Detachable and repairable epoxy vitrimer based on dynamic carbon-sulfur bond and preparation method of detachable and repairable epoxy vitrimer
The preparation of epoxy vitrimer through dynamic carbon-sulfur bond crosslinking solves the problem that traditional epoxy polymer materials cannot be disassembled, repaired, and recycled. It realizes the solvent resistance and renewability of epoxy materials, and has the ability to repair damage and recycle by hot pressing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- INST OF CHEM MATERIAL CHINA ACADEMY OF ENG PHYSICS
- Filing Date
- 2026-01-09
- Publication Date
- 2026-05-12
AI Technical Summary
Traditional epoxy polymer materials form a highly cross-linked network after complete curing, which cannot be disassembled, repaired, or recycled, thus limiting their potential for reuse and recycling.
Using dynamic carbon-sulfur bonds as crosslinking units, a disassembled and repairable epoxy vitrimer is prepared by polymerizing trifunctional epoxy, difunctional thiol and difunctional maleimide, etc. It has solvent resistance and can achieve damage repair and hot-press recycling and remolding at high temperature.
It achieves solvent resistance, disassembly and renewability of epoxy vitrimer, can be completely disassembled in mercapto solution, and can be recycled and reshaped at high temperature by hot pressing, thus improving the recyclability of the material.
Smart Images
Figure CN122011340A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional polymers, specifically relating to a removable and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds and its preparation method. The epoxy vitrimer uses dynamic carbon-sulfur bonds as dynamic units and an epoxy polymer as the backbone, and is obtained by polymerization of trifunctional epoxy, difunctional thiol, difunctional maleimide, and triethylamine. Furthermore, this epoxy vitrimer can achieve damage repair and hot-press recycling at high temperatures, and can be disassembled in a thiol solution. 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 chemical corrosion resistance. However, because it forms a highly cross-linked three-dimensional cross-linked network after complete curing, traditional epoxy polymers cannot be disassembled, repaired, or recycled.
[0003] The Leibler research group in France constructed dynamically cross-linked epoxy-based glass vitrifiers based on reversibly exchangeable ester bonds, creatively achieving stress release, reprocessing, disassembly and recycling, and reusability of epoxy polymers (Science, 2011, 334, 965-968). Subsequently, different dynamic bonds, such as disulfide bonds, imine bonds, and borate ester bonds, were introduced into the epoxy network to achieve functions such as disassembly, reprocessing, and recycling of epoxy polymers. However, exploring more and newer dynamically cross-linked epoxy vitrifiers remains of great significance for enriching their material systems and properties.
[0004] Here, we used a novel dynamic carbon-sulfur bond as the dynamic unit and an epoxy polymer as the backbone to polymerize a dynamically carbon-sulfur bond crosslinked epoxy vitrimer from trifunctional epoxy, difunctional thiol, difunctional maleimide, and triethylamine. This epoxy vitrimer exhibits good solvent resistance, can achieve damage repair and hot-press recycling at high temperatures, and can be decomposed in thiol solutions. Summary of the Invention
[0005] This invention utilizes a polymerization reaction of diphenylmethane bismaleimide, trimethylolpropane triglycidyl ether, dimercaptodiphenyl sulfide, or octanedithiol with triethylamine to obtain a resolvable and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds. The reaction process is as follows: Figure 3 As shown.
[0006] Compared with existing technologies, the present invention has the following advantages: The epoxy vitrimer is prepared by using 10-40 parts by weight of diphenylmethane bismaleimide, 70-10 parts by weight of trimethylolpropane triglycidyl ether, 15-49.9 parts by weight of dimercaptodiphenyl sulfide or octanedithiol, and 5-0.1 parts by weight of triethylamine as raw materials, and is cured at 50-150 degrees Celsius for more than 4 hours (a higher temperature is used when the amount of triethylamine is small, and a lower temperature is used when the amount of triethylamine is large). After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in mercapto solutions. In addition, it can be hot-pressed and recycled at temperatures above 140 degrees Celsius.
[0007] This invention can also use 10-40 parts of diphenylmethane bismaleimide (BMI), 30-70 parts of trimethylolpropane triglycidyl ether, 15-49.9 parts of dimercaptodiphenyl sulfide (TBT) or octanedithiol (ODT), and 3-5 parts of triethylamine as raw materials, and cure at 50-150 degrees Celsius for more than 4 hours. After complete curing, the epoxy vitrimer has good solvent resistance, and can be completely decomposed in a mercapto solution. In addition, it can be hot-pressed and recycled at temperatures above 140 degrees Celsius. Attached Figure Description
[0008] Figure 1 Solvent resistance of repairable epoxy vitrimer based on the disintegration of dynamic carbon-sulfur bonds;
[0009] Figure 2 Based on the removable dynamic carbon-sulfur bond, repairable epoxy vitrimer features hot-press remolding and selective removability.
[0010] Figure 3 A process for preparing repairable epoxy vitrimer based on the disintegration of dynamic carbon-sulfur bonds. Detailed Implementation
[0011] 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.
[0012] Example 1
[0013] Using 10 parts diphenylmethane bismaleimide, 70 parts trimethylolpropane triglycidyl ether, 15 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 50 degrees Celsius for at least 4 hours. After complete curing, this epoxy vitrimer exhibits good solvent resistance (e.g., Figure 1 (As shown). Furthermore, complete disintegration can be achieved in a mercapto solution, and hot-pressing recycling and remolding can be performed at temperatures above 140 degrees Celsius (e.g., Figure 2 (As shown).
[0014] Example 2
[0015] Using 10 parts diphenylmethane bismaleimide, 70 parts trimethylolpropane triglycidyl ether, 15 octanedithiol, and 5 triethylamine as raw materials, the epoxy vitrimer is cured at above 50 degrees Celsius for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at above 140 degrees Celsius.
[0016] Example 3
[0017] Using 10 parts diphenylmethane bismaleimide, 70 parts trimethylolpropane triglycidyl ether, 15 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the epoxy vitrimer was cured at 150°C for more than 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0018] Example 4
[0019] Using 10 parts diphenylmethane bismaleimide, 70 parts trimethylolpropane triglycidyl ether, 15 parts dimercaptodiphenyl sulfide, and 0.1 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, this epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0020] Example 5
[0021] Using 10 parts diphenylmethane bismaleimide, 60 parts trimethylolpropane triglycidyl ether, 25 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0022] Example 6
[0023] Using 10 parts diphenylmethane bismaleimide, 50 parts trimethylolpropane triglycidyl ether, 35 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0024] Example 7
[0025] Using 10 parts diphenylmethane bismaleimide, 40 parts trimethylolpropane triglycidyl ether, 45 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0026] Example 8
[0027] Using 10 parts diphenylmethane bismaleimide, 30 parts trimethylolpropane triglycidyl ether, 49.9 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, this epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0028] Example 9
[0029] Using 20 parts diphenylmethane bismaleimide, 40 parts trimethylolpropane triglycidyl ether, 35 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0030] Example 10
[0031] Using 30 parts diphenylmethane bismaleimide, 30 parts trimethylolpropane triglycidyl ether, 35 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0032] Example 11
[0033] Using 40 parts diphenylmethane bismaleimide, 20 parts trimethylolpropane triglycidyl ether, 35 parts dimercaptodiphenyl sulfide, and 5 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0034] Example 12
[0035] Using 40 parts diphenylmethane bismaleimide, 10 parts trimethylolpropane triglycidyl ether, 45 parts dimercaptodiphenyl sulfide, and 3 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0036] Example 13
[0037] Using 40 parts diphenylmethane bismaleimide, 10 parts trimethylolpropane triglycidyl ether, 49.9 parts dimercaptodiphenyl sulfide, and 0.1 parts triethylamine as raw materials, the epoxy vitrimer was cured at 150°C for more than 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0038] Example 14
[0039] Using 40 parts diphenylmethane bismaleimide, 10 parts trimethylolpropane triglycidyl ether, 49.9 parts octanedithiol, and 0.1 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, the epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0040] Example 15
[0041] Using 10 parts diphenylmethane bismaleimide, 70 parts trimethylolpropane triglycidyl ether, 15 parts octanedithiol, and 0.1 parts triethylamine as raw materials, the mixture was cured at 150°C for at least 4 hours. After complete curing, this epoxy vitrimer exhibits good solvent resistance. Furthermore, it can be completely decomposed in a mercapto solution and can be hot-pressed and reshaped at temperatures above 140°C.
[0042] 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 removable and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds, characterized in that, The raw materials, measured by weight, include: 10-40 parts diphenylmethane bismaleimide, 10-70 parts trimethylolpropane triglycidyl ether, 15-49.9 parts dimercaptodiphenyl sulfide or octanedithiol, and 0.1-5 parts triethylamine.
2. The method for preparing a disassembled and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds as described in claim 1, characterized in that, After mixing all the raw materials, cure the mixture at 50-150 degrees Celsius for more than 4 hours.
3. The method for preparing a disassembled and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds according to claim 2, characterized in that, Once fully cured, the epoxy vitrimer exhibits excellent solvent resistance and can be completely decomposed in thiol solutions.
4. The method for preparing a disassembled and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds according to claim 3, characterized in that, This epoxy vitrimer can be hot-pressed and recycled at temperatures above 140 degrees Celsius.
5. The method for preparing a disassembled and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds according to claim 4, characterized in that, The raw materials, measured by weight, include: 10-40 parts diphenylmethane bismaleimide, 30-70 parts trimethylolpropane triglycidyl ether, 15-49.9 parts dimercaptodiphenyl sulfide or octanedithiol, and 3-5 parts triethylamine.