Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (5): 473-478.DOI: 10.6023/A17020068 Previous Articles     Next Articles

Article

聚芳撑乙炔微孔骨架材料的合成及其气体吸附

徐佳伟a, 张崇b, 王迅昶a, 蒋加兴b, 汪锋a   

  1. a. 武汉工程大学化工与制药学院 武汉 430073;
    b. 陕西师范大学材料科学与工程学院 西安 710062
  • 收稿日期:2017-02-17 出版日期:2017-05-15 发布日期:2017-04-12
  • 通讯作者: 汪锋, 蒋加兴 E-mail:psfwang@wit.edu.cn;jiaxing@snnu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No.51103111)和教育部新世纪优秀人才支持计划(No.NCET-12-0714)资助.

Synthesis and Gas Sorption Properties of Microporous Poly(arylene ethynylene) Frameworks

Xu Jiaweia, Zhang Chongb, Wang Xunchanga, Jiang Jiaxingb, Wang Fenga   

  1. a. School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073;
    b. School of Materials Science and Engineering, Shaanxi Normal University, Xi'an 710062
  • Received:2017-02-17 Online:2017-05-15 Published:2017-04-12
  • Contact: 10.6023/A17020068 E-mail:psfwang@wit.edu.cn;jiaxing@snnu.edu.cn
  • Supported by:

    Project supported by the the Natural Science Foundation of China (No. 51103111) and the Education Ministry of China (No. NCET-12-0714).

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