聚芳撑乙炔微孔骨架材料的合成及其气体吸附

doi:10.6023/A17020068

摘要/Abstract

有机微孔聚合物（MOPs）在气体存储、吸附分离和非均相催化等领域具有优良性质而广受关注.近年来，聚芳撑乙炔微孔骨架材料的研究成为MOPs领域中的热点.分别以三（4-乙炔基）苯胺、甲基三（4-乙炔基苯基）硅烷、苯基三（4-乙炔基苯基）硅烷为基本构筑单元，通过端炔基氧化均聚的方法，制备了三种聚芳撑乙炔微孔骨架材料，研究了结构组成对制备聚合物孔道性能和气体吸附性能的影响.氮气吸附测试结果表明，聚合物的Brunauer-Emmett-Teller （BET）比表面积的范围在602~715 m²·g^-1.由于骨架中含有富氮基团（三苯胺）以及具有较大的比表面积，在1.13 bar/273 K条件下，聚三（4-乙炔基）苯胺（TEPA-MOP）的CO₂吸附能力为1.59 mmol·g^-1.此外，TEPA-MOP和聚苯基三（4-乙炔基苯基）硅烷（TEPP-MOP）具有优良的选择性吸附性能，对CO₂/N₂的选择性吸附分别是69.9和73.2.聚合物TEPA-MOP具有优异的CO₂/N₂的选择吸附性和适中的CO₂吸附能力，因此将在气体吸附与分离方面具有潜在的应用前景.

关键词: 有机微孔聚合物, 聚芳撑乙炔, 氧化均聚, 气体吸附, 分离

Microporous organic polymers (MOPs) have drawn much attention because of their potential applications such as gas storage, separation and heterogeneous catalysis. There is great interest in the design, synthesis and property evaluation of poly(arylene ethynylenes) (PAEs) with intrinsic microporosity. In addition to Sonogashira coupling reaction between terminal alkynes and halides, the oxidative dimerization of terminal alkynes is an alternating strategy for the buildup of the microporous PAE frameworks. In this paper, a series of MOPs were synthesized by the oxidative dimerization of terminal alkynes using triethynyl monomers such as tris(4-ethynylphenyl)amine, tris(4-ethynylphenyl)methylsilane and polytris(4-ethynylphenyl)phenylsilane. The resulting MOPs were characterized by FT-IR spectra, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) measurements. FT-IR spectra indicate the success of the homocoupling reaction for constructing the dialkyne-bridged polymer frameworks. These polymer frameworks exhibit high thermal stability with onset of decomposition temperature above 350 ℃ at 5% mass loss under nitrogen flow. PXRD and TEM measurements revealed that all the polymer frameworks are amorphous solid in nature. These dialkyne-bridged MOPs exhibit moderate surface areas ranging from 602 to 715 m²·g^-1. The incorporation of triphenylamine moieties into the polymer skeleton increases the number of electron donating basic nitrogen sites in the porous frameworks. Thus, the triphenylamine-based polymer polytris(4-ethynylphenyl)amine (TEPA-MOP) with the highest Brunauer-Emmett-Teller (BET) surface area shows the highest CO₂ uptake capacity of 1.59 mmol·g^-1 at 273 K and 1.13 bar among the resulting polymer frameworks. In addition, TEPA-MOP showed the highest H₂ adsorption up to 1.04 wt% at 1.13 bar and 77 K and polytris(4-ethynylphenyl)phenylsilane (TEPP-MOP) displayed the lowest H₂ adsorption of 0.64 wt% at the same conditions. As for separation of CO₂, both TEPA-MOP and TEPP-MOP exhibit relatively high CO₂-over-N₂ selectivities of 69.9 and 73.2 at 273 K, respectively. The above results show that TEPA-MOP might be the good candidate for the balanced CO₂ uptake capacity with impressive CO₂/N₂ selectivity among the microporous PAE frameworks.

Key words: microporous organic polymer, poly(arylene ethynylene), oxidative dimerization, gas adsorption, separation

引用此文

徐佳伟, 张崇, 王迅昶, 蒋加兴, 汪锋. 聚芳撑乙炔微孔骨架材料的合成及其气体吸附[J]. 化学学报, 2017, 75(5): 473-478.

Xu Jiawei, Zhang Chong, Wang Xunchang, Jiang Jiaxing, Wang Feng. Synthesis and Gas Sorption Properties of Microporous Poly(arylene ethynylene) Frameworks[J]. Acta Chim. Sinica, 2017, 75(5): 473-478.

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