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低黏度环氧树脂硼胺-酸酐复合固化体系研究

邢志鹏 乔英杰 张晓红 王晓东

邢志鹏, 乔英杰, 张晓红, 等 . 低黏度环氧树脂硼胺-酸酐复合固化体系研究[J]. 北京航空航天大学学报, 2019, 45(1): 141-148. doi: 10.13700/j.bh.1001-5965.2018.0208
引用本文: 邢志鹏, 乔英杰, 张晓红, 等 . 低黏度环氧树脂硼胺-酸酐复合固化体系研究[J]. 北京航空航天大学学报, 2019, 45(1): 141-148. doi: 10.13700/j.bh.1001-5965.2018.0208
XING Zhipeng, QIAO Yingjie, ZHANG Xiaohong, et al. Low-viscosity epoxy resin boramine-anhydride composite curing system[J]. Journal of Beijing University of Aeronautics and Astronautics, 2019, 45(1): 141-148. doi: 10.13700/j.bh.1001-5965.2018.0208(in Chinese)
Citation: XING Zhipeng, QIAO Yingjie, ZHANG Xiaohong, et al. Low-viscosity epoxy resin boramine-anhydride composite curing system[J]. Journal of Beijing University of Aeronautics and Astronautics, 2019, 45(1): 141-148. doi: 10.13700/j.bh.1001-5965.2018.0208(in Chinese)

低黏度环氧树脂硼胺-酸酐复合固化体系研究

doi: 10.13700/j.bh.1001-5965.2018.0208
基金项目: 

国家自然科学基金 51479037

详细信息
    作者简介:

    邢志鹏  男, 博士。主要研究方向:树脂基复合材料

    乔英杰  男, 博士, 教授。主要研究方向:树脂基复合材料、陶瓷基复合材料、敏感材料与器件

    通讯作者:

    乔英杰, E-mail: qiaoyingjie99@163.com

  • 中图分类号: TQ323.5

Low-viscosity epoxy resin boramine-anhydride composite curing system

Funds: 

National National Science Foundation of China 51479037

More Information
  • 摘要:

    为探究低黏度环氧树脂复合固化反应机理,研究了低黏度环氧树脂硼胺-酸酐复合固化体系的流变性能和固化反应过程,分析了硼胺-酸酐复合比例对复合固化体系流变特性和固化反应过程的影响;利用流变学参数确定了复合固化体系的固化起始时间、凝胶时间点及基于阿伦尼乌斯方程的固化反应活化能。研究结果表明,随着硼胺-酸酐复合固化体系中酸酐复合比例的增加,体系固化反应获得促进,其固化起始时间和凝胶点均降低,同时基于阿伦尼乌斯方程的固化反应活化能降低;采用非等温差示扫描量热(DSC)对硼胺-酸酐复合固化体系过程进行分析,结果表明硼胺-酸酐复合固化体系存在相对独立的双放热峰,随着酸酐复合比例的增加,低温放热峰的峰值增大,高温放热峰的峰值减小,且双峰的峰值温度向高温方向移动。根据2种固化剂的固化反应机理分析,环氧树脂硼胺-酸酐复合固化体系中硼胺固化剂和酸酐固化剂既存在相互协同效应又存在相互竞争作用。

     

  • 图 1  复合固化体系流变性能参数随时间变化曲线(PJ-1)

    Figure 1.  Time variation curves of rheological parameters of composite curing system(PJ-1)

    图 2  不同复合固化体系流变性能参数随时间变化曲线

    Figure 2.  Time variation curves of rheological parameters of different composite curing systems

    图 3  不同复合固化体系非等温DSC曲线

    Figure 3.  Non-isothermal DSC curves of different composite curing systems

    图 4  PJ-3复合固化体系的非等温DSC曲线

    Figure 4.  Non-isothermal DSC curves of PJ-3 composite curing system

    图 5  调整基线后的复合固化体系的非等温DSC曲线

    Figure 5.  Non-isothermal DSC curve of composite curing system after baseline adjustment

    图 6  分峰后PJ-3复合固化体系的非等温DSC曲线

    Figure 6.  Non-isothermal DSC curve of PJ-3 composite curing system after peak splitting

    图 7  PJ-3复合固化体系PEAK′-1、PEAK′-2的外推温度曲线

    Figure 7.  Extrapolation temperature curves of PJ-3 composite curing system of PEAK′-1 and PEAK′-2

    图 8  甲基四氢苯酐的化学结构示意图

    Figure 8.  Schematic of chemical structure of MeTHPA

    图 9  甲基四氢苯酐与环氧树脂的固化反应机理

    Figure 9.  Curing reaction mechanism of MeTHPA and epoxy resin

    图 10  594固化剂的化学结构示意图

    Figure 10.  Schematic of chemical structure of 594 curing agent

    图 11  594固化剂硼氮原子电子吸引示意图

    Figure 11.  Schematic of electron attraction of boron and nitrogen atoms of 594 curing agent

    表  1  复合固化体系试样配方

    Table  1.   Sample formulation of composite curing system

    原料 原料质量份数
    PJ-1 PJ-2 PJ-3 PJ-4
    环氧树脂(ESX) 100 100 100 100
    硼胺固化剂(594) 10 10 10 10
    甲基四氢苯酐(MeTHPA) 5 10 15 20
    下载: 导出CSV

    表  2  复合固化体系的tstG和Δt数值

    Table  2.   Value of ts, tG and Δt of composite curing system

    s
    试样 ts tG Δt
    PJ-1 2196 3490 1294
    PJ-2 1755 2900 1145
    PJ-4 1660 2530 870
    注:Δt=ts-tG
    下载: 导出CSV

    表  3  复合固化体系非等温DSC曲线放热峰峰值温度

    Table  3.   Peak temperature of non-isothermal DSC curve exothermic peak of composite curing system

    试样 PEAK-1峰值温度 PEAK-2峰值温度
    PJ-1 106.28 188.49
    PJ-2 108.69 189.64
    PJ-3 110.47 191.24
    PJ-4 112.15 195.29
    注:测量条件为β=10℃/min。
    下载: 导出CSV

    表  4  不同升温速率下双峰的峰值温度

    Table  4.   Peak temperature of double peaks at different heating rates

    β/(℃·min-1) PEAK′-1 PEAK′-2
    Ti/℃ Tp/℃ Tf/℃ Ti/℃ Tp/℃ Tf/℃
    5 76.24 110.13 152.48 157.82 187.95 220.13
    10 80.52 120.61 164.27 164.27 205.36 246.27
    15 85.37 129.37 174.52 170.49 212.84 260.45
    20 90.66 136.40 183.40 176.81 219.90 265.71
    下载: 导出CSV
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  • 收稿日期:  2018-04-11
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