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侧氰基芳醚硅芳炔树脂的制备与表征

马满平 戴妮娉 李传 刘晓天 袁荞龙 黄发荣

马满平, 戴妮娉, 李传, 等. 侧氰基芳醚硅芳炔树脂的制备与表征[J]. 复合材料学报, 2020, 37(12): 3035-3042. doi: 10.13801/j.cnki.fhclxb.20200507.003
引用本文: 马满平, 戴妮娉, 李传, 等. 侧氰基芳醚硅芳炔树脂的制备与表征[J]. 复合材料学报, 2020, 37(12): 3035-3042. doi: 10.13801/j.cnki.fhclxb.20200507.003
MA Manping, DAI Niping, LI Chuan, et al. Preparation and characterization of a silicon-containing arylacetylene resin with cyano groups[J]. Acta Materiae Compositae Sinica, 2020, 37(12): 3035-3042. doi: 10.13801/j.cnki.fhclxb.20200507.003
Citation: MA Manping, DAI Niping, LI Chuan, et al. Preparation and characterization of a silicon-containing arylacetylene resin with cyano groups[J]. Acta Materiae Compositae Sinica, 2020, 37(12): 3035-3042. doi: 10.13801/j.cnki.fhclxb.20200507.003

侧氰基芳醚硅芳炔树脂的制备与表征

doi: 10.13801/j.cnki.fhclxb.20200507.003
基金项目: 中央高校基本科研业务费专项资金(50321042017001)
详细信息
    通讯作者:

    黄发荣,博士,教授,博士生导师,研究方向为特种聚合物及复合材料 E-mail:fhuanglab@ecust.edu.cn

  • 中图分类号: TB332;TQ323

Preparation and characterization of a silicon-containing arylacetylene resin with cyano groups

  • 摘要: 在无水三氟甲磺酸锌催化下通过2,6-双-(4-乙炔基苯氧基)-苯腈和二甲基二氯硅烷室温反应制备了侧氰基芳醚硅芳炔树脂(CNSA);采用1H-NMR、FTIR、DSC、TGA等分析测试技术表征了CNSA的结构与性能。结果显示,CNSA树脂具有好的溶解性和宽的加工窗口,可在较低温度(<200℃)下发生固化反应;树脂固化物具有好的热性能,在50~400℃之间无玻璃化转变,在N2中质量损失5%的温度Td5达512℃;T300碳纤维平纹布/CNSA(CF/CNSA)复合材料的室温弯曲强度达383.8 MPa,弯曲模量为62.9 GPa。

     

  • 图  1  2,6-双-(4-乙炔基苯氧基)-苯腈(BEPBN)的合成

    Figure  1.  Synthesis of 2,6-bis(4-ethynylphenoxy) benzonitrile (BEPBN)

    BIPBN-2,6-bis(4-iodophenoxy)benzonitrile;BTEPBN-2,6-bis(4-((trimethylsilyl)ethynyl)phenoxy)benzonitrile

    图  2  侧氰基芳醚硅芳炔树脂(CNSA)的合成

    Figure  2.  Synthesis of silicon-containing arylacetylene resin with cyano groups (CNSA)

    图  3  CNSA树脂1H-NMR图谱

    Figure  3.  1H-NMR spectrum of CNSA resin

    图  4  CNSA树脂FTIR图谱

    Figure  4.  FTIR spectrum of CNSA resin

    图  5  CNSA树脂流变曲线

    Figure  5.  Rheological curve of CNSA resin (2℃·min−1)

    图  6  CNSA树脂的DSC曲线(10℃·min−1)

    Figure  6.  DSC curve of CNSA resin(10℃·min−1)

    图  7  不同升温速率的CNSA树脂DSC曲线

    Figure  7.  DSC curves of CNSA resin at different heating rates

    图  8  CNSA树脂的ln(β/Tp2)、lnβ与1 000/Tp的关系

    Figure  8.  ln(β/Tp2) vs 1 000/Tp and lnβ vs 1 000/Tp plot of CNSA resin

    图  9  CNSA树脂不同温度下的FTIR图谱

    Figure  9.  FTIR spectra of CNSA resin at different temperatures

    图  10  CNSA树脂的热交联反应机制

    Figure  10.  Thermal cross-linking mechanisms of CNSA resin

    图  11  CNSA树脂浇铸体的DMA曲线

    Figure  11.  DMA curves of CNSA resin casting

    图  12  CNSA树脂固化物的热失重曲线(10℃·min−1, N2)

    Figure  12.  Thermogravinmetric curve of cured CNSA resin (10℃·min−1, N2)

    图  13  T300碳纤维平纹布/CNSA(CF/CNSA)复合材料弯曲性能

    Figure  13.  Flexural properties of T300 carbon fiber cloth/CNSA (CF/CNSA) composite

    表  1  CNSA室温溶解性

    Table  1.   Solubility of CNSA at room temperature

    SolventSolubilitySolventSolubility
    CHCl3 ++ DMSO ++
    THF ++ CH3CN +
    Toluene + EtOH
    Acetone ++ Hexane
    DMF ++ PE
    Notes: THF— Tetrahydrofuran; DMF—N, N-dimethylformamide; DMSO—Dimethyl sulfoxide; EtOH—Ethyl alcohol; PE—Petroleum ether.
    下载: 导出CSV

    表  2  不同升温速率下CNSA树脂的DSC分析数据

    Table  2.   DSC data of CNSA resin at different heating rates

    Heating rate/
    (℃·min−1)
    Ti/℃Tp/℃Tf/℃∆H/(J·g−1)
    5 168.6 225.7 265.4 351.3
    10 180.3 242.1 280.6 287.6
    15 194.9 251.6 287.5 249.9
    20 193.7 258.2 295.2 246.6
    Notes:Ti, Tp and Tf —Initial curing temperature, peak curing temperature and final curing temperature, respectively; ∆H—Exothermic enthalpy change of curing reactions.
    下载: 导出CSV

    表  3  CNSA树脂的固化反应的DSC分析数据

    Table  3.   DSC data for treatment of CNSA reaction

    β/(℃·min−1)Tp/K1 000/Tp/K−1ln(β/Tp2)lnβ
    5 498.85 2.005 −10.815 1.609
    10 515.21 1.941 −10.187 2.303
    15 524.76 1.906 −9.818 2.708
    20 531.32 1.882 −9.555 2.996
    Notes: β—Heating rate; Tp—Peak temperature of curing reactions.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2020-03-09
  • 录用日期:  2020-04-10
  • 网络出版日期:  2020-05-07
  • 刊出日期:  2020-12-15

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