Properties of self-healing epoxy resin containing PEGDE segments based on Diels-Alder dynamic covalent bond

doi:10.11949/0438-1157.20191567

Abstract

Abstract:

The dienyl structure-containing furan methylamine was used to link the hard segment E-51 epoxy resin (EP) modified by bisphenol A and the soft segment PEGDE to form linear macromolecules, and reacted with bismaleimide containing dienophilic structure to synthesize the soft-hard-soft structure of the intrinsic self-healing epoxy (EP-DA) via thermo reversible Diels-Alder (DA) reaction. The structure and performance of EP-DA were characterized by FTIR, DSC, TGA and electronic universal testing machine. The results show that: DA dynamic covalent bond is successfully introduced into EP-DA, and the temperature of DA forward and reverse reaction is 60 ℃ and 122 ℃ respectively. When the PEGDE and EP content in the EP-DA segment each accounts for 50%, its heat resistance and tensile strength reach the best, the epoxy resin exhibits good reprocessing properties and multiple self-repairing properties. After the damaged specimen is repaired at 60℃ for 4 h, the crack is healed, and the first repair rate is 88. 41%. After three repairs of the same specimen, the repair rate is still more than 68%.

Key words: repairing, Diels-Alder reaction, recovery, polymers, thermoreversibility

摘要：

用含双烯体结构的呋喃甲胺，将硬段为双酚A型E-51环氧树脂(EP)和软段为PEGDE连接成线性大分子，并与含亲双烯体结构的双马来酰亚胺反应，制备出含热可逆Diels-Alder(DA)反应的软-硬-软结构的本征型自修复环氧树脂(EP-DA)。通过FTIR、DSC、TGA和电子万能试验机，对EP-DA结构和性能进行了表征。结果表明：DA动态共价键成功引入EP-DA，且DA正、逆反应的温度分别是60℃、122℃。当EP-DA链段中的PEGDE和EP含量各占50%时，其耐热性和拉伸强度达到最佳。EP-DA还具有良好的再加工性能和多次自修复性能，受损试样在60℃下修复4 h后，裂纹基本愈合，且第一次修复率可达88. 41%，同一试样经过三次修复后，其修复率仍可达68%以上。

关键词: 修复, Diels-Alder反应, 回收, 聚合物, 热可逆性

CLC Number:

TQ 323.5

Lunliang ZHANG, Liying WAN, Juntong HUANG, Xibao LI, Zhijun FENG, Zhi CHEN. Properties of self-healing epoxy resin containing PEGDE segments based on Diels-Alder dynamic covalent bond[J]. CIESC Journal, 2020, 71(6): 2871-2879.

张伦亮, 万里鹰, 黄军同, 李喜宝, 冯志军, 陈智. 基于Diels-Alder动态共价键的含PEGDE片段自修复环氧树脂性能研究[J]. 化工学报, 2020, 71(6): 2871-2879.

Figures/Tables 14

Table 1 Raw material feed ratios of synthetic polymer EP-DA

Samples	PEGDE/g	EP/g	FA/g	1,8-BMI/g
EP-DA₃₀	30	70	22.31	41.21
EP-DA₅₀	50	50	20.81	38.34
EP-DA₇₀	70	30	19.25	35.48

Fig.1 Synthetic routes of EP-DA

Fig.2 FTIR spectra of PEGDE, EP, PEGDE-EP-FA and EP-DAa—PEGDE; b—EP; c—PEGDE-EP-FA; d—EP-DA

Fig.4 TGA curves of EP-DA with different components of PEGDE and EP

Fig.3 DSC curves of PEGDE-EP-FA and 1,8-BMI mixture cured at 60 ℃ for different time

Fig.5 Stress-strain curves of EP-DA with different components of PEGDE and EP

Fig.7 EP-DA50 reprocessing performance

Fig.6 Swelling and dissolution experiment of EP-DA50

Fig.8 Tensile strength of EP-DA50 heated at 60°C for different times

Fig.9 EP-DA50 sample self-healing micrograph

Fig.10 Mechanism diagram of EP-DA repair process based on thermoreversible DA dynamic covalent bonds

Fig.11 EP-DA50 multiple self-healing performance

Fig.12 Stress-strain curves of EP-DA50 under different repair times

Table 2 Tensile test and repair rates under multiple self-healing of samples

Samples	Stress/MPa	Elongation at break/%	Healing efficiency/%
EP-DA₅₀ 0#	24.26	38.47	—
EP-DA₅₀ 1#	21.36	36.04	88.41
EP-DA₅₀ 2#	18.40	31.97	76.17
EP-DA₅₀ 3#	16.56	26.88	68.54

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