CN-122011340-A - Detachable and repairable epoxy vitrimer based on dynamic carbon-sulfur bond and preparation method thereof

Abstract

The invention belongs to the field of functional polymers, and in particular relates to a detachable and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds and a preparation method thereof, wherein epoxy vitrimer is prepared from diphenylmethane bismaleimide, trimethylolpropane triglycidyl ether, dimercaptodiphenyl sulfide or octadithiol and triethylamine through a curing reaction at 50-150 ℃ for more than 4 hours. After curing is complete, the epoxy vitrimer has good solvent resistance, and simultaneously, complete disassembly can be realized in a specific mercapto solvent, and in addition, hot press recovery and reshaping can be realized at high temperature.

Inventors

• CHEN MAO
• ZOU JINGWEN
• KOU YAN

Assignees

• 中国工程物理研究院化工材料研究所

Dates

Publication Date

20260512

Application Date

20260109

Claims (5)

1. 1. The detachable and repairable epoxy vitrimer based on the dynamic carbon-sulfur bond is characterized by comprising, by weight, 10-40 parts of diphenylmethane bismaleimide, 10-70 parts of trimethylolpropane triglycidyl ether, 15-49.9 parts of dimercaptodiphenyl sulfide or octadithiol and 0.1-5 parts of triethylamine.
2. 2. The method for preparing the detachable repairable epoxy vitrimer based on the dynamic carbon-sulfur bond, which is disclosed in claim 1, is characterized in that all the raw materials are mixed and then are cured and reacted for more than 4 hours at 50-150 ℃.
3. 3. The method for preparing the detachable and repairable epoxy vitrimer based on the dynamic carbon-sulfur bond according to claim 2, wherein the epoxy vitrimer has good solvent resistance after complete curing, and can be completely detached in a mercapto solution.
4. 4. The method for preparing the detachable repairable epoxy vitrimer based on the dynamic carbon-sulfur bond according to claim 3, wherein the epoxy vitrimer can realize hot-press recycling and reshaping at 140 ℃.
5. 5. The preparation method of the detachable and repairable epoxy vitrimer based on the dynamic carbon-sulfur bond, which is disclosed in claim 4, is characterized in that the raw materials comprise, by weight, 10-40 parts of diphenylmethane bismaleimide, 30-70 parts of trimethylolpropane triglycidyl ether, 15-49.9 parts of dimercaptodiphenyl sulfide or octadithiol, and 3-5 parts of triethylamine.

Description

Detachable and repairable epoxy vitrimer based on dynamic carbon-sulfur bond and preparation method thereof Technical Field The invention belongs to the field of functional polymers, and particularly relates to a detachable and repairable epoxy vitrimer based on a dynamic carbon-sulfur bond and a preparation method thereof. The epoxy vitrimer takes a dynamic carbon-sulfur bond as a dynamic unit, and an epoxy polymer as a framework, and is prepared by polymerizing trifunctional epoxy, difunctional mercapto, difunctional maleimide and triethylamine. Meanwhile, the epoxy vitrimer can realize damage repair and hot-pressing recovery and reshaping at high temperature, and can realize disassembly in a sulfhydryl solution. Background Epoxy is used as a typical thermosetting polymer, and is widely applied to various fields such as automobile industry, wind power blades, electronic products and the like as an adhesive, a coating and pouring sealant due to the advantages of stable structure, excellent performance, chemical corrosion resistance and the like. However, the traditional epoxy polymer cannot be disassembled, repaired and recycled because it forms a highly crosslinked bulk crosslinked network after being fully cured. The Leibler subject group constructs a dynamic cross-linked epoxy glass polymer (vitrimer) based on reversible exchange ester bonds, and creatively realizes the characteristics of stress release, reprocessing, disassembly and recovery, recycling and the like of the epoxy polymer (Science, 2011, 334, 965-968). Then, disulfide bonds, imine bonds, borate bonds and other different dynamic bonds are introduced into the epoxy network for realizing the functions of disassembling, reshaping, recycling and the like of the epoxy polymer. However, exploring more and more dynamically crosslinked epoxy vitrimer remains of great importance for enriching its material system and properties. Here, we polymerized a trifunctional epoxy, a difunctional mercapto, a difunctional maleimide and a triethylamine with a novel dynamic carbon-sulfur bond as a dynamic unit and an epoxy polymer as a backbone to obtain a dynamic carbon-sulfur bond crosslinked epoxy vitrimer. The epoxy vitrimer has good solvent resistance, can realize damage repair and hot-pressing recovery and reshaping at high temperature, and can realize disassembly in a sulfhydryl solution. Disclosure of Invention The invention uses diphenylmethane bismaleimide, trimethylolpropane triglycidyl ether, dimercapto diphenyl sulfide or octadithiol and triethylamine to carry out polymerization reaction, and the detachable and repairable epoxy vitrimer based on dynamic carbon-sulfur bonds is obtained, and the reaction flow is shown in figure 3. Compared with the prior art, the epoxy vitrimer has the following effects that 10-40 parts of diphenylmethane bismaleimide, 70-10 parts of trimethylolpropane triglycidyl ether, 15-49.9 parts of dimercaptodiphenyl sulfide or octanedithiol and 5-0.1 part of triethylamine are used as raw materials according to the weight fraction, and the curing reaction is carried out for more than 4 hours at 50-150 ℃. After the curing is completed, the epoxy vitrimer has good solvent resistance, and meanwhile, complete disassembly can be realized in a sulfhydryl solution, and in addition, hot-press recovery and reshaping can be realized at the temperature of more than 140 ℃. The invention can also take 10-40 parts of diphenylmethane Bismaleimide (BMI), 30-70 parts of trimethylolpropane triglycidyl ether, 15-49.9 parts of dimercaptodiphenyl sulfide (TBT) or Octadithiol (ODT) and 3-5 parts of triethylamine as raw materials, and the curing reaction is carried out for more than 4 hours at 50-150 ℃. After the curing is completed, the epoxy vitrimer has good solvent resistance, and meanwhile, complete disassembly can be realized in a sulfhydryl solution, and in addition, hot-press recovery and reshaping can be realized at the temperature of more than 140 ℃. Drawings FIG. 1 solvent resistance of repairable epoxy vitrimer based on dynamic carbon-sulfur bond detachability; FIG. 2 is a graph of hot press reforming and selectively detachable characteristics of repairable epoxy vitrimer based on a dynamic carbon-sulfur bond; FIG. 3 is a process flow of the preparation of repairable epoxy vitrimer based on a dynamic carbon-sulfur bond. Detailed Description The technical scheme of the invention is not limited to the following specific embodiments, and also comprises the amplification of the same proportion or different proportions or other reasonable combinations of related materials. Example 1 10 Parts of diphenylmethane bismaleimide, 70 parts of trimethylolpropane triglycidyl ether, 15 parts of dimercapto diphenyl sulfide and 5 parts of triethylamine are used as raw materials, and the curing reaction is carried out for more than 4 hours at 50 ℃. After curing is complete, the epoxy vitrimer has good solvent resistance (as shown in FIG. 1). In addition, co