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硫化DOPO衍生物阻燃环氧树脂的性能与阻燃机制

许志彦 侯泽明 叶小林 张玉鹏 侯学清 张道海 蔡晓东 周国永 谭芳 宝冬梅

许志彦, 侯泽明, 叶小林, 等. 硫化DOPO衍生物阻燃环氧树脂的性能与阻燃机制[J]. 复合材料学报, 2022, 39(10): 1-13 doi: 10.13801/j.cnki.fhclxb.20211228.001
引用本文: 许志彦, 侯泽明, 叶小林, 等. 硫化DOPO衍生物阻燃环氧树脂的性能与阻燃机制[J]. 复合材料学报, 2022, 39(10): 1-13 doi: 10.13801/j.cnki.fhclxb.20211228.001
Zhiyan XU, Zeming HOU, Xiaolin YE, Yupeng ZHANG, Xueqing HOU, Daohai ZHANG, Xiaodong CAI, Guoyong ZHOU, Fang TAN, Dongmei BAO. Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-13. doi: 10.13801/j.cnki.fhclxb.20211228.001
Citation: Zhiyan XU, Zeming HOU, Xiaolin YE, Yupeng ZHANG, Xueqing HOU, Daohai ZHANG, Xiaodong CAI, Guoyong ZHOU, Fang TAN, Dongmei BAO. Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-13. doi: 10.13801/j.cnki.fhclxb.20211228.001

硫化DOPO衍生物阻燃环氧树脂的性能与阻燃机制

doi: 10.13801/j.cnki.fhclxb.20211228.001
基金项目: 国家自然科学基金(51863004);贵州省省级科技计划项目(黔科合基础[2020]1Y211,黔科合基础-ZK[2021]一般248);贵州省2018年度高层次创新型人才培养-千层次人才项目
详细信息
    通讯作者:

    宝冬梅,博士,教授,硕士生导师,研究方向为聚合物基阻燃复合材料  E-mail:dongtian1314521@163.com

  • 中图分类号: TB332

Properties and flame retardant mechanism of sulfuretted DOPO derivative in epoxy resin

  • 摘要: 为了获得综合性能好的阻燃环氧树脂(EP)复合材料,将9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS)的衍生物应用于EP。首先,通过DOPS和马来酸酐(MAH)反应合成磷杂菲衍生物马来酸酐-9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(MAH-DOPS),采用FTIR、1H NMR、31P NMR等手段确定其结构;其次,分别将DOPS和MAH-DOPS添加到EP中,通过共混制备复合材料DOPS/EP和MAH-DOPS/EP;再次,对比了DOPS/EP和MAH-DOPS/EP的热稳定性、阻燃性能和力学性能;最后,探讨了MAH-DOPS对EP的燃烧性能和热降解行为的影响,深入分析其阻燃机制。通过对比发现:阻燃剂DOPS的初始分解温度(T5%,205.4℃)低于MAH-DOPS(235.2℃),在添加相同质量分数的阻燃剂时,复合材料DOPS/EP的热稳定性也低于MAH-DOPS/EP,与阻燃剂热稳定性一致;阻燃剂DOPS和MAH-DOPS均能改善EP的阻燃性能,MAH-DOPS/EP具有更优异的阻燃效果。当阻燃剂添加量为15wt%时,MAH-DOPS/EP和DOPS/EP的极限氧指数(LOI) 值分别为28.6%和29.1%,分别达到UL-94 V-0级和V-1级。力学测试结果表明,与EP相比,MAH-DOPS/EP的弯曲强度提高了45.8%,而DOPS/EP下降了62.5%,DOPS/EP体系的力学性能下降明显,几乎失去使用价值。锥形量热测试表明,复合材料MAH-DOPS/EP的平均热释放速率(av-HRR)和总热释放量(THR)显著降低。TG-IR结果表明,MAH-DOPS/EP热解产生的含磷自由基捕捉了H∙、O∙或HO∙等自由基,起到了自由基淬灭作用;SEM-EDS结果表明,MAH-DOPS/EP能够形成更加完整致密的炭层,炭层中P含量较高。研究表明,MAH-DOPS通过抑制火焰和成炭分别在气相和凝聚相发挥阻燃作用,并以气相阻燃机制为主。

     

  • 图  1  马来酸酐-9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(MAH-DOPS)的合成反应

    Figure  1.  Synthetic route of maleic anhydride-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (MAH-DOPS)

    THF—Tetrahydrofuran; TEA—Triethylamine

    图  2  DOPS和MAH-DOPS的红外图谱

    Figure  2.  FTIR spectra of DOPS and MAH-DOPS

    图  3  两种阻燃剂在氮气下的TG-DTG曲线

    Figure  3.  TG -DTG curves of two flame retardants in N2

    图  4  EP及其复合材料在氮气下的TG-DTG曲线

    Figure  4.  TG-DTG curves of EP and EP composites in N2

    图  5  EP和MAH-DOPS/EP在氮气下的TG (a)和DTG (b)曲线

    Figure  5.  TG (a) and DTG (b) curves of EP and MAH-DOPS/EP in N2

    图  6  EP和MAH-DOPS/EP的热释放速率(HRR) (a)和总热释放量(THR) (b)曲线

    Figure  6.  Heat release rate (a) and Total heat release (b) curves of EP and MAH-DOPS/EP

    图  7  EP和MAH-DOPS/EP的总烟释放量(TSR) (a)和CO生成量(COP) (b)曲线

    Figure  7.  Total smoke release (a) and CO production (b) curves of EP and MAH-DOPS/EP

    图  8  不同温度下EP、MAH-DOPS/EP裂解产物吸光度图((a)、(b)) ;EP、MAH-DOPS/EP三维TG-IR曲线((c)、(d))

    Figure  8.  The absorbance of pyrolysis products of EP, MAH-DOPS/EP at different temperatures ((a), (b)); 3D TG-IR curves of EP, MAH-DOPS/EP ((c), (d))

    图  9  锥量测试后残炭的数码照片:(a) EP;(b) 5wt%MAH-DOPS/EP;(c) 10wt%MAH-DOPS/EP; (d) 15wt%MAH-DOPS/EP

    Figure  9.  Digital photographs of char residues after cone calorimeter test: (a) EP; (b) 5wt%MAH-DOPS/EP; (c) 10wt%MAH-DOPS/EP; (d) 15wt%MAH-DOPS/EP

    图  10  锥量测试后残炭的SEM图

    Figure  10.  SEM images of char residues after cone calorimeter test

    图  11  阻燃剂对EP力学性能的影响

    Figure  11.  Influence of flame retardants on mechanical properties of EP

    表  1  阻燃环氧树脂的配方

    Table  1.   Formulation of flame retardant epoxy resin

    SampleComposition/g
    EPMTHPABDMAMAH-DOPSDOPS
    5wt%MAH-DOPS/EP1008519.79
    5wt%DOPS/EP1008519.79
    10wt%MAH-DOPS/EP10085120.67
    10wt%DOPS/EP10085120.67
    15wt%MAH-DOPS/EP10085132.82
    15wt%DOPS/EP10085132.82
    Notes: EP—Epoxy resin; MTHPA—Methyl tetrahydrophthalic anhydride; BDMA—N,N-dimethylbenzylamine; MAH-DOPS—Maleic anhydride-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide; DOPS—9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide.
    下载: 导出CSV

    表  2  两种阻燃剂在氮气下的TG、DTG数据

    Table  2.   TG and DTG data of two flame retardants in N2

    SampleT5%/℃T10%/℃T50%/℃TP1/℃TP2/℃Rmax1Rmax2Char residue
    at 600℃/%
    DOPS205.4216.9341.6225.5381.50.310.833.57
    MAH-DOPS235.2248.7435.4245.1469.70.340.8615.81
    Notes: T5%—Temperature corresponding to weight loss 5% of material; T10%—Temperature corresponding to weight loss 10% of material; T50%—Temperature corresponding to weight loss 50% of material; TP—Temperature corresponding to maximum thermal degradation rate; Rmax—Maximum thermal degradation rate.
    下载: 导出CSV

    表  3  EP及其复合材料在氮气下的TG、DTG数据

    Table  3.   TG and DTG data of EP and EP composites in N2

    SampleT5%/℃T10%/℃T50%/℃TP1/℃TP2/℃Rmax1Rmax2Char residue at 600℃/%
    EP345.1369.7410.1407.61.617.22
    5wt%MAH-DOPS/EP271.2326.5400.8402.61.508.90
    10wt%MAH-DOPS/EP292.8342.8393.2395.11.5311.42
    10wt%DOPS/EP230.2276.5409.8308.1449.70.370.793.52
    15wt%MAH-DOPS/EP319.2357.1402.8392.51.4911.93
    下载: 导出CSV

    表  4  EP及其复合材料的LOI和UL-94数据

    Table  4.   LOI and UL-94 data of EP an EP composites

    SampleLOI/%UL-94
    t1/t2(s)DrippingRating
    EP19.5-/-NON.R.
    5wt%DOPS/EP26.2>50/>50NON.R.
    5wt%MAH-DOPS/EP24.919.21/15.08NOV-2
    10wt%DOPS/EP30.75.81/43.53NOV-2
    10wt%MAH-DOPS/EP27.115.37/13.42NOV-1
    15wt%DOPS/EP29.112.27/1.91NOV-1
    15wt%MAH-DOPS/EP28.65.01/4.45NOV-0
    Notes: LOI—Limiting oxygen index; t1/t2—First and second combustion time in UL-94 test; UL-94—Vertical combustion test; N.R.—No rating.
    下载: 导出CSV

    表  5  EP和MAH-DOPS/EP的锥形量热测试数据

    Table  5.   CONE data of EP and MAH-DOPS/EP

    SampleTTI/sav-HRR/
    (kW·m−2)
    PHRR/
    (kW·m−2)
    THR/
    (MJ·m−2)
    av-EHC/
    (MJ·kg−1)
    TSR/
    (m2·m−2)
    av-COY/
    (kg·kg−1)
    EP66218.88918.01155.5731.412251.690.21
    5wt%MAH-DOPS/EP55129.55697.8396.9828.312859.350.27
    10wt%MAH-DOPS/EP58132.37644.5481.4327.822873.670.33
    15wt%MAH-DOPS/EP52137.43603.6771.3728.753098.420.37
    Notes: TTI—Time to ignition; av-HRR—Average heat release rate; PHRR—Peak heat release rate; THR—Total heat release; av-EHC—Average effective heat of combustion; TSR—Total smoke release; av-COY—Average carbon monoxide yield.
    下载: 导出CSV

    表  6  MAH-DOPS/EP残炭的EDS数据

    Table  6.   EDS data of char residues of MAH-DOPS/EP

    SampleChar residueComposites
    C/wt%O/wt%P/wt%S/wt%P/wt%S/wt%
    5wt%MAH-DOPS/EP67.7024.177.061.070.470.48
    10wt%MAH-DOPS/EP64.4529.575.320.280.940.97
    15wt%MAH-DOPS/EP66.0129.184.010.811.411.46
    下载: 导出CSV

    表  7  EP和MAH-DOPS/EP的力学性能

    Table  7.   Mechanical properties of EP and MAH-DOPS/EP

    SampleBending strength/MPaBending modulus/MPaTensile strength/MPaNotched izod impact strengh/(kJ·m−2)
    EP96.472326.6875.193.11
    5wt%MAH-DOPS/EP125.333224.8352.392.94
    10wt%MAH-DOPS/EP140.664099.7047.562.89
    15wt%MAH-DOPS/EP116.463258.9730.632.67
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-10-11
  • 录用日期:  2021-12-10
  • 修回日期:  2021-12-02
  • 网络出版日期:  2021-12-28
  • 刊出日期:  2022-10-15

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