Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (04): 20-28.doi: 10.13475/j.fzxb.20240602101

• Fiber Materials • Previous Articles     Next Articles

Self-healing and reprocessing performance of benzyl glycidyl ether modified epoxy vitrimer

LI Jingkang1, HUANG Liang1, CHEN Shishi1, BI Shuguang1(), RAN Jianhua1, TANG Jiagong2   

  1. 1. State Key Laboratory of New Textile Materials and Advanced Processing, Wuhan Textile University, Wuhan, Hubei 430200, China
    2. Jingsui Technology Co., Ltd., Wuhan, Hubei 430058, China
  • Received:2024-06-11 Revised:2024-10-29 Online:2025-04-15 Published:2025-06-11
  • Contact: BI Shuguang E-mail:sgbi@wtu.edu.cn

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Abstract:

Objective The primary objective of this research is to enhance self-healing and reprocessing capabilities of epoxy vitrimers, which are integral to sustainable recycling and reuse of carbon fiber reinforced polymers (CFRPs) in high-performance industries. The significance of this work is underscored by the need to overcome the limitations of traditional epoxy resins, which are characterized by irreversible covalent bonds that hinder their reprocessability and recyclability. By introducing the small molecule reactive diluent benzyl glycidyl ether (BGE), this study aims to adjust the network structure, thereby accelerating the ester exchange reaction rate and reducing the self-healing time and reprocessing temperature.

Method The methodology of this research involves synthesis of epoxy vitrimers through the incorporation of BGE into bisphenol F epoxy resin (BPF-170) and methyl tetrahydrophthalic anhydride (MTHPA), catalyzed by zinc acetylacetonate (ZAA). The epoxy equivalent ratio of BPF-170 to BGE was systematically varied to fine-tune the network structure. The synthesized materials were characterized using a suite of analytical techniques, including Fourier-transform infrared spectroscopy for chemical structure analysis, differential scanning calorimetry for thermal property determination, thermogravimetric analysis for thermal stability assessment, dynamic mechanical analysis (DMA) for thermomechanical property evaluation, and tensile tests for mechanical performance measurement.

Results The modified epoxy vitrimer formulation TEPV-BGE3, with a BPF-170 to BGE epoxy equivalent ratio of 7∶3, exhibited a substantially reduced glass transition temperature (Tg) from 87.2 to 60.4 ℃, and a decreased vitrimer freezing temperature (Tv) from 80 to 52 ℃. The material maintains high thermal stability, with a 5% weight loss temperature (T95%) of 270 ℃ and a tensile strength of (17.81 ± 1.05) MPa. The self-healing time at 120 ℃ for a 100 μm wide scratch is significantly reduced from 132.3 min to 25.3 min, demonstrating a remarkable improvement in self-healing efficiency. Furthermore, the reprocessing capability of carbon fiber laminates was enhanced, allowing for reshaping within 60 min at 180 ℃. The molecular structure analysis elucidated the curing mechanism and the dynamic ester bond exchange process, indicating the successful introduction of a reversible crosslinking system that facilitates self-healing and reprocessing.

Conclusion The integration of BGE into epoxy vitrimers has been demonstrated to enhance significantly their self-healing and reprocessing properties. The optimized formulation, TEPV-BGE3, exhibits a reduced Tg of 60.4 ℃ and Tv of 52 ℃, enabling faster self-healing at 120 ℃ and efficient reprocessing of carbon fiber laminates within 60 min at 180 ℃. The material's high thermal stability, with a 5% weight loss temperature (T95%) of 270 ℃, and a tensile strength of (17.81 ± 1.05) MPa indicate its suitability for demanding applications. The findings suggest that with precise control over the network structure and composition, it is possible to tailor the properties of epoxy vitrimers to meet specific application requirements while maintaining high thermal and mechanical performance.

Key words: expoxy vitrimer, carbon fiber composite material, dynamic ester bond, self-healing, benzyl glycidyl ether

CLC Number: 

  • TB332

Tab.1

Experimental raw materials and formulations"

样品 质量/g
BPF-170 BGE ZAA MTHPA
TEPV 10 0 0.85 4.89
TEPV-BGE1 9 1.31 0.85 4.89
TEPV-BGE2 8 2.61 0.85 4.89
TEPV-BGE3 7 3.92 0.85 4.89
TEPV-BGE4 6 5.23 0.85 4.89

Fig.1

FT-IR curves of epoxy vitrimer"

Fig.2

DSC heating curves (a) and thermal expansion curves (b) of epoxy vitrimer after curing"

Fig.3

Tensile stress-strain curve of epoxy vitrimer.(a)TEPV and TEPV-BGE1-3; (b)TEPV-BGE4"

Fig.4

Thermal weight loss curves of epoxy vitrimer"

Tab.2

Time of self-healing, thermal welding, and reprocessing min"

样品 自修复时间 热焊接时间 再加工时间
TEPV 132.3 ± 5.5 31.0 ± 3.6 6.1 ± 0.4
TEPV-BGE1 91.0 ± 3.6 23.7 ± 2.1 4.7 ± 0.5
TEPV-BGE2 67.7 ± 4.5 16.3 ± 1.5 3.4 ± 0.3
TEPV-BGE3 25.3 ± 3.0 6.0 ± 1.0 2.3 ± 0.2
TEPV-BGE4 5.7 ± 0.6 2.3 ± 0.6 1.6 ± 0.1

Fig.5

Photos of self-healing and reprocessing of epoxy glass polymer (a) and its carbon fiber composite materials (b)"

Fig.6

Curing mechanism (a) and dynamic ester bond exchange (b) schematic diagram of TEPV"

Fig.7

Curing mechanism (a) and dynamic ester bond exchange (b) schematic diagram of TEPV-BGE"

Fig.8

Storage modulus (a) and tanδ curves(b) of epoxy vitrimer"

Tab.3

Thermal performance parameters of epoxy vitrimer"

样品 Er/MPa 交联密度/(mol·m-3)
TEPV 12.50 1 282.26
TEPV-BGE1 7.45 795.20
TEPV-BGE2 3.44 391.32
TEPV-BGE3 2.44 283.41
TEPV-BGE4 1.20 145.15
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