化学学报 ›› 2015, Vol. 73 ›› Issue (6): 629-633.DOI: 10.6023/A15020091 上一篇    下一篇

所属专题: 共价有机多孔聚合物

研究论文

芴基共价三嗪骨架聚合物的室温合成和取代基效应研究

于森a, 徐雍捷a, 蒋加兴b, 任世杰a   

  1. a 四川大学高分子科学与工程学院 四川大学高分子材料工程国家重点实验室 成都 610065;
    b 陕西师范大学材料科学与工程学院 西安 710062
  • 收稿日期:2015-02-02 出版日期:2015-06-14 发布日期:2015-03-24
  • 通讯作者: 蒋加兴, 任世杰 E-mail:rensj@scu.edu.cn;jiaxing@snnu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No. 21404074)、教育部博士点基金(20130181120054)和高分子材料工程国家重点实验室自主课题(Sklpme2014-3-10)资助.

Room Temperature Synthesis and Substituent Effect Study of Fluorene-Based Covalent Triazine-Based Frameworks

Yu Sena, Xu Yongjiea, Jiang Jiaxingb, Ren Shijiea   

  1. a College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065;
    b School of Materials Science and Engineering, Shaanxi Normal University, Xi'an 710062
  • Received:2015-02-02 Online:2015-06-14 Published:2015-03-24
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21404074), the Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20130181120054) and the State Key Laboratory of Polymer Materials Engineering (Grant No. SKLPME2014-3-10).

高效合成和功能性基团的引入是当前有机微孔聚合物材料研究的热点. 采用强质子酸催化的腈基三聚环化反应, 室温合成制备了一系列带有不同取代基的芴基共价三嗪骨架聚合物(FCTF1~FCTF3), 系统研究了取代基的变化对所得材料光学性能、多孔性能及CO2吸附能力的影响. 其中乙基取代的聚合物FCTF2具有最高的BET比表面积(621 m2/g)和CO2吸附能力(1.8 mmol/g, 273 K/1.1 bar). 该研究有助于加深对有机微孔聚合物结构与性能关系的理解, 对该类材料的分子设计有借鉴意义.

关键词: 有机微孔聚合物, 芴, 共价三嗪骨架聚合物, 多孔性, CO2吸附

Efficient synthesis and the introduction of functional group are the focus of current research on microporous organic polymers (MOPs). In this report, a series of new covalent triazine-based framework polymers (CTFs) based on fluorene with different substituents (FCTF1~FCTF3) has been synthesized using trifluoromethanesulfonic acid (TFMS) catalyzed cyclotrimerization reactions at room temperature. The chemical structures of the polymers were confirmed by FTIR and elemental analysis. In the FTIR spectra, the nearly absence of peaks at around 2220 cm-1 along with the emergence of strong triazine absorption bands around 1500, 1360 and 800 cm-1 indicated qualitatively a high degree of polymerization. Thermogravimetric analysis (TGA) under nitrogen atmosphere revealed a high thermal stability with 5% weight loss at temperature up to 364 (FCTF1), 452 (FCTF2) and 238 ℃ (FCTF3). The solid UV-Vis spectra showed that the polymers could all absorb light from UV to visible light region. In the photoluminescence measurement, FCTF1~FCTF3 exhibited bright blue fluorescence with maximum emission wavelengths at 437 nm, 455 nm and 439 nm respectively. The specific surface areas of the polymers changed dramatically according to the substituent attached to the fluorine unit, with BET surface areas changing from nearly nil (FCTF3) to 621 m2/g (FCTF2) when the substituent changed from butyl to ethyl. Pore size distributions were calculated using nonlocal density functional theory (NL-DFT) and porous polymers FCTF1 and FCTF2 showed main pore sizes in the micropore region. CO2 adsorption capacities of the polymers were also measured and FCTF1 and FCTF2 showed high CO2 uptake of 1.7 and 1.8 mmol/g respectively at 273 K/1.1 bar. The isosteric heats of adsorption were calculated from the CO2 isotherms measured at 273 and 298 K. FCTF1 and FCTF2 showed adsorption heats of 26.4 and 22.7 kJ/mol respectively at the zero coverage, indicative strong binding affinity of the polymers with CO2. To the best of our knowledge, this is the first report on the substituent effect of fluorene-based CTFs and this research can probably enhance the understanding of the structure-property relationship of porous organic polymer materials.

Key words: microporous organic polymers, fluorene, covalent triazine-based frameworks, porosity, CO2 adsorption