Volume 142, Issue 15 e56720

RESEARCH ARTICLE

Cure Kinetics and Thermal Recyclability of Epoxy Vitrimer Based on Triple Dynamic Covalent Bonds

Zengheng Hao,

Zengheng Hao

China Merchants Chongqing Communications Research & Design Institute Co Ltd., Chongqing, China

Chongqing Zhixiang Paving Technology Engineering Co Ltd., Chongqing, China

Contribution: Funding acquisition (equal), Project administration (lead), Writing - original draft (lead)

Search for more papers by this author

Fu Bo,

Fu Bo

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Contribution: Data curation (equal), Investigation (equal), Methodology (equal)

Search for more papers by this author

Yan Wu,

Corresponding Author

Yan Wu

[email protected]

orcid.org/0000-0001-8286-1514

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Correspondence:

Yan Wu ([email protected])

Contribution: Conceptualization (lead), Funding acquisition (equal), Writing - review & editing (equal)

Search for more papers by this author

Xuejuan Cao,

Xuejuan Cao

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Contribution: Methodology (equal), Project administration (equal)

Search for more papers by this author

Zengheng Hao,

Zengheng Hao

China Merchants Chongqing Communications Research & Design Institute Co Ltd., Chongqing, China

Chongqing Zhixiang Paving Technology Engineering Co Ltd., Chongqing, China

Contribution: Funding acquisition (equal), Project administration (lead), Writing - original draft (lead)

Search for more papers by this author

Fu Bo,

Fu Bo

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Contribution: Data curation (equal), Investigation (equal), Methodology (equal)

Search for more papers by this author

Yan Wu,

Corresponding Author

Yan Wu

[email protected]

orcid.org/0000-0001-8286-1514

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Correspondence:

Yan Wu ([email protected])

Contribution: Conceptualization (lead), Funding acquisition (equal), Writing - review & editing (equal)

Search for more papers by this author

Xuejuan Cao,

Xuejuan Cao

College of Material Science and Engineering, Chongqing Jiaotong University, Chongqing, China

Contribution: Methodology (equal), Project administration (equal)

Search for more papers by this author

First published: 09 January 2025

https://doi.org/10.1002/app.56720

Citations: 2

Funding: This work was supported by the National Natural Science Foundation of China (52178440), the National Key Technologies Research and Development Program of China (2022YFB2602605), the Open Fund Project of National Mountain Highway Engineering Technology Research Center, and the Postgraduate Research Innovation Project of Chongqing Jiaotong University (CYS240505).

Share a link

Email
Wechat
Bluesky

ABSTRACT

Epoxy vitrimers have aroused increasing research attention owing to their stable physicochemical properties, recyclability, and reprocessability, and they even achieve rapid self-healing by the design of multiple dynamic covalent. However, based on the requirement of optimized curing process, research on cure kinetics of multiple dynamic epoxy vitrimer with flexibility is overtly insufficient, compared with single dynamic epoxy vitrimers. Herein, an amine curing agent with imine group (DN) and epoxy with disulfide and β-hydroxyl ester groups (EP) were synthesized, respectively, and the thermoset epoxy was fabricated from either diglycidyl ether of bisphenol A (E51) or EP cured with DN. The comparison of E51/DN and EP/DN crosslinked network on cure kinetics, mechanical properties, and self-healing performance was investigated in detail. The activation energy (E _a) of curing reaction for E51D_0.25 was low at 31.79 kJ/mol, while EPD_0.25 had a higher E _a of 58.81 kJ/mol due to complex reactions. Especially, when the conversion was up to 80%, the E _a of EPD_0.25 showed a sharp increment due to the combined effect of crosslinked network and reaction of β-hydroxyl groups. In terms of performance, compared with single dynamic network (E51D_0.25), the flexibility, self-healing, and recyclability of vitrimer were all improved through introduction of triple dynamic bonds.

Conflicts of Interest

The authors declare no conflicts of interest.

Open Research

Data Availability Statement

The authors have nothing to report.

References

1X. Li, X. Gao, J. Liu, et al., “Bi-Functional Epoxy Coating With Long-Term Protection for Q235 Steel Prepared by Incorporating Melamine-Grafted and Carbon-Black-Modified Graphene Oxide,” Surface and Coating Technology 485 (2024): 130883.
10.1016/j.surfcoat.2024.130883
CAS Web of Science® Google Scholar
2Y. Yu, K. He, Z. Hang, W. Liu, and W. Zhao, “Effects of Adhesive Layer Thickness on the Fracture Properties of a Concrete-Epoxy Resin Interface,” Theoretical and Applied Fracture Mechanics 130 (2024): 104239.
10.1016/j.tafmec.2023.104239
CAS Web of Science® Google Scholar
3K. Yang, W. Chen, Y. Zhao, et al., “Enhancing Dielectric Strength of Thermally Conductive Epoxy Composites by Preventing Interfacial Charge Accumulation Using Micron-Sized Diamond,” Composites Science and Technology 221 (2022): 109178.
10.1016/j.compscitech.2021.109178
CAS Web of Science® Google Scholar
4X. Zhang, H. Lin, Y. Hu, D. Ding, F. Cai, and Y. Wu, “Electric Tree Intrinsic Self-Healing Epoxy Insulating Materials Based on Disulfide Bond,” Polymer Degradation and Stability 218 (2023): 110567.
10.1016/j.polymdegradstab.2023.110567
CAS Web of Science® Google Scholar
5N. Tratnik, N. R. Tanguy, and N. Yan, “Recyclable, Self-Strengthening Starch-Based Epoxy Vitrimer Facilitated by Exchangeable Disulfide Bonds,” Chemical Engineering Journal 451 (2023): 138610.
10.1016/j.cej.2022.138610
CAS Web of Science® Google Scholar
6Y. Zhang, S. Zhang, M. Zhai, B. Wei, B. Lyu, and L. Liu, “Self-Healing and Recyclable Castor Oil-Based Epoxy Vitrimer Based on Dual Dynamic Bonds of Disulfide and Ester Bonds,” ACS Applied Polymer Materials 6 (2024): 8399–8408.
10.1021/acsapm.4c01208
CAS Web of Science® Google Scholar
7C. Su, J. Cheng, J. Zhang, and F. Gao, “Tertiary Amine-Based Autocatalytic Transesterification Epoxy Vitrimer: Effect of Tertiary Amine Structure and Covalent Incorporation on the Properties of Vitrimers,” Polymer 300 (2024): 126958.
10.1016/j.polymer.2024.126958
CAS Web of Science® Google Scholar
8F. Liu, L. Wang, S. Xiang, et al., “A Curing Agent for Facile Fabrication of Intrinsically Flame-Retardant Epoxy Vitrimers with Catalyst-Free Mixed Carboxylate/Phosphonate Transesterification,” ACS Applied Polymer Materials 6 (2024): 8159–8168.
10.1021/acsapm.4c01048
CAS Web of Science® Google Scholar
9H. Zhang, L. Zhou, F. Zhang, et al., “Aromatic Disulfide Epoxy Vitrimer Packaged Electronic Devices: Nondestructive Healing and Recycling,” Polymer 255 (2022): 125163.
10.1016/j.polymer.2022.125163
CAS Web of Science® Google Scholar
10M. Chen, S. Duan, L. Zhou, et al., “Recyclable Polymer-Bonded Explosives Enabled by Thiol-Cured Disulfide-Based Epoxy Vitrimers,” Polymer 276 (2023): 125949.
10.1016/j.polymer.2023.125949
CAS Web of Science® Google Scholar
11T. Yan, H. Jiang, W. Pang, et al., “Preparation and Self-Healing Properties of Epoxy Vitrimer Materials Based on Imine Bonds,” Journal of Applied Polymer Science 141 (2024): e55684.
10.1002/app.55684
CAS Web of Science® Google Scholar
12C. Luo, W. Wang, W. Yang, et al., “High-Strength and Multi-Recyclable Epoxy Vitrimer Containing Dual-Dynamic Covalent Bonds Based on the Disulfide and Imine Bond Metathesis,” ACS Sustainable Chemistry & Engineering 11 (2023): 14591–14600.
10.1021/acssuschemeng.3c04345
CAS Web of Science® Google Scholar
13L. Huang, Y. Yang, Z. Niu, et al., “Boronic Ester Bonds Crosslinked Vitrimer Elastomers With Mechanical Robustness, Shape Memory, Self-Healing and Recyclability Properties,” Composites Science and Technology 228 (2022): 109621.
10.1016/j.compscitech.2022.109621
CAS Web of Science® Google Scholar
14Y. Zeng, J. Li, S. Liu, and B. Yang, “Rosin-Based Epoxy Vitrimers With Dynamic Boronic Ester Bonds,” Polymers 13 (2021): 3386.
10.3390/polym13193386
CAS PubMed Web of Science® Google Scholar
15I. Lorero, A. Rodríguez, M. Campo, and S. G. Prolongo, “Thermally Remendable, Weldable, and Recyclable Epoxy Network Crosslinked With Reversible Diels-Alder Bonds,” Polymer 259 (2022): 125334.
10.1016/j.polymer.2022.125334
CAS Web of Science® Google Scholar
16O. Konuray, J. M. Salla, J. M. Morancho, X. Fernández-Francos, M. García-Alvarez, and X. Ramis, “Time-Temperature-Transformation (TTT) Diagram of Dual-Curable Epoxy Thermosets Obtained via Two Sequential Epoxy-Amine Condensations,” Thermochimica Acta 678 (2019): 178305.
10.1016/j.tca.2019.178305
Web of Science® Google Scholar
17L. S. Cividanes, E. A. Simonetti, M. B. Moraes, F. W. Fernandes, and G. P. Thim, “Influence of Carbon Nanotubes on Epoxy Resin Cure Reaction Using Different Techniques: A Comprehensive Review,” Polymer Engineering and Science 54 (2014): 2461–2469.
10.1002/pen.23775
CAS Web of Science® Google Scholar
18B. Jiang, Y. D. Huang, S. He, L. X. Tang, and H. L. Wang, “Quality Analysis and Control Strategies for Epoxy Resin and Prepreg,” Trends in Analytical Chemistry 74 (2015): 68–78.
10.1016/j.trac.2015.03.028
CAS Web of Science® Google Scholar
19H. Ma, X. Zhang, F. Ju, and S. B. Tsai, “A Study on Curing Kinetics of Nano-Phase Modified Epoxy Resin,” Scientific Reports 8 (2018): 3045.
10.1038/s41598-018-21208-0
PubMed Web of Science® Google Scholar
20S. Vyazovkin, “Isoconversional Kinetics of Polymers: The Decade Past,” Macromolecular Rapid Communications 38 (2017): 1600615.
10.1002/marc.201600615
CAS Web of Science® Google Scholar
21S. Vyazovkin, D. Achilias, X. Fernandez-Francos, A. Galukhin, and N. Sbirrazzuoli, “ICTAC Kinetics Committee Recommendations for Analysis of Thermal Polymerization Kinetics,” Thermochimica Acta 714 (2022): 179243.
10.1016/j.tca.2022.179243
CAS Web of Science® Google Scholar
22J. Vogelwaid, F. Hampel, M. Bayer, et al., “In Situ Monitoring of the Curing of Highly Filled Epoxy Molding Compounds: The Influence of Reaction Type and Silica Content on Cure Kinetic Models,” Polymers 16 (2024): 1056.
10.3390/polym16081056
CAS PubMed Web of Science® Google Scholar
23F. Gholinezhad, R. Golhosseini, and O. M. Jazani, “Non-Isothermal DSC Curing Kinetics Study of Silicone-Modified Epoxy/ABS/GO Nanocomposite,” Polymer Composites 43 (2022): 3794–3808.
10.1002/pc.26656
CAS Web of Science® Google Scholar
24F. I. Anagwu and A. A. Skordos, “Cure Kinetics, Glass Transition Advancement and Chemo-Rheological Modelling of an Epoxy Vitrimer Based on Disulphide Metathesis,” Polymer 288 (2023): 126427.
10.1016/j.polymer.2023.126427
CAS Web of Science® Google Scholar
25S. Yang, S. Zhang, F. Luo, H. Li, and F. Gao, “Curing and Thermal Degradation Behavior of Epoxy-Based Vitrimers,” Journal of Applied Polymer Science 141 (2024): e55057.
10.1002/app.55057
CAS Web of Science® Google Scholar
26S. Tang, H. Lin, K. Dong, J. Zhang, and C. Zhao, “Closed-Loop Recycling and Degradation of Guaiacol-Based Epoxy Resin and Its Carbon Fiber Reinforced Composites With S-S Exchangeable Bonds,” Polymer Degradation and Stability 210 (2023): 110298.
10.1016/j.polymdegradstab.2023.110298
CAS Web of Science® Google Scholar
27B. Li, G. Zhu, Y. Hao, R. Li, X. Zhang, and X. Guo, “High-Performance Epoxy Vitrimer Composites Based on Double Dynamic Covalent Bonds,” Journal of Polymer Science 62 (2024): 1468–1479.
10.1002/pol.20230819
CAS Google Scholar
28M. Jouyandeh, F. Tikhani, N. Hampp, et al., “Highly Curable Self-Healing Vitrimer-Like Cellulose-Modified Halloysite Nanotube/Epoxy Nanocomposite Coatings,” Chemical Engineering Journal 396 (2020): 125196.
10.1016/j.cej.2020.125196
CAS Web of Science® Google Scholar
29N. Supriya, K. B. Catherine, and R. Rajeev, “DSC-TG Studies on Kinetics of Curing and Thermal Decomposition of Epoxy–Ether Amine Systems,” Journal of Thermal Analysis and Calorimetry 112 (2013): 201–208.
10.1007/s10973-012-2805-5
CAS Web of Science® Google Scholar
30S. Yang, J. Bai, X. Sun, and J. Zhang, “Robust and Healable Poly(Disulfides) Supramolecular Adhesives Enabled by Dynamic Covalent Adaptable Networks and Noncovalent Hydrogen-Bonding Interactions,” Chemical Engineering Journal 461 (2023): 142066.
10.1016/j.cej.2023.142066
CAS Web of Science® Google Scholar
31M. Chen, L. Zhou, Y. Wu, X. Zhao, and Y. Zhang, “Rapid Stress Relaxation and Moderate Temperature of Malleability Enabled by the Synergy of Disulfide Metathesis and Carboxylate Transesterification in Epoxy Vitrimers,” ACS Macro Letters 8 (2019): 255–260.
10.1021/acsmacrolett.9b00015
CAS PubMed Web of Science® Google Scholar
32C. Luo, W. Yang, W. Qi, et al., “Cost-Efficient and Recyclable Epoxy Vitrimer Composite With Low Initial Viscosity Based on Exchangeable Disulfide Crosslinks,” Polymer Testing 113 (2022): 107670.
10.1016/j.polymertesting.2022.107670
CAS Web of Science® Google Scholar
33L. Cheng, S. Liu, and W. Yu, “Recyclable Ethylene-Vinyl Acetate Copolymer Vitrimer Foams,” Polymer 222 (2021): 123662.
10.1016/j.polymer.2021.123662
CAS Web of Science® Google Scholar

Citing Literature

Volume142, Issue15

April 15, 2025

e56720

Cure Kinetics and Thermal Recyclability of Epoxy Vitrimer Based on Triple Dynamic Covalent Bonds

ABSTRACT

Conflicts of Interest

Open Research

Data Availability Statement

References

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Cure Kinetics and Thermal Recyclability of Epoxy Vitrimer Based on Triple Dynamic Covalent Bonds

ABSTRACT

Conflicts of Interest

Open Research

Data Availability Statement

References

Citing Literature

References

Related

Information