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低烟低热薄壁阻燃聚碳酸酯材料的制备与性能

江惠 刘杰 张璐 李三喜 唐涛 王松

江惠, 刘杰, 张璐, 等. 低烟低热薄壁阻燃聚碳酸酯材料的制备与性能[J]. 复合材料学报, 2024, 42(0): 1-11.
引用本文: 江惠, 刘杰, 张璐, 等. 低烟低热薄壁阻燃聚碳酸酯材料的制备与性能[J]. 复合材料学报, 2024, 42(0): 1-11.
JIANG Hui, LIU Jie, ZHANG Lu, et al. Preparation and Properties of thin-wall flame-retardant polycarbonate materials with low heat release and smoke[J]. Acta Materiae Compositae Sinica.
Citation: JIANG Hui, LIU Jie, ZHANG Lu, et al. Preparation and Properties of thin-wall flame-retardant polycarbonate materials with low heat release and smoke[J]. Acta Materiae Compositae Sinica.

低烟低热薄壁阻燃聚碳酸酯材料的制备与性能

基金项目: 国家自然科学基金(No. 51991353,51991350)
详细信息
    通讯作者:

    刘杰,博士,副研究员,研究方向为高分子阻燃材料、聚合物碳化反应研究 E-mail: liujie@ciac.ac.cn

    王松,博士,教授,研究方向为高分子材料、吸附材料研究 E-mail: wangsong@sut.edu.cn

  • 中图分类号: (TB332)

Preparation and Properties of thin-wall flame-retardant polycarbonate materials with low heat release and smoke

Funds: National Natural Science Foundation of China(No. 51991353,51991350)
  • 摘要: 兼具低烟低热和薄壁阻燃的无卤无氟聚碳酸酯(PC)的制备是该领域面临的一个挑战。以八甲基环四硅氧烷和硼酸为原料,通过缩聚反应制备了一种聚硼硅氧烷(PBS)阻燃剂,将其与硼酚醛树脂(LPR)复配制备了PBS-LPR/PC复合材料。结果表明,在PBS和LPR总添加量为10 wt%,质量比3∶1时,在PC中表现出最佳的协同阻燃效果,1.6 mm厚的PC样品能够通过UL-94垂直燃烧测试的V-0级别。与PC相比,该样品的峰值放热率(pHRR)、峰值产烟率(pSPR)、总热释放(THR)和总烟生成(TSP)分别降低了76%、64%、49%和65%。阻燃机制研究表明PBS和PC的交联成炭以及LPR的原位成炭是阻燃性能提高的主要原因。7.5%PBS-2.5%LPR/PC的缺口冲击强度是PC的2.3倍,材料表现出高韧的特性。

     

  • 图  1  聚硼硅氧烷(PBS)的合成路线

    Figure  1.  The synthesis route of polyborosiloxane (PBS)

    图  2  PC及其复合材料在氮气气氛下的TGA(a) 和DTG(b) 曲线

    Figure  2.  TGA (a) and DTG (b) curves of PC and its composites under nitrogen atmosphere

    图  3  锥形量热测试得到的PC及PBS-LPR/PC复合材料的热释放速率(a), 总热释放量(b), 烟释放速率(c),总生烟量曲线(d)

    Figure  3.  HRR(a), THR(b),SPR(c), TSP(d) curves of PC and PBS-LPR/PC composites obtained by cone calorimeter

    图  4  PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)复合材料锥形量热测试后残炭的数码照片,SEM照片和EDS分析;a,a1表示顶部和侧面残炭形貌,a2表示SEM照片

    Figure  4.  Morphologies、SEM images and EDS analysis of char residues from PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)composites of digital photos,SEM photos and EDS analysis after the cone calorimeter;a,a1 represent the top and side Morphologies,a2 indicates the SEM images

    图  5  PC复合材料残炭的EDS (a)和FTIR(b)谱图

    Figure  5.  EDS (a) and FTIR (b) spectra of the char residue for PC composites

    图  6  温度扫描流变法测定的 PC复合材料的复合黏度曲线(a)和360-400℃的局部放大图(b)

    Figure  6.  The plots for complex viscosities (a) and local magnification (b) at 360-400℃ for PC composites with by temperature-scanning rheology.

    图  7  PC及其复合材料主要降解产物的GC谱图

    Figure  7.  The GC spectrogram of PC and its composites mainly degraded products

    图  8  PBS-LPR/PC复合材料的阻燃机制示意图

    Figure  8.  Schematic illustration for the flame-retardant mechanism of PBS/LPR/PC composites

    图  9  PC和PBS-LPR/PC复合材料的缺口冲击强度

    Figure  9.  The notched impact strength of PC and PBS-LPR/PC composites

    图  10  PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)的缺口冲击淬断面的SEM照片

    Figure  10.  SEM images of notched impact cross section of PC(a), 10%LPR/PC(b), 2.5%PBS-7.5%LPR/PC(c), 5%PBS-5%LPR/PC(d), 7.5%PBS-2.5%LPR/PC(e), 10%PBS/PC(f)

    表  1  PBS-LPR/PC复合材料的组成

    Table  1.   Composition of PC and PBS-LPR/PC composites

    Samples PC /wt% PBS/wt% LPR /wt%
    PC 100.0 0.0 0.0
    10%LPR/PC 90.0 0.0 10.0
    2.5%PBS-7.5%LPR/PC 90.0 2.5 7.5
    5%PBS-5%LPR/PC 90.0 5.0 5.0
    7.5%PBS-2.5%LPR/PC 90.0 7.5 2.5
    10%PBS/PC 90.0 10.0 0
    Notes: LPR−Phenolic Resin; PC—Polycarbonate.
    下载: 导出CSV

    表  2  PC和PBS-LPR/PC复合材料在氮气气氛下的热稳定性数据

    Table  2.   Thermal stability data of PC and PBS-LPR/PC composites in nitrogen atmosphere

    Samples T5% /℃ Tmax /℃ Residue /%
    PC 476 521 24.0
    PBS 219 407 2.8
    LPR 148 573 69.7
    10%LPR/PC 452 517 28.3
    2.5%PBS-7.5%LPR/PC 445 515 27.5
    5%PBS-5%LPR/PC 408 516 26.4
    7.5%PBS-2.5%LPR/PC 378 512 24.3
    10%PBS/PC 394 512 24.4
    Notes: T5%−5% decomposition temperature in the first; Tmax−Maximum decomposition temperature
    下载: 导出CSV

    表  3  PC和PBS-LPR/PC复合材料的LOI和UL-94数据

    Table  3.   LOI and UL-94 data of PC and PBS-LPR/PC composites

    Sample LOI /% UL-94/ (1.6 mm)
    t1 /s t2 /s Dripping Rating
    PC 27.2 19.5±2.2 4.6±1.7 Yes V-2
    10%LPR/PC 28.8 18.6±16.5 0.9±0.2 Yes V-2
    2.5%PBS-7.5%LPR/PC 35.8 27.2±22.1 24.8±21.0 Yes NR
    5%PBS-5%LPR/PC 32.1 6.2±4.2 2.6±1.9 No V-0
    7.5%PBS-2.5%LPR/PC 36.1 4.9±2.7 1.7±1.1 No V-0
    10%PBS/PC 32.9 3.1±1.1 5.6±5.6 Yes V-2
    Notes: t1−Self-extinguishing time after the first ignition;t2−Self-extinguishing time after the second ignition.
    下载: 导出CSV

    表  4  PC及PBS-LPR/PC复合材料的锥形量热测试数据

    Table  4.   Data of cone calorimeter for PC and PBS-LPR/PC composites

    Samples PC 10%LPR/PC 2.5%PBS-7.5%LPR/PC 5%PBS-5%LPR/PC 7.5%PBS-2.5%LPR/PC 10%PBS/PC
    TTI /s 138 115 129 107 135 114
    pHRR/(kW·m−2) 590 218 153 149 139 212
    THR/(MJ·m−2) 65.9 49.2 43.1 40.7 33.4 51.8
    pSPR/(m2·s−1) 0.22 0.10 0.07 0.08 0.08 0.07
    TSP/m2 16.8 18.2 10.7 8.4 5.9 9.7
    MARHE/(kW·m−2) 172 109 65 67 54 93
    FPI/(m2·s·kW−1) 0.223 0.528 0.843 0.718 0.969 0.538
    CHR/% 19.1 21.6 38.1 32.8 30.0 18.4
    Notes: TTI−Time to ignition; pHRR−Peak heat release rate; THR−Total heat release at 600 s; pSPR−Peak smoke production rate; TSP−Total smoke production at 600 s; MARHE−Maximum average heat release rate; FPI−Fire performance index; CHR−Char residue.
    下载: 导出CSV

    表  5  GC/MS测定PC及其复合材料主要降解产物组成

    Table  5.   The composition of the main degradation products from PC and its composites obtained by GC/MS measurements.

    Number Structure PC 10%LPR/PC 7.5%PBS-2.5%LPR/PC 10%PBS/PC
    1 CO2、H2O 0.7 0.6 1.04 0.5
    2 5.8 3.1 1.26 2.3
    3 5.6 13.6 11.6 24.6
    4 2.6 5.2 4.1 6.2
    5 3.6 0 2.6 0.9
    7 4.1 10.7 1.3 3.7
    8 17.9 2.0 0 9.3
    Monophenolics 40.3 35.2 21.9 47.5
    11 56.1 61.1 72.3 31.9
    6 0.5 3.2 4.8 6.3
    9 2.8 0.3 0.4 0.7
    10 0.1 0.2 0.2 0.4
    12 0 0 0.4 5.2
    下载: 导出CSV
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  • 收稿日期:  2023-11-30
  • 修回日期:  2024-02-13
  • 录用日期:  2024-02-19
  • 网络出版日期:  2024-03-22

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