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磷杂菲-厚朴酚基环氧低聚物的合成及其固化树脂阻燃性能

谢煜彬 胡国梁 张笑晴 雷彩红

谢煜彬, 胡国梁, 张笑晴, 等. 磷杂菲-厚朴酚基环氧低聚物的合成及其固化树脂阻燃性能[J]. 复合材料学报, 2024, 42(0): 1-14.
引用本文: 谢煜彬, 胡国梁, 张笑晴, 等. 磷杂菲-厚朴酚基环氧低聚物的合成及其固化树脂阻燃性能[J]. 复合材料学报, 2024, 42(0): 1-14.
XIE Yubin, HU Guoliang, ZHANG Xiaoqing, et al. Synthesis and flame-retardant properties of the epoxy resin based on phenanthroline and magnolol[J]. Acta Materiae Compositae Sinica.
Citation: XIE Yubin, HU Guoliang, ZHANG Xiaoqing, et al. Synthesis and flame-retardant properties of the epoxy resin based on phenanthroline and magnolol[J]. Acta Materiae Compositae Sinica.

磷杂菲-厚朴酚基环氧低聚物的合成及其固化树脂阻燃性能

基金项目: 国家自然科学基金面上项目(No.52073065)
详细信息
    通讯作者:

    张笑晴,博士,副教授,硕士生导师,研究方向为阻燃添加剂、阻燃高分子材料;新型生物基材料;复合材料界面设计及性能调控 E-mail: zhangxq@gdut.edu.cn

  • 中图分类号: TQ322; TB332

Synthesis and flame-retardant properties of the epoxy resin based on phenanthroline and magnolol

Funds: National Natural Science Foundation of China (No.52073065)
  • 摘要: 商用环氧树脂主要由不可再生的石油基原料制得,且存在易燃、离火不自熄的问题,限制了它在电子电气和轨道交通等领域的广泛应用。因此,以生物质化合物厚朴酚、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物 (DOPO)和环氧氯丙烷为原料,合成了一种磷杂菲-厚朴酚基环氧低聚物(ED-0.5),并以4,4'-二氨基二苯基甲烷(DDM)为环氧固化剂,制备高阻燃效率的环氧固化树脂(ED-0.5/DDM)。通过FTIR、NMR表征了其化学结构,利用DSC和TGA研究了环氧固化树脂的固化动力学和热稳定性,采用极限氧指数、垂直燃烧、锥形量热仪探究了环氧固化树脂的阻燃性能,通过TG-FTIR 和SEM分别对固化物热解气相组成和燃烧后残炭形貌结构进行了分析,探究其阻燃机制。结果表明,ED-0.5/DDM树脂热稳定性和热机械性能均优于传统双酚A环氧树脂,固化反应活化能略高。ED-0.5/DDM环氧固化树脂极限氧指数(LOI)可达到52.5%,UL-94测试达到V-0等级,热释放速率峰值和总热释放量分别降低 70.9%和58.2%,残炭增加1565.2%。ED-0.5/DDM环氧固化树脂可通过捕获猝灭自由基,产生大量不燃气体,形成致密炭层,发挥气相和凝聚相协同阻燃作用。

     

  • 图  1  磷杂菲-厚朴酚基环氧低聚物(ED-0.5)合成路线

    Figure  1.  Synthesis route of epoxy oligomer with Magnolol and phosphaphenanthrene (ED-0.5)

    图  2  DOPO-M,E-DBP 和 ED-0.5 在不同波数范围内的红外谱图;(a) 4000-500 cm−1,(b) 1700- 1400 cm−1 和(c) 1400-600 cm−1

    Figure  2.  FTIR spectra of DOPO-M, E-DBP and ED-0.5 at various wavenumber ranges: (a) 4000-500 cm−1 , (b) 1700-1400 cm−1 , and (c) 1400-600 cm−1,(b) 1700-1400 cm−1 , and (c) 1400-600 cm−1

    图  3  ED-0.5(a)核磁共振氢谱(b)核磁共振磷谱

    Figure  3.  ED-0.5(a)1H-NMR spectrum (b)31P-NMR spectrum

    图  4  (a) DGEBA/DDM 和 ED-0.5/DDM在10 K·min−1 的 DSC 曲线;(b) DGEBA/DDM 和(c) ED-0.5/DDM 在不同升温速率下的 DSC 曲线

    Figure  4.  DSC curves of DGEBA/DDM and ED-0.5/DDM at 10 K·min−1 (a); DSC curves of (b) DGEBA/DDM and (c) ED-0.5/DDM at different heating rates

    图  5  (a) DGEBA/DDM 和 ED-0.5/DDM体系固化树脂的DSC曲线;(b) DMA 测试中 DGEBA/DDM和ED-0.5 DDM体系固化树脂的储能模量和Tanδ随着温度的变化图

    Figure  5.  (a) DSC curves of DGEBA/DDM and ED-0.5/DDM system cured resins; (b) DMA spectra for the storage modulus and Tan δ against temperature of DGEBA/DDM and ED-0.5/DDM system cured resins.

    图  6  氮气氛围中 DGEBA/DDM 和 ED-0.5/DDM体系固化树脂的TGA(a)和DTG 曲线(b)

    Figure  6.  TGA (a) and DTG (b) curves of DGEBA/DDM and ED-0.5/DDM system cured resins (N2 atmosphere)

    图  7  UL-94 测试的数码照片;(a)DGEBA/DDM,(b)ED-0.5/DDM

    Figure  7.  Digital photographs of UL-94: (a) DGEBA/DDM, (b) ED-0.5/DDM

    图  8  在45%氧气浓度的条件下(a) DGEBA/DDM,(g) ED-0.5/DDM的LOI测试数码照片

    Figure  8.  Digital photographs of LOI test at 45% oxygen atmosphere: (a) DGEBA/DDM, (b) ED-0.5/DDM

    图  9  锥形量热测试的 DGEBA/DDM 和 ED-0.5/DDM固化树脂的HRR(a),THR(b),和RCY(c) 随时间的变化曲线

    Figure  9.  HRR (a), THR (b), and RCY (c) versus time curves form CC tests for cured DGEBA/DDM and ED-0.5/DDM

    图  10  DGEBA/DDM(a)和 ED-0.5/DDM(b)的碎片产物的实时红外谱图

    Figure  10.  Real-time FTIR spectra of volatile products for DGEBA/DDM (a) and ED-0.5/DDM (b)

    图  11  残炭的数码照片;(a)DGEBA/DDM,(b)ED-0.5/DDM,

    Figure  11.  Digital photographs of the residual char: (a) DGEBA/DDM and (b) ED-0.5/DDM

    图  12  (a) E51-DDM 残炭的 SEM 图像;(b) ED-0.5/DDM残炭外层的 SEM 图像(c) ED-0.5/DDM残炭内层的 SEM 图像

    Figure  12.  SEM images of char for DGEBA/DDM (a), SEM image of residual carbon in the outer layer of ED- 0.5/DDM and residual carbon in the inner layer of ED-0.5/DDM(c)

    图  13  DGEBA/DDM和ED-0.5/DDM固化树脂残炭的红外谱图

    Figure  13.  FTIR spectra of char for DGEBA/DDM and ED-0.5/DDM cured resins

    表  1  环氧固化树脂的组成

    Table  1.   Formulations of flame-retardant epoxy thermoset

    Sample Components /wt% Phosphorus/
    wt%
    Gel
    content/%
    Resin DDM
    DGEBA/DDM 79.8 20.2 - 99.4
    ED-0.5/DDM 90.2 9.8 3.1 97.6
    Notes:DGEBA-Bisphenol A epoxy resin; DDM-4,4 '-diaminodiphenylmethane; Phosphorus-Theoretical content calculated according to the phosphorus content of the resin; Gel content-insoluble gel fraction as a result of inter-molecule cross-linking formation.
    下载: 导出CSV

    表  2  关于ED-0.5的1H-NMR和环氧值滴定的数据

    Table  2.   The date of H-NMR spectrum and epoxy value titration about ED-0.5.

    Sample D(——)P(——)
    (1H-NMR)
    Epoxy value titration
    Average
    quality/g
    Average
    volume/mL
    Average epoxy
    value /(mol·100g−1
    Average molecular
    weight /(g·mol−1)
    D (——)P(——)
    (Calculate)
    DGEBA - 0.41 21.97±0.1 0.536±0.002 373.1±2.6 0.10±0.1
    ED-0.5 0.52±0.1 0.60 12.90±0.1 0.215±0.001 930.2±4.3 0.51±0.1
    Notes:D(——)P(——)(1H-NMR)-average degree of polymerization measured by 1H-NMR; D(——)P(——) (Calculate)-average degree of polymerization calculated by epoxy titration.
    下载: 导出CSV

    表  3  环氧固化树脂的非等温固化动力学参数

    Table  3.   Non-isothermal curing kinetics parameters of the cured resins

    Sample Peak Temperature (TP)/(K·min−1) Ec(K)/
    (kJ·mol−1)
    Ec (O)/
    (kJ·mol−1)
    Gel Content/%
    5 10 15 20 25
    DGEBA/DDM 420.7 438.9 450.1 458.2 466.5 50.7 55.2 99.4
    ED-0.5/DDM 397.2 412.2 422.2 427.8 436.9 52.8 56.8 97.6
    Notes: Ec(K)-activation energy of reaction calculated by Kissinger equation; Ec (O)-activation energy of reaction calculated by Ozawa equation.
    下载: 导出CSV

    表  4  DGEBA/DDM和ED-0.5/DDM体系固化树脂的热分析数据

    Table  4.   Thermal analysis data of DGEBA/DDM and ED-0.5/DDM system cured resins

    Sample DGEBA/DDM ED-0.5/DDM
    Tg /℃ DSC 150.6 167.5
    DMA 167.1 185.6
    Storage modulus at 30℃/MPa Value 850.4 2072.5
    Increase - +143.7%
    Storage modulus at Tg-DMA +30 K/MPa 11.44 153.47
    Content of Biphenyl structure/% - 44.8
    Content of benzene ring/% 52.4 52.3
    ve × 103/(mol·m−3) 0.98 12.59
    Thermal decomposition temperature /℃ Td5% 367.3 396.2
    The temperature of the maximum thermal decomposition rate /℃ Tmax1 385.1 415.8
    Tmax2 - 483.6
    Char yield at 700℃/% Value 20.2 41.2
    Note: Tg-glass-transition temperature; ve -Crosslinking density.
    下载: 导出CSV

    表  5  DGEBA/DDM和ED-0.5/DDM固化树脂阻燃性能参数

    Table  5.   Flame-retardant property of DGEBA/DDM and ED-0.5/DDM cured resins.

    SampleUL-94LOI/%
    t1/st2/sDrippingRating
    DGEBA/DDM124+-YESNO Rating26.0
    ED-0.5/DDM0.80.8NOV-052.5
    Notes: t1- Average combustion times after the first applications of the flame; t2 - Average combustion times after the second applications of the flame: LOI-Limiting Oxygen Index.
    下载: 导出CSV

    表  6  DGEBA/DDM 和 ED-0.5/DDM固化树脂的锥形量热测试的数据

    Table  6.   Cone calorimetric data of the DGEBA/DDM and the ED-0.5/DDM cured resins.

    Sample DGEBA/DDM ED-0.5/DDM Max-relative value
    TTI/s 46 29
    pHRR/(kW·m−2) 1629.4 474.4 −70.9%
    THR/(MJ·m−2) 141.3 59.0 −58.2%
    Av-EHC/(MJ·kg) 32.7 25.9 −20.8%
    RCY/% 2.3 38.3 +1565.2%
    Notes: TTI-Time to ignition; pHRR-Peak heat release rate; THR-Total heat release; av-EHC-Average effective heat combustion; RCY-Residue char yield.
    下载: 导出CSV
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  • 文章访问数:  57
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出版历程
  • 收稿日期:  2024-01-19
  • 修回日期:  2024-03-20
  • 录用日期:  2024-03-28
  • 网络出版日期:  2024-04-29

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