High-toughness, repairable and recoverable epoxy vitrimer and preparation method thereof

Abstract

The invention belongs to the field of functional polymers, and particularly relates to a high-toughness, repairable and recoverable epoxy vitrimer and a preparation method thereof.The epoxy vitrimer is obtained through a ring-opening polymerization reaction of dithiodiphenyl diglycidyl ether, bisphenol A diglycidyl ether and isocyanuric acid tris [2-(3-mercaptopropionyloxy) ethyl ester] at the temperature ranging from the room temperature to 100 DEG C. The epoxy vitrimer has the advantages that the epoxy vitrimer is high in toughness, can be repaired and recoverable, and can be recycled; after being completely cured, the high-toughness characteristic is shown, the tensile strength is not lower than 40 MPa, and the elongation at break is not lower than 140%. Meanwhile, the epoxy vitrimer can realize the characteristics of being repairable and recoverable at a high temperature.

Description

Technical Field

[0001] This invention belongs to the field of functional polymers, specifically relating to a high-strength, tough, repairable, and recyclable epoxy vitrimer and its preparation method. This epoxy vitrimer exhibits high strength and toughness, with a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Simultaneously, this epoxy vitrimer achieves repairability and recyclability at high temperatures and can be disintegrated in both thiol-based and alkaline solutions. Background Technology

[0002] Epoxy, as a typical thermosetting polymer, is widely used in many fields such as the automotive industry, wind turbine blades, and electronic products due to its advantages such as structural stability, excellent performance, and resistance to chemical corrosion. However, because it forms a highly cross-linked three-dimensional cross-linked network after complete curing, traditional epoxy polymers exhibit high brittleness (the elongation at break is usually below 10%), and cannot be disassembled, repaired, or recycled.

[0003] In 2011, the Leibler research group in France constructed dynamically cross-linked epoxy by introducing reversibly exchangeable ester bonds, creatively achieving stress release, reprocessing, disassembly and recycling, and reusability properties of epoxy polymers (Science, 2011, 334, 965-968). In 2016, aromatic disulfide bonds were introduced as reversible dynamic bonds into thermosetting epoxy polymers to construct high-performance epoxy polymer and carbon fiber composites that are disassembled, repairable, and recyclable (Material Horizon, 2016, 3, 241-247). Although the aforementioned epoxy vitrimers achieved repairable and disassembleable properties through dynamic cross-linking structures, their strength and toughness remain similar to traditional epoxy. Their tensile strength and elongation at break are still at a relatively low level, making them susceptible to damage when subjected to significant stress and strain during use.

[0004] Therefore, achieving high strength and toughness in dynamically cross-linked epoxy vitrimer while maintaining its repairability and disassembly remains a significant challenge and is crucial for improving its application performance under high stress and strain conditions. Summary of the Invention

[0005] This invention relates to a polymerization reaction of dithiodiphenyl diglycidyl ether, bisphenol A diglycidyl ether, and tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate to obtain a high-strength, tough, repairable, and recyclable epoxy vitrimer.

[0006] Compared with existing technologies, the present invention has the following advantages: The epoxy vitrimer is composed of 10-30 parts by weight of dithiodiphenyl diglycidyl ether, 25-59.99 parts by weight of bisphenol A diglycidyl ether, 30-40 parts by weight of tri[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 0.01-5 parts by weight of catalyst (triazabicyclo, diazabicyclo, or tertiary amine). It is cured at room temperature to 100 degrees Celsius for more than 4 hours, and after complete curing, its tensile strength is not less than 40 MPa, and its elongation at break is not less than 140%. Furthermore, the epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius, and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, exhibiting high strength and toughness, repairability, and recyclability.

[0007] Optionally, the epoxy vitrimer is composed of 10-15 parts by weight of dithiodiphenyl diglycidyl ether, 45-59.99 parts by weight of bisphenol A diglycidyl ether, 30-35 parts by weight of tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 0.01-1 parts by weight of catalyst.

[0008] Optionally, the epoxy vitrimer is composed of 15-30 parts by weight of dithiodiphenyl diglycidyl ether, 25-45 parts by weight of bisphenol A diglycidyl ether, 30-35 parts by weight of tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 1-5 parts by weight of catalyst. Attached Figure Description

[0009] Figure 1 High-strength, tough, repairable, and recyclable epoxy vitrimer tensile properties;

[0010] Figure 2 High-strength, tough, repairable, and recyclable epoxy vitrimer for repairing damage or fracture surfaces;

[0011] Figure 3 High-strength, tough, repairable, and recyclable epoxy vitrimer is hot-pressed and recycled. Detailed Implementation

[0012] The technical solution of the present invention is not limited to the following specific embodiments, but also includes the same or different scales of related materials or other reasonable combinations.

[0013] Example 1

[0014] The mixture consisted of 10 parts dithiodiphenyl diglycidyl ether, 59.99 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 0.01 parts triazabicyclo catalyst. It was cured at 100°C for 4 hours. Figure 1As shown, its tensile strength is not less than 40 MPa and its elongation at break is not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, exhibiting high strength and toughness, repairability, and recyclability.

[0015] Example 2

[0016] Composed of 10 parts dithiodiphenyl diglycidyl ether, 59.99 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 0.01 parts triazabicyclocatalyst, this epoxy vitrimer, cured at 100°C for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80°C (as demonstrated by repairing the ear of a rabbit sample with a broken ear made of epoxy vitrimer material). Figure 2 As shown, hot pressing and recycling can be achieved at temperatures above 180 degrees Celsius, exhibiting high strength and toughness, repairability, and recyclability.

[0017] Example 3

[0018] Composed of 10 parts dithiodiphenyl diglycidyl ether, 55 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 5 parts tertiary amine catalyst, this epoxy vitrimer, cured at 100°C for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80°C and can be hot-pressed and reshaped at temperatures above 180°C (hot-pressing and reshaping of fragmented epoxy vitrimer pieces), demonstrating high strength, toughness, repairability, and recyclability. Figure 3 As shown.

[0019] Example 4

[0020] Composed of 10 parts dithiodiphenyl diglycidyl ether, 55 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 5 parts triazabicyclic catalyst, this epoxy vitrimer, cured at room temperature for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, demonstrating high strength, toughness, repairability, and recyclability.

[0021] Example 5

[0022] Composed of 20 parts dithiodiphenyl diglycidyl ether, 45 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 5 parts triazabicyclic catalyst, this epoxy vitrimer, cured at room temperature for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, demonstrating high strength, toughness, repairability, and recyclability.

[0023] Example 6

[0024] Composed of 30 parts dithiodiphenyl diglycidyl ether, 35 parts bisphenol A diglycidyl ether, 30 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 5 parts triazabicyclic catalyst, this epoxy vitrimer, cured at room temperature for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, demonstrating high strength, toughness, repairability, and recyclability.

[0025] Example 7

[0026] Composed of 10 parts dithiodiphenyl diglycidyl ether, 45 parts bisphenol A diglycidyl ether, 40 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 5 parts triazabicyclic catalyst, this epoxy vitrimer, cured at room temperature for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, demonstrating high strength, toughness, repairability, and recyclability.

[0027] Example 8

[0028] Composed of 30 parts dithiodiphenyl diglycidyl ether, 25 parts bisphenol A diglycidyl ether, 40 parts tris[2-(3-mercaptopropionyloxy)ethyl isocyanurate], and 5 parts triazabicyclic catalyst, this epoxy vitrimer, cured at room temperature for 4 hours, exhibits a tensile strength of not less than 40 MPa and an elongation at break of not less than 140%. Furthermore, this epoxy vitrimer can repair cracks or fracture surface damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius, demonstrating high strength, toughness, repairability, and recyclability.

[0029] The above embodiments are merely preferred embodiments of the present invention. The embodiments of the present invention are not limited to the above embodiments. It should be understood that those skilled in the art can design many other modifications and embodiments based on this application, and these modifications and embodiments will also fall within the scope and spirit of the principles disclosed in this application.

Claims

1. A high-strength, tough, repairable, and recyclable epoxy vitrimer, characterized in that... The epoxy vitrimer is composed of 10-30 parts by weight of dithiodiphenyl diglycidyl ether, 25-59.99 parts by weight of bisphenol A diglycidyl ether, 30-40 parts by weight of tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 0.01-5 parts by weight of catalyst.

2. The high-strength, tough, repairable, and recyclable epoxy vitrimer according to claim 1, characterized in that, The epoxy vitrimer is composed of 10-15 parts by weight of dithiodiphenyl diglycidyl ether, 45-59.99 parts by weight of bisphenol A diglycidyl ether, 30-35 parts by weight of tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 0.01-1 parts by weight of catalyst.

3. The high-strength, tough, repairable, and recyclable epoxy vitrimer according to claim 1, characterized in that, The epoxy vitrimer is composed of 15-30 parts by weight of dithiodiphenyl diglycidyl ether, 25-45 parts of bisphenol A diglycidyl ether, 30-35 parts of tris[2-(3-mercaptopropionyloxy)ethyl ester] isocyanurate, and 1-5 parts of catalyst.

4. The high-strength, tough, repairable, and recyclable epoxy vitrimer according to any one of claims 1 to 3, characterized in that, The catalyst is one or more of triazabicyclo, diazabicyclo, and tertiary amines.

5. The method for preparing the high-strength, tough, repairable, and recyclable epoxy vitrimer according to any one of claims 1 to 4, characterized in that, The raw materials are cured at room temperature to 100 degrees Celsius for more than 4 hours to obtain epoxy vitrimer.

6. The method for preparing the high-strength, tough, repairable, and recyclable epoxy vitrimer according to claim 5, characterized in that, After complete curing, its tensile strength is not less than 40MPa, its elongation at break is not less than 140%, and it can repair cracks or cross-sectional damage at temperatures above 80 degrees Celsius and can be hot-pressed and recycled at temperatures above 180 degrees Celsius.

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