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聚苯醚型邻苯二甲腈树脂及其复合材料

张鑫伟 陆奇 王芳 刘敏 周权

张鑫伟, 陆奇, 王芳, 等. 聚苯醚型邻苯二甲腈树脂及其复合材料[J]. 复合材料学报, 2024, 42(0): 1-9.
引用本文: 张鑫伟, 陆奇, 王芳, 等. 聚苯醚型邻苯二甲腈树脂及其复合材料[J]. 复合材料学报, 2024, 42(0): 1-9.
ZHANG Xinwei, LU Qi, WANG Fang, et al. Polyphenylene ether type phthalonitrile resin and its composite materials[J]. Acta Materiae Compositae Sinica.
Citation: ZHANG Xinwei, LU Qi, WANG Fang, et al. Polyphenylene ether type phthalonitrile resin and its composite materials[J]. Acta Materiae Compositae Sinica.

聚苯醚型邻苯二甲腈树脂及其复合材料

基金项目: 国家自然科学基金 (52173074);中央高校基本科研业务费专项资金资助(JKD01231701)
详细信息
    通讯作者:

    刘敏,博士,副教授,硕士生导师,研究方向为高分子聚合物膜材料 E-mail: liumin@ecust.edu.cn

    周权,博士,教授,博士生导师,研究方向为耐高温树脂及其复合材料 E-mail: qzhou@ecust.edu.cn

  • 中图分类号: TB332

Polyphenylene ether type phthalonitrile resin and its composite materials

Funds: National Natural Science Foundation of China (No.52173074); supported by “the Fundamental Research Funds for the Central Universities (No.JKD01231701)
  • 摘要: 为保留聚苯醚树脂优异介电性能的同时提升其耐溶剂性和热稳定性,拓宽其在高频高速覆铜板领域的应用,本文以K2CO3为缚酸剂,通过4-硝基邻苯二甲腈的亲核取代合成了一种聚苯醚型的邻苯二甲腈树脂(PPOCN)。通过FTIR、DSC、TGA、流变性分析对树脂的结构、固化行为、耐热性以及加工性能进行了综合分析,通过介电分析仪、动态热机械分析及力学性能测试评估了复合材料的各项性能。结果表明,PPOCN具备交联反应活性,固化物的玻璃化转变温度(Tg)为295 ℃,5%热失重温度(Td5%)为419.3 ℃,与聚苯醚原料相比热稳定性显著提高。以PPOCN为基体树脂,二氨基二苯甲烷(DDM)为固化剂制备的纤维增强复合材料具备优异的力学性能和介电性能,弯曲强度为863.9 MPa,层间剪切强度为68.6 MPa,1 GHz频率下的介电常数为3.15,损耗角正切为0.003。PPOCN在保留了聚苯醚树脂优异介电性能的同时,兼具优异的力学性能和优良的热性能。

     

  • 图  1  PPOCN的合成路线图

    Figure  1.  Synthetic routes of PPOCN

    图  2  SA90、4-硝基邻苯二甲腈和PPOCN的红外光谱

    Figure  2.  Infrared spectra of SA90、4-nitrophthalonitrile and PPOCN

    图  3  SA90和PPOCN的核磁共振碳谱

    Figure  3.  13C-NMR spectra of SA90 and PPOCN

    图  4  PPO树脂的DSC测试结果

    Figure  4.  DSC curve of PPO resin

    图  5  胺基催化邻苯二甲腈的聚合机制

    Figure  5.  Mechanism of amine catalyzed polymerization of phthalonitrile

    图  6  PPOCN及PHDM-1的流变曲线

    Figure  6.  Rheological curves of PPOCN and PHDM-1

    图  7  PHDM/石英纤维布(QF)复合材料的的DMA曲线

    Figure  7.  DMA curves of PHDM/Quartz fiber cloth (QF) composite materials

    图  8  PHDM/QF复合材料的介电性能测试结果(a)介电常数(b)损耗角正切

    Figure  8.  Test results of dielectric properties of PHDM/QF composite materials(a) Dielectric constant (b) Tan Delta

    图  9  PHDM/QF复合材料力学强度(a)弯曲强度(b)层间剪切强度

    Figure  9.  Mechanical strength of PHDM/QF composite materials(a) flexural strength (b) interlaminar shear strength

    图  10  PHDM-1/QF复合材料耐溶剂性测试前(a)后(b)外观变化

    Figure  10.  Appearance changes of PHDM-1/QF composite materials before(a) and after(b) solvent resistance testing

    表  1  不同比例的PHDM树脂配方

    Table  1.   PHDM resin formula with different proportions

    SampleResin mass ratio
    PPOCNDDM
    PPOCN1000
    PHDM-11001
    PHDM-21002
    PHDM-31003
    Notes: PPOCN−Polyphenylene ether type phthalonitrile resin; DDM—4,4'-diaminodiphenylmethane; PHDM−Blends of PPOCN and DDM
    下载: 导出CSV

    表  2  PPO树脂固化物的TGA数据

    Table  2.   TGA data of PPO resin cured products

    Samples Td5% /℃ 800℃ Mass
    retention/%
    N2 Air N2 Air
    SA90 357.3 349.5 21.4 0.49
    PPOCN 417.6 409.9 55.46 0.529
    PHDM-1 416.2 401.4 55.77 0.524
    PHDM-2 418.5 406.0 54.22 0.536
    PHDM-3 419.3 409.6 55.33 0.673
    Notes:Td5%−5% weight loss temperature
    下载: 导出CSV
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  • 收稿日期:  2024-01-26
  • 修回日期:  2024-03-21
  • 录用日期:  2024-03-22
  • 网络出版日期:  2024-04-22

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