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可膨胀石墨与甲基膦酸二甲酯协效阻燃聚甲基丙烯酸甲酯

徐文总 周耀成 边子唯 宣子怡 余世源

徐文总, 周耀成, 边子唯, 等. 可膨胀石墨与甲基膦酸二甲酯协效阻燃聚甲基丙烯酸甲酯[J]. 复合材料学报, 2024, 42(0): 1-12.
引用本文: 徐文总, 周耀成, 边子唯, 等. 可膨胀石墨与甲基膦酸二甲酯协效阻燃聚甲基丙烯酸甲酯[J]. 复合材料学报, 2024, 42(0): 1-12.
XU Wenzong, ZHOU Yaocheng, BIAN Ziwei, et al. Expandable graphite and dimethyl methylphosphonate synergistic flame retardant polymethyl methacrylate[J]. Acta Materiae Compositae Sinica.
Citation: XU Wenzong, ZHOU Yaocheng, BIAN Ziwei, et al. Expandable graphite and dimethyl methylphosphonate synergistic flame retardant polymethyl methacrylate[J]. Acta Materiae Compositae Sinica.

可膨胀石墨与甲基膦酸二甲酯协效阻燃聚甲基丙烯酸甲酯

基金项目: 安徽省自然科学联合基金(2208085 UM03,2308085 UM01);安徽省重点研发计划项目(202304 a05020023)
详细信息
    通讯作者:

    徐文总,博士,教授,硕士生导师,研究方向为阻燃高分子 E-mail: wenzongxu@ahjzu.edu.cn

  • 中图分类号: TB332

Expandable graphite and dimethyl methylphosphonate synergistic flame retardant polymethyl methacrylate

Funds: Natural Science Foundation of Anhui Province (Joint Foundation)(No.2208085 UM03,No.2308085 UM01); Anhui Province key research and development program(No.202304 a05020023)
  • 摘要: 聚甲基丙烯酸甲酯(PMMA)是一种用途广泛的高分子材料,为了改变其易燃烧的缺点,本文采用原位聚合法制备了一系列含甲基膦酸二甲酯(DMMP)和可膨胀石墨(EG)的聚甲基丙烯酸甲酯复合材料。通过极限氧指数、锥形量热仪和垂直燃烧测试研究了其阻燃性能,结果表明在添加10%复配阻燃剂,且DMMP与EG的比例为1∶1时, 复合材料5%DMMP-EG/PMMA的阻燃效果最好。样品通过UL-94 V-0评级,与未加阻燃剂的PMMA相比,其极限氧指数(LOI)从18%增加到27.4%。热释放速率峰值(pHRR)显著降低87%,总热释放量率(THR)降低33%。动态力学性能测试表明,5%DMMP-EG/PMMA的玻璃化转变温度和储能模量远远高于10%DMMP/PMMA,复配可膨胀石墨可以改善因磷酸酯加入导致的材料变软现象。最后, 通过TG-IR、不同温度下的红外光谱分析和残炭的拉曼光谱分析了复合材料的阻燃机制,良好的阻燃效果是由于DMMP与EG在气相与凝聚相两相中的协同阻燃作用。

     

  • 图  1  PMMA复合材料的极限氧指数测试(LOI)

    Figure  1.  limiting oxygen index (LOI) of PMMA composite materials

    图  2  PMMA复合材料:(a) HRR;(b) THR; (c) SPR; (d) TSP; (e) COP; (f) CO2P

    Figure  2.  Cone calorimetric analysis of PMMA samples:(a)HRR, (b)THR, (c)SPR, (d) TSP, (e)COP, (f)CO2P

    图  3  PMMA复合材料在垂直燃烧测试中的视频截图

    Figure  3.  Video screenshots of PMMA composites during the vertical combustion test

    图  4  PMMA复合材料的导热率

    Figure  4.  Thermal conductivity of PMMA composite

    图  5  PMMA复合材料的拉伸强度和断裂伸长率

    Figure  5.  The tensile strength、elongation at break of PMMA composites

    图  6  PMMA复合材料的冲击强度

    Figure  6.  The impact strength of PMMA composites

    图  7  PMMA复合材料:(a)储能模量曲线;(b)损耗模量曲线;(d)玻璃化转变温度曲线

    Figure  7.  PMMA composite material: (a)curve of storage with temperature; (b)curve of loss modulus with temperature; (c)curve of tan with temperature

    图  8  PMMA复合材料的:(a)TGA曲线和(b)DTG曲线

    Figure  8.  (a) TGA curves of PMMA composites: (b) DTG curves of PMMA composite

    图  9  PMMA复合材料的维卡软化温度

    Figure  9.  The vicat softening temperature of PMMA

    图  10  锥形量热测试后的残炭数码照片:(a)PMMA;(b) 10%DMMP/PMMA;(c) 5%DMMP-EG/PMMA;(d) 10%EG/PMMA

    Figure  10.  Digital pictures of residues after the cone calorimeter test:(a)PMMA; (b) 10%DMMP/PMMA; (c) 5%DMMP-EG/PMMA; (d) 10%EG/PMMA

    图  11  锥形量热测试后的残炭SEM图片:(a) 5%DMMP-EG/PMMA;(b) 10%EG/PMMA

    Figure  11.  SEM micrographs of char residue after calorimeter:(a) 5%DMMP-EG/PMMA; (b) 10%EG/PMMA

    图  12  锥形量热测试后焦渣的拉曼曲线:(a)5%DMMP-EG/PMMA;(b)10%EG/PMMA

    Figure  12.  Raman curves of char residue after cone calorimeter test: (a) 5%DMMP-EG/PMMA; (b)10%EG/PMMA

    图  13  PMMA复合材料的变温红外测试:(a)纯PMMA;(b) 5%DMMP-EG/PMMA

    Figure  13.  Infrared curves at different temperatures of PMMA composite: (a) PMMA; (b) 5%DMMP-EG/PMMA

    图  14  (a) 纯PMMA的3 D光谱图;(b) 5%DMMP-EG/PMMA的3 D光谱图;(c)最大分解速率下的热解产物光谱曲线;(d)PMMA4在820 cm−1和1020 cm−1处的吸收曲线

    Figure  14.  3 D images of thermal degradation products of PMMA (a) and 5%DMMP-EG/PMMA (b); (c) FTIR spectrum of gaseous pyrolysis products for PMMA and PMMA4 at the maximum evolution rate; (d) changes in absorbance of PMMA4 at 820 cm−1 and 1020 cm−1.

    图  15  EG/DMMP阻燃体系的阻燃机制

    Figure  15.  Flame retardant mechanism of EG/DMMP flame retardant system

    表  1  PMMA中阻燃剂的配方

    Table  1.   The formulation of all PMMA samples

    SamplePMMA10%DMMP/PMMA2%DMMP-EG/PMMA5%DMMP-EG/PMMA8%DMMP-EG/PMMA10%EG/PMMA
    MMA/wt%1009090909090
    DMMP/wt%0108520
    EG/wt%0025810
    Notes: PMMA- Polymethyl methacrylate; DMMP- Dimethyl methylphosphonate; EG- Expandable graphite
    下载: 导出CSV

    表  2  PMMA复合材料的阻燃性能具体数据

    Table  2.   Results of the Cone Calorimeter Test

    PMMA10%DMMP/PMMA5%DMMP-EG/PMMA10%EG/PMMA
    pHRR/(kW·m−2)103911441361561
    THR/(MJ·m−2)110867582
    pSPR/(m2·s−1)0.0360.0750.0100.002
    TSP/m22.665.911.450.22
    pCOPR/(g·s−1)0.00430.05540.00020.0002
    TTI/s20242820
    Av-EHC/(MJ·kg−1)31.823.426.627.8
    FPI/(m2·s·kW−1)0.0190.0210.2060.128
    FGI/(kW·m−2·s−1)9.6211.320.490.77
    Notes: pHRR-Peak value of heat release rate; THR-Total heat release; pSPR- Peak value of Smoke release rate; TSP- Total Smoke release rate; TTI-Time to ignition; Av-EHC-Average effective heat of combustion; FPI-Fire performance Index; FGI-Fire growth Index
    下载: 导出CSV

    表  3  PMMA复合材料的UL-94测试等级

    Table  3.   UL-94 test grade of PMMA composites

    SampleDrippingRating
    PMMANoNR
    10% DMMP/PMMANoNR
    5%DMMP-EG/PMMANoV-0
    10% EG/PMMANoNR
    下载: 导出CSV

    表  4  PMMA复合材料力学测试的具体数据

    Table  4.   Results of PMMA composite material mechanics test


    Impact Strength/
    (kJ·m−2)
    TensileStrength/
    MPa
    Elongationat break/% Hardness/
    HD
    Tg(DMA)/
    PMMA 14.43 51.24 2.71 90 136.3
    10%DMMP/PMMA 15.93 43.04 8.42 80 78.6
    2%DMMP-EG/PMMA 13.75 38.26 2.91 84
    5%DMMP-EG/PMMA 12.52 30.17 0.63 87 136.0
    8%DMMP-EG/PMMA 10.55 24.07 0.27 87
    10%EG/PMMA 9.78 14.48 0.18 88 136.0
    Notes: Tg-Glass transition temperature
    下载: 导出CSV

    表  5  PMMA复合材料的热重数据

    Table  5.   TGA data of the PMMA composites

    T5%/℃Tmax/℃Char Residue/%
    PMMA2723730.5%
    10%DMMP/PMMA2193910.7%
    5%DMMP-EG/PMMA2483826.3%
    10%EG/PMMA1613799.1%
    Notes: T5%-5% mass loss temperature ; Tmax-Maximum mass loss temperature.
    下载: 导出CSV
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  • 收稿日期:  2024-01-24
  • 修回日期:  2024-03-11
  • 录用日期:  2024-03-18
  • 网络出版日期:  2024-04-20

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