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加成型酚醛改性双马树脂及其复合材料性能

姜伟芳 王林祥 郑庆 袁荞龙 黄发荣

姜伟芳, 王林祥, 郑庆, 等. 加成型酚醛改性双马树脂及其复合材料性能[J]. 复合材料学报, 2022, 40(0): 1-13
引用本文: 姜伟芳, 王林祥, 郑庆, 等. 加成型酚醛改性双马树脂及其复合材料性能[J]. 复合材料学报, 2022, 40(0): 1-13
Weifang JIANG, Lixiang WANG, Qing ZHENG, Qiaolong YUAN, Farong HUANG. Properties of bismaleimide resin modified by addition-curing phenolic and their composites[J]. Acta Materiae Compositae Sinica.
Citation: Weifang JIANG, Lixiang WANG, Qing ZHENG, Qiaolong YUAN, Farong HUANG. Properties of bismaleimide resin modified by addition-curing phenolic and their composites[J]. Acta Materiae Compositae Sinica.

加成型酚醛改性双马树脂及其复合材料性能

基金项目: 上海航天科技创新基金(SAST2019-106),中央高校基本科研业务费专项资金资助(JKD01211701)
详细信息
    通讯作者:

    袁荞龙,博士,教授,研究方向为耐高温树脂的制备改性及其复合材料性能研究 E-mail: qlyuan@ecust.edu.cn

  • 中图分类号: TB332

Properties of bismaleimide resin modified by addition-curing phenolic and their composites

  • 摘要: 双马来酰亚胺(BMI)树脂因其优异的性能已在航空航天、电子和其他工业领域获得应用,为满足其在高速飞行器结构件中需求,用加成型酚醛树脂改性BMI体系以改善其热-力学性能。通过Williamson醚化反应合成了炔丙基醚化酚醛树脂(PN)和烯丙基醚化酚醛树脂(AN),采用熔融共混法分别与N,N’-(4,4’-亚甲基二苯基)双马来酰亚胺(BDM)和2,2’-二烯丙基双酚A(DABPA)树脂体系(BD)共混,制备了三元热固性树脂:PN改性BD(BDPN)和AN改性BD(BDAN)。研究了两种加成型酚醛树脂改性的BD树脂体系的加工工艺性和固化行为的变化,并对改性前后固化树脂及其复合材料的热、力学性能进行了研究。结果表明共混树脂体系都在极性溶剂中有好的溶解性,加工窗口都有50℃以上。BDPN和BDAN固化反应只有一个放热峰,最高放热峰值温度比BD树脂低。用FTIR跟踪验证了BD、BDPN和BDAN树脂体系发生的Ene、Diels-Alder、Claisen重排和炔基与马来酰亚胺环的聚合反应。PN热氧稳定性好,改性的BDPN固化树脂空气中质量损失5%的温度(Td5)高于400℃,800℃残留率(Yr800℃)由3.7%提升至23.1%。BD、BDPN和BDAN固化物的极限氧指数(LOI)分别为30.2%、32.5%和31.0%,都属难燃材料。PN和AN改性的BD树脂浇铸体冲击强度和弯曲模量分别提高了19%和30%,但弯曲强度都因交联密度的下降而有所下降。BDPN和BDAN固化物的吸水率都低于BD树脂,沸水中40 h时BDPN和BDAN分别比BD树脂降低了8.6%和14%。室温下T300碳纤维增强BDAN复合材料(T300CF/BDAN)弯曲强度、弯曲模量和层间剪切强度(ILSS)高于BD基复合材料;200℃下T300CF/BDPN的弯曲强度达575 MPa,保留率高达98.6%。炔丙基醚化酚醛树脂改性双马来酰亚胺树脂体系有望应用于耐200℃的复合材料结构件,为耐热双马来酰亚胺树脂的制备提供新的途径。

     

  • 图  1  炔丙基醚化和烯丙基醚化酚醛树脂合成路径

    Figure  1.  Synthesis routes of propargyl novolac and allyl novolac

    图  2  BD (N,N’-(4,4’-亚甲基二苯基)双马来酰亚胺-2,2’-二烯丙基双酚A (BDM-DABPA))、BDPN (BDM-DABPA-炔丙基醚化酚醛树脂(PN))和BDAN (BDM-DABPA-烯丙基醚化酚醛树脂(AN))共混树脂的黏温曲线

    Figure  2.  Viscosity of the BD (N,N'-(4,4'-diphenylmethylane)bismaleimide-2,2'-diallyl bisphenol A (BDM-DABPA)), BDPN(BDM/DABPA/propargyl etherified novolac (PN)) and BDAN(BDM-DABPA-allyl etherified phenolic (AN)) blended resins against temperature

    图  3  PN、AN (a)和共混树脂(b) 的DSC图

    Figure  3.  DSC curves of PN, AN, (a) and blended resins (b)

    4  共混树脂的固化机制 (a) 和BD (b)、BDPN (c)、BDAN (d)共混树脂的红外跟踪谱图

    4.  Proposed curing reactions in the blended resins (a) and FTIR spectra of BD (b), BDPN (c), and BDAN(d) resins

    图  5  PN、AN和共混树脂固化物在N2 (a) 和空气 (b) 气氛下的TGA及DTG曲线图、共混树脂未固化前的DSC图 (c) 和共混树脂固化后的DMA图 (d)

    Figure  5.  TGA and DTG curves of the cured PN, AN and blended resin in N2 (a) and air (b) atmosphere, DSC curves of uncured blended resins (c) and DMA curves of cured blended resins (d)

    图  6  共混树脂BD(a)、BDPN(b)和BDAN(c)浇铸体的冲击断面SEM图以及BDPN(d)和BDAN(e)浇铸体断面EDS能谱图

    Figure  6.  SEM images of fracture surfaces of cured BD (a), BDPN (b) and BDAN(c) resins and EDS images of fracture surfaces of cured BDPN (d) and BDAN(e) resins

    图  7  共混树脂固化物吸水率随时间的变化曲线图

    Figure  7.  The changes of water absorption of the cured blended resins with time

    图  8  T300CF增强的BD (a)、BDPN (b) 和BDAN (c) 复合材料在室温下的SEM断面和T300CF增强的BD (d)、BDPN(e)和BDAN (f) 复合材料在200℃下的SEM断面图

    Figure  8.  SEM images of fracture surfaces of T300CF reinforced BD (a)、BDPN (b) and BDAN (c) composites at room temperature and T300CF reinforced BD (d)、BDPN (e) and BDAN (f) composites at 200℃

    表  1  AN、PN和共混树脂的DSC数据结果

    Table  1.   DSC results of the AN, PN and blended resins

    ResinTi/℃Tp1/℃Tp2/℃Tf/℃ΔH/(J·g−1)ΔH-cured/(J·g−1)Retention of ΔH/%
    PN188253329659.3
    AN175221349383288.7
    BD145196248287402.049.912.4
    BDPN182232306392.025.36.5
    BDAN175235289299.313.54.5
    Notes: Ti is the initial exothermic temperature; Tp1 is the first exothermic peak temperature; Tp2 is the second exothermic peak temperature; Tf is the end exothermic temperature; ΔH is the exothermic enthalpy of uncured resins; ΔH-cured is the exothermic enthalpy of cured resins.
    下载: 导出CSV

    表  2  PN、AN和共混树脂固化物的TGA、DTG、DMA及未固化树脂DSC数据结果

    Table  2.   TGA, DTG and DMA results of the cured PN, AN and blended resins, and DSC results of the uncured resins

    ResinN2AirTg-uncured /°CTg-cured /°CMC
    Td5 /°CYr800°C /%Td max /°CTd5 /°CYr800°C /%Td1 max /°C
    PN40658.4743240930.76412---
    AN40345.464504190.81445---
    BD39932.704514183.7044311.93313129.54
    BDPN40345.8443840823.1343820.32320130.14
    BDAN40735.8945240911.8445023.95240180.51
    Notes: Td5 is the temperature at 5% mass loss; Yr800°C is the residual yield at 800℃; Td max is the maximum temperature of thermogravimetric rate ; Tg-uncured is the glass transition temperature of uncured resins; Tg-cured is the glass transition temperature of cured resins; MC is the average molecular weight of polymer between cross-linked nodes.
    下载: 导出CSV

    表  3  共混树脂的极限氧指数

    Table  3.   The LOI of the cured blended resins

    Cured ResinYr600°C /%LOI (Van K-H)Real LOI
    BD44.3235.230.2
    BDPN51.5838.132.5
    BDAN46.7636.231.0
    Notes: Yr600°C is the char yield at 600℃; LOI is the limited oxygen index.
    下载: 导出CSV

    表  4  共混树脂浇铸体的力学性能

    Table  4.   Mechanical properties of blended resins

    Cured ResinImpact strength
    /(kJ m-2)
    Flexural strength
    /MPa
    Flexural modulus
    /GPa
    BD14.7±1.35151.0±5.483.0±0.24
    BDPN14.8±0.11146.1±13.393.9±0.04
    BDAN17.5±0.79139.0±7.073.9±0.06
    下载: 导出CSV

    表  5  T300CF/共混树脂复合材料在室温以及200℃下的力学性能

    Table  5.   Mechanical properties of T300CF / blended resin composites at room temperature and 200℃

    MatrixTemperature/
    Flexural
    strength/MPa
    Retention of
    flexural strength/%
    Flexural modulus/
    GPa
    ILSS/
    MPa
    Retention of ILSS/
    %
    BD25572.1±3.7053.1±1.3444.3±1.13
    BDPN583.1±17.8454.1±2.5040.4±2.47
    BDAN639.3±14.0154.9±0.6446.0±0.69
    BD200563.3±16.6798.539.2±0.3088.5
    BDPN575.0±10.0098.632.1±0.4479.4
    BDAN543.3±6.6785.026.4±0.2957.4
    Note:ILSS is the interlaminar shear strength.
    下载: 导出CSV

    表  6  共混树脂的DMA分析结果

    Table  6.   DMA analysis results of blended resins

    Cured ResinEg/MPa aEr/MPa bEg/ Er
    BD1494.4297.45.0
    BDPN399.1212.21.9
    BDAN560.775.57.4
    Notes: a Eg is the modulus at the temperature T1(T1=Tg-20℃) obtained from DMA data; b Er is the modulus at the temperature T2(T2=Tg+20℃) obtained from DMA data.
    下载: 导出CSV
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  • 收稿日期:  2022-01-04
  • 录用日期:  2022-02-19
  • 修回日期:  2022-01-28
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