 

机构地区：[1]陕西师范大学材料科学与工程学院,西安710062

出　　处：《化学学报》2015年第6期634-640,共7页Acta Chimica Sinica

基　　金：国家自然科学(青年)基金(No.21304055);中央高校基本科研业务费专项基金(No.GK201501002)的支持~~

摘　　要：共轭微孔聚合物由于其在气体吸附与分离、非均相催化和光电子等领域的巨大应用前景而广受关注.本文以四苯基乙烯为基本构筑单元,通过Sonogashira-Hagihara偶联反应制备了3种共轭微孔聚合物新材料,研究了结构组成和构建模块对制备聚合物孔性能和气体吸附性能的影响.氮气吸附测试结果表明,由1,1,2,2-四炔四苯基乙烯自聚合制备的TPE-CMP1具有较大的比表面积,为1096 m2·g-1.在1.13 bar/273 K条件下,TPE-CMP1的CO2吸附能力为2.36mmol·g-1;在1.13 bar/77.3 K条件下,TPE-CMP1对H2的吸附能力为1.35 wt%.另外,制备的共轭微孔聚合物展示出较高的CO2/N2选择性吸附值.由于这类多孔聚合物材料具有合成方法简单、优良的物理化学及热稳定性、高的比表面积和CO2吸附性能,因此将在气体吸附与分离方面具有潜在的应用前景.Conjugated microporous polymers(CMPs) are attracting increasing attention due to their potential applications in areas such as gas adsorption, separation, heterogeneous catalysis and photoelectron. A series of CMPs based on tetraphenylethylene has been synthesized via Pd-catalyzed Sonogashira-Hagihara coupling reaction. During polymerization, all of the polymer networks precipitated from solution as yellow powders that are totally insoluble in common organic solvents tested because of their highly crosslinked structures. Thermogravimetric analysis indicated that all of the polymer networks are thermally stable up to 400 in nitrogen atmosphere. Th℃ e high physicochemical and thermal stability could be attributed to the rigid nature of these aromatic polymers, composed solely of strong carbon-carbon and carbon-hydrogen bonds. The absence of the C≡H stretching peaked at around 3280 cm-1 and the C—Br stretching peaked at around 500 cm-1 in the FT-IR spectra for the polymer networks demonstrated that most of the ethynyl and bromine functional groups in the starting materials have been consumed by coupling reaction. Powder X-ray diffraction measurements revealed that all of the polymer networks are amorphous in nature. It was found that the homo-coupled polymer network of TPE-CMP1 from 1,1,2,2-tetrakis(4-ethynylphenyl)ethene shows the highest Brunauer-Emmet-Teller specific surface area up to 1096 m2·g-1among the resulting polymer networks. TPE-CMP1 exhibits a CO2 uptake ability of 2.36 mmol·g-1 at 1.13 bar and 273 K with a H2 uptake capacity of 1.35 wt% at 1.13 bar and 77.3 K. All of the polymer networks show high CO2/N2 selectivity around 30∶1 and high isosteric heat of adsorption for CO2 up to 27.6 k J·mol-1. Given the facile preparation strategy, the high physicochemical and thermal stability, the high surface area, and the outstanding CO2 sorption performances, these polymer networks are promising candidates for potential applications in post-combustion CO2 capture and sequestration technology.

关 键 词：共轭微孔聚合物 四苯基乙烯 Sonogashira-Hagihara偶联反应 比表面积 气体吸附 

分 类 号：TQ317[化学工程—高聚物工业] TQ424.3