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基于微流控技术的阻燃微胶囊的制备及其改性环氧树脂的性能与阻燃机制

陆亦洲 耿海春 沈金荣 方园

陆亦洲, 耿海春, 沈金荣, 等. 基于微流控技术的阻燃微胶囊的制备及其改性环氧树脂的性能与阻燃机制[J]. 复合材料学报, 2022, 40(0): 1-12
引用本文: 陆亦洲, 耿海春, 沈金荣, 等. 基于微流控技术的阻燃微胶囊的制备及其改性环氧树脂的性能与阻燃机制[J]. 复合材料学报, 2022, 40(0): 1-12
Yizhou LU, Haichun GENG, Jinrong SHEN, Yuan FANG. Preparation of flame retardant microcapsules based on microfluidic technology and properties and flame-retardant mechanism of modified epoxy resin[J]. Acta Materiae Compositae Sinica.
Citation: Yizhou LU, Haichun GENG, Jinrong SHEN, Yuan FANG. Preparation of flame retardant microcapsules based on microfluidic technology and properties and flame-retardant mechanism of modified epoxy resin[J]. Acta Materiae Compositae Sinica.

基于微流控技术的阻燃微胶囊的制备及其改性环氧树脂的性能与阻燃机制

基金项目: 江苏省自然科学基金—面上项目 (BK20201361);
详细信息
    通讯作者:

    方 园,博士,副研究员,硕士生导师,研究方向为复合材料结构劣化机理、阻燃及性能提升 E-mail: yuanfang@njtech.edu.cn

  • 中图分类号: (TB332)

Preparation of flame retardant microcapsules based on microfluidic technology and properties and flame-retardant mechanism of modified epoxy resin

Funds: Natural Science Foundation of Jiangsu Province -- General Project(BK20201361)
  • 摘要: 为了进一步提高环氧树脂的阻燃性能,采用微流控技术制备了以乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)为壳,高效磷-氮阻燃剂(FR-PN)为芯材的FR-PN@ETPTA阻燃微胶囊,并将其运用于环氧树脂(EP)中;对比了FR-PN/EP、FR-PN@ETPTA/EP的热稳定性、阻燃性能和力学性能;探讨了FR-PN@ETPTA阻燃微胶囊对EP的燃烧性能和热降解行为的影响,揭示了FR-PN@ETPTA阻燃微胶囊的阻燃机制。试验结果表明:FR-PN@ETPTA阻燃微胶囊能够改善EP的阻燃性能,当阻燃微胶囊添加量为10wt%时,树脂的LOI值增加至37.3%,UL-94等级达到V-0级。环氧树脂中添加FR-PN阻燃剂或FR-PN@ETPTA阻燃微胶囊会降低树脂的拉伸性能和弯曲性能,但加入阻燃微胶囊试件的拉伸性能和弯曲性能优于加入阻燃剂的试件,且添加10wt%阻燃微胶囊后,树脂的冲击强度比纯EP增加了39%。研究表明,阻燃微胶囊改性环氧树脂的阻燃机制是气相阻燃与凝聚相阻燃相结合。

     

  • 图  1  高效磷-氮阻燃剂@乙氧基化三羟甲基丙烷三丙烯酸酯(FR-PN@ETPTA)阻燃微胶囊的制备过程示意图

    Figure  1.  Illustration of the scheme for producing phosphorus-nitrogen flame retardant@ethoxylated trimethylpropane triacrylate (FR-PN@ETPTA) flame retardant microcapsules

    图  2  FR-PN@ETPTA阻燃微胶囊的SEM图

    Figure  2.  SEM images of FR-PN@ETPTA flame retardant microcapsules

    图  3  FR-PN@ETPTA阻燃微胶囊粒径分布图

    Figure  3.  Particle size distribution of FR-PN@ETPTA flame retardant microcapsules

    图  4  环氧树脂样品的热重分析曲线

    Figure  4.  Thermogravimetric analysis curve of epoxy resins specimens

    图  5  环氧树脂样品HRR曲线和THR曲线

    Figure  5.  The heat release rate and total heat release curves of epoxy resins specimens

    图  6  环氧树脂样品的TSR曲线、CO生成量曲线和CO2生成量曲线

    Figure  6.  The curve of TSR, CO production and CO2 production of epoxy resin samples

    图  7  环氧树脂样品的热重-红外联用分析曲线

    Figure  7.  Thermogravimetric-infrared analysis curves of epoxy resin specimens

    图  8  环氧树脂样品锥形量热测试后炭层图

    Figure  8.  Carbon layer figure of epoxy resin specimens after conical calorimetry test

    图  9  环氧树脂样品燃烧测试前的SEM图

    Figure  9.  SEM images of epoxy resin specimens before combustion test

    图  10  环氧树脂样品炭层的SEM图

    Figure  10.  SEM images of carbon layer of epoxy resin specimens

    图  11  环氧树脂样品炭层的XRD谱图

    Figure  11.  XRD spectra of carbon layer of epoxy resin specimens

    图  12  阻燃微胶囊在环氧树脂中的阻燃机制

    Figure  12.  The flame-retardant mechanism of flame retardant microcapsules in epoxy resins

    图  13  环氧树脂样品的拉伸性能和弯曲性能

    Figure  13.  The tensile and bending properties of epoxy resin specimens

    图  14  环氧树脂试件的冲击性能

    Figure  14.  The impact properties of epoxy resin specimens

    表  1  阻燃环氧树脂的配方

    Table  1.   Formulation of flame retardant epoxy resin

    SpecimenEP/wt%FR-PN/
    wt%
    FR-PN@
    ETPTA/
    wt%
    EP 100 -- --
    FR-PN-1/EP 100 6 --
    FR-PN-2/EP 100 8 --
    FR-PN-3/EP 100 10 --
    FR-PN-4/EP 100 12 --
    FR-PN@ETPTA-1/EP 100 -- 6
    FR-PN@ETPTA -2/EP 100 -- 8
    FR-PN@ETPTA -3/EP 100 -- 10
    FR-PN@ETPTA -4/EP 100 -- 12
    下载: 导出CSV

    表  2  环氧树脂样品的热重分析数据

    Table  2.   Thermogravimetric analysis data of epoxy resins specimens

    SpecimenT5%/℃T10%/℃T50%/℃Tmax/℃W700℃/%
    EP 278 307 366 353 18.4
    FR-PN-3/EP 140 166 398 390 19.8
    FR-PN@ETPTA-3/EP 146 261 403 393 24.8
    Note: T5%, T10% and T50% represent the temperature when the sample mass loss rate is 5%, 10% and 50%, respectively; Tmax represents the temperature when the thermal decomposition rate is the maximum; W700℃ represents the residual weight of the sample at 700℃.
    下载: 导出CSV

    表  3  阻燃环氧树脂的LOI和UL-94数据

    Table  3.   LOI and UL-94 data of flame retardant epoxy resin

    SpecimenLOIUL-94
    tf/sDrippingRating
    EP 21% >250 Yes N.R.
    FR-PN-1/EP 23.5% >250 No N.R.
    FR-PN-2/EP 25.3% >250 No N.R.
    FR-PN-3/EP 33.7% 32.5 No V-0
    FR-PN-4/EP 38.8% 28.8 No V-0
    FR-PN@ETPTA-1/EP 23.5% >250 No N.R.
    FR-PN@ETPTA-2/EP 30.6% 82 No V-1
    FR-PN@ETPTA-3/EP 37.3% 26.8 No V-0
    FR-PN@ETPTA-4/EP 39.6% 21.1 No V-0
    Note: tf represents the total flame burning time of a group of 5 specimens.
    下载: 导出CSV

    表  4  环氧树脂样品的锥形量热数据

    Table  4.   Data from cone calorimetry of epoxy resins specimens

    SpecimenPHRR/(kW·m−2)THR/(MJ·m−2)TSR/(m2·m−2)COY/(kg·kg−1)CO2Y/(kg·kg−1)TTI/sav-EHC/(MJ·kg−1)
    EP 1492.0 123.4 2084.5 0.28 3.8 37 32.5
    FR-PN-3/EP 596.7 93.8 2959.5 0.32 0.9 40 26.7
    FR-PN@ETPTA-3/EP 554.5 86.9 2616.6 0.30 0.8 41 24.3
    Note: PHRR-Peak heat release rate; THR-Total heat release; TSR-Total smoke rate; COY-Creation quantity of CO; CO2−Creation quantity of CO2; TTI-Time to ignition; av-EHC-Mean effective heat of combustion.
    下载: 导出CSV
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  • 收稿日期:  2022-04-18
  • 录用日期:  2022-06-03
  • 修回日期:  2022-05-17
  • 网络出版日期:  2022-06-15

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