新型环氧树脂芳胺固化剂的合成及其固化性能*

doi:10.11901/1005.3093.2014.031

材料研究学报

2014, Vol. 28

Issue (9): 715-720 DOI: 10.11901/1005.3093.2014.031

本期目录 | 过刊浏览

新型环氧树脂芳胺固化剂的合成及其固化性能*

熊需海¹,刘思扬¹,陈平^1,²(

),卢放²,任荣¹

1. 沈阳航空航天大学航空航天工程学院辽宁省高性能聚合物基复合材料重点实验室沈阳 110136
2. 大连理工大学化工学院精细化工国家重点实验室大连 116024

Synthesis and Performance of a Novel Aromatic Amine Curing Agent for Epoxy Resin

Xuhai XIONG¹,Siyang LIU¹,Ping CHEN^1,^2,^**(

),Fang LU²,Rong REN¹

1. Liaoning Key Laboratory of Advanced Polymer Matrix Composites Manufacturing Technology, Faculty of Aerospace Engineering, Shenyang Aerospace University, Shenyang 1101362.
2. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024

引用本文:

熊需海,刘思扬,陈平,卢放,任荣. 新型环氧树脂芳胺固化剂的合成及其固化性能*[J]. 材料研究学报, 2014, 28(9): 715-720.
Xuhai XIONG, Siyang LIU, Ping CHEN, Fang LU, Rong REN. Synthesis and Performance of a Novel Aromatic Amine Curing Agent for Epoxy Resin[J]. Chinese Journal of Materials Research, 2014, 28(9): 715-720.

全文: PDF(1043 KB) HTML

摘要:

以酚酞型双马来酰亚胺(PBMI)和芳香二胺(DDE)为原料, 经迈克尔加成反应制备出新型环氧树脂芳胺固化剂(PBMI-DDE), 红外光谱和核磁共振等分析方法证实了新型固化剂的分子结构。用动态差示扫描量热法(DSC)确定了该固化剂和环氧树脂的固化工艺并对固化动力学进行了研究。采用Kissinger方程、FWO方程计算出固化反应活化能分别为 46.7 kJ/mol, 49.1 kJ/mol, 并结合Crane方程计算出反应级数为0.88。动态热机械分析表明, 完全固化的树脂体系玻璃化转变温度为153℃; 热失重研究结果显示, 新型环氧树脂体系具有优异的热稳定性。

关键词 ：有机高分子材料, 芳胺固化剂, 环氧树脂, 迈克尔加成反应, 固化动力学

Abstract：

A new curing agent (PBMI-DDE) for epoxy resin was synthesized from phthalide-containing bismaleimide (PBMI) and aromatic amine (DDE) according to the Michael addition reaction. The chemical structure of PBMI-DDE was characterized by ¹H NMR spectroscopy and Fourier transform infrared spectroscopy (FTIR). The curing performance and kinetics of E-51/ PBMI-DDE was studied by DSC. Apparent activation energy evaluated according to Kissinger model or FWO model is 46.7 or 49.1 kJ/mol, respectively, and the calculated reaction order is 0.88 based on Crane method. The DMA and TGA results show that the cured resin possesses excellent thermostability with a glass transition temperature 153℃ for the completely cured resin.

Key words： organic polymer materials aromatic amine epoxy resin Michael addition reaction cure kinetics

收稿日期: 2014-01-14

基金资助:* 国家自然科学基金51303107, 国防“十二五”基础科研A352*******, 辽宁省教育厅优秀人才计划LR2013002项目资助。

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https://www.cjmr.org/CN/10.11901/1005.3093.2014.031 或 https://www.cjmr.org/CN/Y2014/V28/I9/715

图1 PBMI-DDE的合成路线

图2 PBMI-DDE和PBMI的红外光谱图

图3 PBMI-DDE的核磁共振谱

图4 E-51/PBMI-DDE体系在不同升温速率下的DSC曲线

表1 E-51/ PBMI-DDE体系在不同升温速率下固化反应参数

图5 特征温度T与升温速度β的关系

图6 ln(β/TP2)和lnβ对1000/Tp关系图

图7 Flynn-Wall- Ozawa 法分析曲线

图8 E-51/ PBMI-DDE固化物的DMA曲线

图9 E-51/ PBMI-DDE固化物的TG和DTG曲线

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