基于<strong>Diels-Alder</strong>反应的自修复环氧树脂的制备和修复行为

doi:10.11901/1005.3093.2019.072

材料研究学报

2019, Vol. 33

Issue (8): 635-640 DOI: 10.11901/1005.3093.2019.072

研究论文

本期目录 | 过刊浏览

基于Diels-Alder反应的自修复环氧树脂的制备和修复行为

何霞,王飞,赵翰文,王彦平,冯利邦(

)

兰州交通大学材料科学与工程学院兰州 730070

Preparation and Healing Behavior of Self-healing Epoxy Resins Based on Diels-Alder Reaction

Xia HE,Fei WANG,Hanwen ZHAO,Yanping WANG,Libang FENG(

)

School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China

引用本文:

何霞, 王飞, 赵翰文, 王彦平, 冯利邦. 基于Diels-Alder反应的自修复环氧树脂的制备和修复行为[J]. 材料研究学报, 2019, 33(8): 635-640.
Xia HE, Fei WANG, Hanwen ZHAO, Yanping WANG, Libang FENG. Preparation and Healing Behavior of Self-healing Epoxy Resins Based on Diels-Alder Reaction[J]. Chinese Journal of Materials Research, 2019, 33(8): 635-640.

全文: PDF(5370 KB) HTML

摘要:

先使环氧氯丙烷与糠胺反应合成含有呋喃环的双环氧基糠基缩水甘油胺(DGFA)，再与双马来酰亚胺发生Diels-Alder(DA)反应制备出热可逆自修复环氧树脂EP-DA。用FT-IR表征了EP-DA的化学结构和热可逆性。模拟了实际使用过程中环氧树脂受到冲击破环而内部产生裂纹、进行热处理使裂纹愈合实现了材料的自修复过程。根据宏观定性观察和弯曲载荷恢复的定量测量，证实了这种环氧树脂具有良好的自修复性能且可实现多次破坏的自修复。这种环氧树脂具有优异的再加工性能，可实现废旧环氧树脂的回收再利用。

关键词 ：有机高分子材料, 自修复, Diels-Alder反应, 环氧树脂, 热可逆

Abstract：

The di-epoxy group-based N,N-diglycidyl-furfurlamine (DGFA) containing furan ring was synthesized via the reaction between epichlorohydrin and decylamine. Then a thermo-reversible epoxy resin (EP-DA) with self-healing performance is prepared by Diels-Alder (DA) reaction between the synthesized DGFA and bismaleimide. The structure and thermal reversibility of the prepared EP-DA were characterized by Fourier transform infrared spectroscopy (FT-IR). Results show that the as-prepared EP-DA exhibits excellent thermal reversibility, which is confirmed by the appearance observation and absence of the infrared absorption peak of DA bonds before and after heat treated at 130^oC. The as-prepared EP-DA has outstanding self-healing performance, which was approved via the qualitative observation of crack evolution and quantitative measurement of flexural load restoring by simulating crack repair. The width of cracks in EP-DA decreases gradually with the extending heat treatment time, while crack disappears completely when which is treated at 130^oC for 6 min, indicating that the self-healing rate is very high and cracks in EP-DA have been repaired apparently in 6 min. The EP-DA with cracks can be repaired completely upon heat treatment at 130^oC for 30 min and followed by 48 h at 70^oC; Moreover, the EP-DA has outstanding multiple damage/self-repair performance, and cracks within EP-DA can be repaired for more than three times. The repair efficiency of EP-DA after cut in half and then put together can reach 71.7%, 61.6%, and 54.5% after damage/heat treatment for three times in turn. Additionally, the as-prepared epoxy resin exhibits excellent reprocessing performance and which makes the recycling of waste epoxy resin possible.

Key words： organic polymer materials self-healing Diels-Alder reaction epoxy resin thermal reversibility

收稿日期: 2019-01-21

ZTFLH:

TQ323

基金资助:国家自然科学基金(No. 51463010);Supported by National Natural Science Foundation of China(No. 51463010)

作者简介: 何霞，女，1993年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.072 或 https://www.cjmr.org/CN/Y2019/V33/I8/635

图1 EP-DA的制备过程

图2 DGFA、BMI、EP-DA的红外光谱

图3 EP-DA在70oC反应不同时间后的弯曲载荷-位移曲线

图4 带冲击裂纹的EP-DA试样在不同温度热处理时裂纹随时间的变化

图5 在130℃热处理不同时间EP-DA试样的弯曲强度

图6 EP-DA的化学结构的变化

图7 DA及r-DA反应分子结构变化示意图

图8 EP-DA自修复过程机理示意图

图9 EP-DA多次自修复的代表性弯曲载荷-位移曲线

表1 EP-DA试样在三点弯曲试验中的力学性能和修复效率

图10 EP-DA再加工过程示意图

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