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含乙烯基全氟聚醚-b-聚硅氧烷制备及其在硅橡胶中的性能

吕宁宁 冯裕智 文敬滨 温萍 路明霄 唐旭东

吕宁宁, 冯裕智, 文敬滨, 等. 含乙烯基全氟聚醚-b-聚硅氧烷制备及其在硅橡胶中的性能[J]. 复合材料学报, 2024, 42(0): 1-9.
引用本文: 吕宁宁, 冯裕智, 文敬滨, 等. 含乙烯基全氟聚醚-b-聚硅氧烷制备及其在硅橡胶中的性能[J]. 复合材料学报, 2024, 42(0): 1-9.
LV Ningning, FENG Yuzhi, WEN Jingbin, et al. Preparation of vinyl-containing perfluoropolyether-b-polysiloxane and its properties in silicone rubber[J]. Acta Materiae Compositae Sinica.
Citation: LV Ningning, FENG Yuzhi, WEN Jingbin, et al. Preparation of vinyl-containing perfluoropolyether-b-polysiloxane and its properties in silicone rubber[J]. Acta Materiae Compositae Sinica.

含乙烯基全氟聚醚-b-聚硅氧烷制备及其在硅橡胶中的性能

详细信息
    通讯作者:

    唐旭东,博士,教授,博士生导师,研究方向为高分子复合材料 E-mail: tangxd@tust.edu.cn

  • 中图分类号: TQ333.93; TB332

Preparation of vinyl-containing perfluoropolyether-b-polysiloxane and its properties in silicone rubber

  • 摘要: 耐溶剂性能差是制约硅橡胶发展与应用的重要因素之一,氟改性是解决该问题的有效手段之一。通过叔丁醇钾引发环硅氧烷阴离子开环制备了多乙烯基聚硅氧烷(Vi-PSi),与全氟聚醚硅氧烷反应制备含乙烯基全氟聚醚-b-聚硅氧烷嵌段共聚物(PFPE-b-PMVS),采用FT IR、1H NMR确定了其结构,并研究了PFPE-b-PMVS对甲基乙烯基硅橡胶(MVQ)力学性能、硫化性能、耐溶剂性能和热稳定性的影响。结果表明,随着PFPE-b-PMVS含量的增加,高温硫化交联后,改性MVQ的拉伸强度先增加后降低,当PFPE-b-PMVS添加量为2%时,拉伸强度和断裂伸长率可达11.38 MPa和396%;焦烧时间(t10)和正硫化时间(t90)随着PFPE-b-PMVS的增加而降低;耐溶剂性能随PFPE-b-PMVS添加量的增加吸附量降低,当PFPE-b-PMVS添加量为20%时,在对二甲苯溶剂中,吸附溶剂比未改性MVQ降低83.22%;热失重10%温度随PFPE-b-PMVS用量增加而降低。

     

  • 图  1  硅醇封端Vi-PSi(a)、全氟聚醚硅氧烷(b)和PFPE-b-PMVS(c)的FTIR谱图

    Figure  1.  FTIR spectra of Silanol-sealed Vi-PSi (a), Per-fluoropolyether siloxane (b), and PFPE-b-PMVS (c)

    图  2  全氟聚醚硅氧烷(a)和PFPE-b-PMVS(b)的1H NMR谱图

    Figure  2.  1H NMR spectra of Perfluoropolyether siloxane(a) and PFPE-b-PMVS(b)

    图  3  改性MVQ的拉伸性能和硬度

    (a) MVQ(I);(b) MVQ(II);(c) MVQ(III);(d)改性MVQ的硬度

    Figure  3.  The tensile properties and hardness of modified MVQ

    (a) MVQ(I); (b) MVQ(II); (c) MVQ(III); (d) Hardness of modified MVQ

    图  4  改性MVQ的耐溶剂性能

    (a)乙醇;(b)丙酮;(c)对二甲苯;(d)10#航空液压油

    Figure  4.  Solvent resistance of modified MVQ

    (a) Ethyl alcohol; (b) Acetone; (c) Para-xylene; (d) 10# Aviation hydraulic oil

    图  5  改性MVQ的体积变化

    Figure  5.  Volume change of modified MVQ

    图  6  改性MVQ的高温拉伸性能

    Figure  6.  The high temperature tensile properties of modified MVQ

    图  7  改性MVQ的DSC曲线

    Figure  7.  DSC curve of modified MVQ

    图  8  改性剂PFPE-b-PMVS的TGA和DTG曲线(a)和改性MVQ的TGA曲线(b)

    Figure  8.  TGA and DTG curves (a) of PFPE-b-PMVS and TGA curves (b) of modified MVQ

    图  9  改性MVQ的XPS曲线

    Figure  9.  DSC curve of modified MVQ

    图  10  MVQ(III-2%)的EDS图谱

    Figure  10.  EDS spectrum of MVQ (III-2%)

    表  1  改性硅橡胶(MVQ)的配方表

    Table  1.   Formula table of modified methyl vinyl silicone rubber (MVQ)

    Sample IV/g I/g II/g III/g
    MVQ 161.5 0 0 0
    MVQ(I-1%) 161.5 1 0 0
    MVQ(I-2%) 161.5 2 0 0
    MVQ(I-3%) 161.5 3 0 0
    MVQ(II-1%) 161.5 0 1 0
    MVQ(II-2%) 161.5 0 2 0
    MVQ(II-3%) 161.5 0 3 0
    MVQ(III-1%) 161.5 0 0 1
    MVQ(III-2%) 161.5 0 0 2
    MVQ(III-3%) 161.5 0 0 3
    MVQ(III-4%) 161.5 0 0 4
    MVQ(III-10%) 161.5 0 0 10
    MVQ(III-20%) 161.5 0 0 20
    Notes: IV—mixed silicone rubber, I - vinyl silicone oil, II—Perfluoropolyether allyl ether(PFPE-Ally) and III—Vinyl-containing perfluoropolyether-b-polysiloxane block copolymer (PFPE-b-PMVS).
    下载: 导出CSV

    表  2  改性MVQ的硫化性能

    Table  2.   The vulcanization properties of modified MVQ

    Sample t10/s t90/s ML/
    (dN·m)
    MH/
    (dN·m)
    (MH-ML)/
    (dN·m)
    MVQ 120 1207 1.02 27.78 26.76
    MVQ(I-1%) 88 1056 0.86 27.02 26.16
    MVQ(I-2%) 79 916 0.72 27.13 26.41
    MVQ(I-3%) 52 797 0.67 27.35 26.68
    MVQ(II-1%) 67 645 0.97 26.34 25.37
    MVQ(II-2%) 63 666 0.89 26.25 25.36
    MVQ(II-3%) 60 645 0.81 26.07 25.26
    MVQ(III-1%) 83 690 0.92 27.13 26.21
    MVQ(III-2%) 80 643 0.88 27.08 26.2
    MVQ(III-3%) 76 638 0.83 27.15 26.32
    MVQ(III-4%) 72 597 0.78 26.87 26.09
    MVQ
    (III-10%)
    68 544 1.19 29.69 28.5
    MVQ
    (III-20%)
    62 505 1.27 29.36 28.09
    Notes: MH and ML are the maximum and minimum torque values, re-spectively;t10 for scorching time and t90 for positive vulcanization time.
    下载: 导出CSV
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  • 收稿日期:  2024-03-18
  • 修回日期:  2024-05-20
  • 录用日期:  2024-05-25
  • 网络出版日期:  2024-06-17

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