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沥青增塑熔纺聚丙烯腈基碳纤维前驱体纤维的制备与性能

陈建永 韩娜 吴潮 孙志恒 吴宇通 孙忠顺 王乐军 张兴祥

陈建永, 韩娜, 吴潮, 等. 沥青增塑熔纺聚丙烯腈基碳纤维前驱体纤维的制备与性能[J]. 复合材料学报, 2022, 39(10): 1-11 doi: 10.13801/j.cnki.fhclxb.20211119.002
引用本文: 陈建永, 韩娜, 吴潮, 等. 沥青增塑熔纺聚丙烯腈基碳纤维前驱体纤维的制备与性能[J]. 复合材料学报, 2022, 39(10): 1-11 doi: 10.13801/j.cnki.fhclxb.20211119.002
Jianyong CHEN, Na HAN, Chao WU, Zhiheng SUN, Yutong WU, Zhongshun SUN, Lejun WANG, Xingxiang ZHANG. Preparation and properties of pitch plasticized melt spinning polyacrylonitrile-based carbon fibers precursor[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-11. doi: 10.13801/j.cnki.fhclxb.20211119.002
Citation: Jianyong CHEN, Na HAN, Chao WU, Zhiheng SUN, Yutong WU, Zhongshun SUN, Lejun WANG, Xingxiang ZHANG. Preparation and properties of pitch plasticized melt spinning polyacrylonitrile-based carbon fibers precursor[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-11. doi: 10.13801/j.cnki.fhclxb.20211119.002

沥青增塑熔纺聚丙烯腈基碳纤维前驱体纤维的制备与性能

doi: 10.13801/j.cnki.fhclxb.20211119.002
基金项目: 天津市科技重大专项(18ZXJMTG00110);天津工业大学纤维培育基金(TGF-21-A4)
详细信息
    通讯作者:

    韩娜,博士,教授,博士生导师,研究方向为高性能纤维的结构设计与应用 E-mail: hanna@tiangong.edu.cn

    张兴祥,博士,教授,博士生导师,研究方向为高性能纤维材料的制备与应用 E-mail: zhangxingxiang@tiangong.edu.cn

  • 中图分类号: TQ342+.74

Preparation and properties of pitch plasticized melt spinning polyacrylonitrile-based carbon fibers precursor

  • 摘要: 为了降低聚丙烯腈(PAN)的熔点和提升熔纺PAN纤维的性能,本文以各向同性萘沥青(INP)和煤焦油沥青(ICP)作为增塑剂,比较了二者对85∶14∶1 摩尔百分比的聚(丙烯腈-丙烯酸甲酯-4-丙烯酰氧基二苯甲酮)三元共聚物(P(AN-MA-ABP))的增塑效果。优选1wt%的INP与P(AN-MA-ABP)充分混合、熔融纺丝、牵伸制备了1wt%INP/P(AN-MA-ABP)共聚物纤维,并研究了紫外(UV)辐照时间对1wt%INP/P(AN-MA-ABP)共聚物纤维的影响。结果表明:相比于稠环结构的ICP,长链含硫杂环结构的INP具有良好的增塑效果。制备的1wt%INP/P(AN-MA-ABP)共聚物纤维直径约52 μm,拉伸强度约250 MPa,表面光滑,结构致密。UV辐照时间从0 min增加到60 min,纤维表面氧含量由17.3%提高到26.0%。氮气条件下,环化起始温度由303.8℃降到292.4℃,环化峰值温度由318.0℃降到308.8℃。空气条件下,环化起始温度由299.9℃降到295.0℃,环化峰值温度由316.4℃降到312.6℃。UV辐照20 min,氮气条件下800℃时纤维的碳收率由41.0%提高到43.4%。UV辐照降低了1wt%INP/P(AN-MA-ABP)共聚物纤维的环化起始温度、峰值温度、焓值,提高了碳收率,有利于后续热处理。

     

  • 图  1  聚(丙烯腈-丙烯酸甲酯-4-丙烯酰氧基二苯甲酮)(P(AN-MA-ABP))三元共聚物的FT-IR图谱

    Figure  1.  FT-IR spectrum of poly (acrylonitrile-methyl acrylate-4-acryloxy dibenzophenone) terpolymer (P(AN-MA-ABP)) terpolymer

    图  2  P(AN-MA-ABP)三元共聚物的1H NMR图谱

    Figure  2.  1H NMR spectrum of P(AN-MA-ABP) terpolymer

    AN—Acrylonitrile; MA—Methyl acrylate; ABP—Acryloyl benzophenone

    图  3  INP和ICP的FT-IR图谱

    Figure  3.  FT-IR spectra of INP and ICP

    图  4  INP/P(AN-MA-ABP)和ICP/P(AN-MA-ABP)熔体流动指数 (MFI) 曲线

    Figure  4.  MFI curves of INP/P(AN-MA-ABP) and ICP/P(AN-MA-ABP) melt

    图  5  INP/P(AN-MA-ABP)和ICP/P(AN-MA-ABP)熔体黏度随剪切速率的变化曲线

    Figure  5.  Viscosity curves of INP/P(AN-MA-ABP) and ICP/P(AN-MA-ABP) melt with shear rate

    图  6  1wt%INP/P(AN-MA-ABP)三元共聚物纤维的EDS图:(a)表面的元素含量;(b)表面的元素分布

    Figure  6.  EDS diagram of 1wt%INP/P(AN-MA-ABP) terpolymer fibers: (a) Surface element content; (b) Surface element distribution

    图  7  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的凝胶含量

    Figure  7.  Gel contents of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV for different time

    图  8  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的FT-IR图谱

    Figure  8.  FT-IR spectra of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV for different time

    图  9  空气气氛下UV辐照PAN的环化机制图

    Figure  9.  Mechanism of PAN cyclization under UV irradiation in air atmosphere

    图  10  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的DSC曲线:(a)氮气;(b)空气

    Figure  10.  DSC curves of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV for different time: (a) Nitrogen; (b) Air

    图  11  氮气条件下UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的TGA和DTG曲线

    Figure  11.  TGA and DTG curves of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV at different time under nitrogen condition

    图  12  UV辐照1wt%INP/P(AN-MA-ABP)三元共聚物纤维的SEM图像

    Figure  12.  SEM images of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV

    表  1  样品的组成编号

    Table  1.   Composition number of the samples

    SampleP(AN-MA-ABP)/wt%INP/
    wt%
    ICP/
    wt%
    0.5wt%INP/P(AN-MA-ABP)99.50.5/
    1wt%INP/P(AN-MA-ABP)99.01.0/
    3wt%INP/P(AN-MA-ABP)97.03.0/
    5wt%ICP/P(AN-MA-ABP)95.0/5.0
    Notes: INP—Isotropic naphthalene pitch; ICP—Isotropic coal tar pitch; P(AN-MA-ABP)—Poly (acrylonitrile-methyl acrylate-4-acryloxy dibenzophenone) terpolymer.
    下载: 导出CSV

    表  2  P(AN-MA-ABP)三元共聚物的组成与性质

    Table  2.   Composition and properties of P(AN-MA-ABP) terpolymers

    Feed ratio
    /mol%
    Composition
    /mol%
    Mn/(g·mol−1)Mw/(g·mol−1)Mw/MnMelt processible
    85∶14∶184.3∶14.3∶1.425000520002.1Yes
    85∶14∶184.5∶14.2∶1.349000740001.5No
    85∶14∶184.4∶14.3∶1.315000300002.0Yes
    85∶14∶184.2∶14.4∶1.421000420002.0Yes
    Notes: Mn—Number average molecular weight; Mw —Weight average molecular weight.
    下载: 导出CSV

    表  3  同性萘沥青(INP)和煤焦油沥青(ICP)的元素组成(单位:wt%)

    Table  3.   Element composition of isotropic naphthalene pitch (INP) and coal tar pitch (ICP) (Units: wt%)

    PitchCHNSO
    INP67.62.10.227.11.2
    ICP84.75.11.20.45.5
    下载: 导出CSV

    表  4  熔纺聚丙烯腈(PAN)纤维的力学性能

    Table  4.   Mechanical properties of melt-spun PAN fibers

    SampleDiameter/
    μm
    Tensile
    strength/
    MPa
    Elongation/%
    P(AN-MA-ABP)51±1.8247.3±6.415.5±2.4
    0.5wt%INP/P(AN-MA-ABP)51±2.3245.6±8.117.5±2.6
    1wt%INP/P(AN-MA-ABP)50±2.1241.6±7.818.1±3.4
    3wt%INP/P(AN-MA-ABP)50±2.5214.3±8.317.2±4.5
    5wt%ICP/P(AN-MA-ABP)52±1.7175.9±7.923.2±5.1
    下载: 导出CSV

    表  5  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的原子浓度数据和原子比

    Table  5.   Atomic concentration data and atomic ratio of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV at different time

    ElementAtomic concentration/at%
    Non-irradiatedUV 20 minUV 40 minUV 60 min
    C74.672.069.967.0
    O17.321.322.326.0
    N8.16.77.87.0
    O/C0.20.30.30.4
    N/C0.10.10.10.1
    下载: 导出CSV

    表  6  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的DSC热力学数据

    Table  6.   DSC thermodynamic data of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV at different time

    AtmosphereUV irradiation time/minTonset
    /℃
    TM
    /℃
    Hc
    /(J·g−1)
    Nitrogen0303.8318.0537.8
    20296.4310.6474.8
    40294.0309.1443.7
    60292.4308.8442.1
    Air0299.9316.4725.8
    20299.6314.4683.7
    40297.7314.2678.4
    60295.0312.6676.4
    Notes: Tonset—Onset temperature of exothermic reaction (10℃/min); TM—Maximum temperature of exothermic reaction (10℃/min); ΔHc—Enthalpy of exothermic reaction (10℃/min).
    下载: 导出CSV

    表  7  UV辐照不同时间的1wt%INP/P(AN-MA-ABP)三元共聚物纤维的力学性能

    Table  7.   Mechanical properties of 1wt%INP/P(AN-MA-ABP) terpolymer fibers irradiated by UV at different time

    UV irradiation timeTensile strength/MPaElongation/%
    0 min252.8±6.315.5±2.4
    20 min247.5±7.815.8±3.5
    40 min243.6±8.316.9±2.6
    60 min231.5±7.116.1±2.2
    下载: 导出CSV
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  • 收稿日期:  2021-09-03
  • 录用日期:  2021-11-11
  • 修回日期:  2021-10-15
  • 网络出版日期:  2021-11-22
  • 刊出日期:  2022-10-15

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