CN114989563A - Method for regulating and controlling aromatic dithioepoxy mechanotropic wave band - Google Patents
Method for regulating and controlling aromatic dithioepoxy mechanotropic wave band Download PDFInfo
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- CN114989563A CN114989563A CN202210612118.4A CN202210612118A CN114989563A CN 114989563 A CN114989563 A CN 114989563A CN 202210612118 A CN202210612118 A CN 202210612118A CN 114989563 A CN114989563 A CN 114989563A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a method for regulating and controlling an aromatic dithio epoxy mechano-chromic waveband through the change of a molecular structure. The aromatic disulfide epoxy can realize repairability, detachability and reprocessing molding of the thermosetting material by utilizing the dynamic disulfide bonds in the crosslinking network. In addition, the dynamic disulfide bond is homolytic under the action of external force to generate sulfur free radicals for developing color, and more importantly, the color generated by the mechanochromism is influenced by the groups around the sulfur free radicals. Based on the method, the aromatic disulfide epoxy with different structures is prepared by changing the types of the epoxy resin, and the relation between the mechanochromic waveband and the structure is researched. According to the weight portion, 50-100 portions of different epoxy resins and 20-80 portions of epoxy curing agent are cured at high temperature to obtain the aromatic disulfide epoxy polymer with different structures. The prepared aromatic disulfide epoxy polymer not only has dynamic properties of repairability, detachability and the like, but also can realize the regulation and control of 20nm in a mechanochromic wave band.
Description
Technical Field
The invention belongs to the field of high polymer materials, and mainly researches a regulation and control method of aromatic dithioepoxy mechanotropic wave bands.
Background
Mechanical forces often lead to bond scission and chain slippage of polymeric materials, especially thermoset materials, which cannot be recovered once they are destroyed, resulting in failure of a large amount of polymeric materials, resulting in a series of problems such as resource waste and environmental pollution. With the continuous development of dynamic bonds, the method proposes that the dynamic bonds and cross-linked polymers are combined together to form a covalent adaptive network, the dynamic adjustment and rearrangement of a molecular topological structure are realized, and the thermosetting polymer material is endowed with dynamic performances such as self-healing, disassembly, reprocessing and molding and the like. The mechanical color-changing polymer formed by introducing a mechanical carrier (mechanical chromophore) into the thermosetting polymer can further endow the thermosetting polymer with mechanical color-changing performance, and the stimulus generated by mechanical force can cause color change, so that the materials or equipment parts needing repair or replacement can be visually observed, and the mechanical color-changing polymer has important significance for prolonging the service life of the materials and detecting damage.
The aromatic disulfide epoxy is an epoxy polymer material prepared by taking dynamic aromatic disulfide bonds as crosslinking points, and the dynamic disulfide bonds contained in a crosslinking network can realize repairability, detachability and reprocessing molding of the material. In addition, the dynamic disulfide bond is subjected to homolytic cleavage under the action of external force to generate a sulfur free radical, the sulfur free radical can be used as a free radical type mechanical chromophore for developing color, and more importantly, the color generated by the mechanical discoloration is influenced by the groups around the sulfur free radical.
The invention provides a method for regulating and controlling an aromatic dithio epoxy mechano-chromic waveband through the change of a molecular structure. Aromatic disulfide epoxy with different structures is prepared by changing the types of epoxy resin, and the relation between the mechanochromic waveband and the structure is researched. According to the weight portion, 50-100 portions of different epoxy resins and 20-80 portions of epoxy curing agent are cured at high temperature to obtain the aromatic disulfide epoxy polymer with different structures. The prepared aromatic disulfide epoxy polymer not only has the dynamic properties of repairability, detachability and reprocessing molding, but also can realize the regulation and control of 20nm in the mechanochromism wave band.
Disclosure of Invention
The invention provides a method for regulating and controlling aromatic dithioepoxy mechanotropic wave band by changing molecular structure. The aromatic disulfide epoxy polymer with different structures is prepared by changing the types of epoxy resin, 50-100 parts by weight of different types of epoxy resin and 20-80 parts by weight of epoxy curing agent in total are cured at high temperature to completely obtain the aromatic disulfide epoxy polymer with different structures, the epoxy polymer has good repairable, detachable and reprocessed dynamic performance, and more importantly, the mechanochromic wave band can realize the regulation and control of 20 nm.
The epoxy curing agent is an aromatic amino compound containing dynamic disulfide bonds.
The epoxy resin comprises aliphatic epoxy resin, such as 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and the like; alicyclic-containing epoxy resins such as hydrogenated bisphenol a epoxy resin, 1, 2-cyclohexanedicarboxylic acid diglycidyl ether, and the like; aromatic epoxy resins such as bisphenol a diglycidyl ether, triglycidyl p-aminophenol and the like.
Drawings
FIG. 1 is a schematic representation of the mechanochromic mechanism of aromatic dithioepoxy polymers.
FIG. 2 is a disassembly of bisphenol A aromatic dithioepoxy polymer.
FIG. 3 shows the photochromic wavelength bands of aromatic dithioepoxy polymers of different structures.
Detailed Description
The technical solution of the present invention is not limited to the following embodiments, and includes any combination of the embodiments.
The first embodiment is as follows: an aromatic dithiochromic epoxy polymer is prepared by completely curing 50-100 parts by weight of aromatic epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature to obtain the aromatic dithiochromic epoxy polymer containing a plurality of (more than two) benzene rings.
The epoxy resin is bisphenol A diglycidyl ether, and the epoxy curing agent is 4-aminophenyl disulfide (4-AFD).
The aromatic dithiochromic epoxy polymer containing a plurality of (more than two) benzene rings not only has good repairable, detachable and reprocessed dynamic performance, but also has the disassembly as shown in figure 2; meanwhile, the material also has the mechano-discoloration performance, and the wave band of the mechano-discoloration is 650nm, as shown in figure 3.
The second embodiment is as follows: an aromatic dithio-based reversible photochromic epoxy polymer is prepared by completely curing 50-100 parts by weight of alicyclic epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature.
The epoxy resin is hydrogenated bisphenol A diglycidyl ether, and the epoxy curing agent is 4-aminophenyl disulfide (4-AFD).
The alicyclic-containing aromatic dithiochromic epoxy polymer not only has good repairable, detachable and reprocessed dynamic performance; meanwhile, the material also has the mechanochromic performance, and the wave band of the mechanochromic performance is 640nm, as shown in figure 3.
The third concrete implementation mode: an aromatic dithiochromic epoxy polymer is prepared by completely curing 50-100 parts by weight of aliphatic epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature.
The epoxy resin is 1, 4-butanediol diglycidyl ether, and the epoxy curing agent is 4-aminophenyl disulfide (4-AFD).
The aliphatic aromatic dithiochromic epoxy polymer not only has good repairable, detachable and reprocessed dynamic performance; meanwhile, the material also has the mechanochromic property, and the wave band of the mechanochromic property is 660nm, as shown in figure 3.
The fourth concrete implementation mode: an aromatic dithiochromic epoxy polymer is prepared by completely curing 50-100 parts by weight of aromatic epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature to obtain the aromatic dithiochromic epoxy polymer containing a plurality of (more than two) benzene rings.
The epoxy resin is triglycidyl p-aminophenol, and the epoxy curing agent is 4-aminophenyl disulfide (4-AFD).
The aromatic dithio photochromic epoxy polymer containing a plurality of (more than two) benzene rings not only has good dynamic properties of repairability, detachability and reprocessing molding, but also has the mechanochromic property, and the waveband of the mechanochromic property is 651 nm.
The fifth concrete implementation mode is as follows: an aromatic dithiochromic epoxy polymer is prepared by completely curing 50-100 parts by weight of alicyclic epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature to obtain the alicyclic-containing aromatic dithiochromic epoxy polymer.
The epoxy resin is 1, 2-cyclohexanedicarboxylic acid diglycidyl ether, and the epoxy curing agent is 4-aminophenyl disulfide (4-AFD).
The aromatic dithio photochromic epoxy polymer containing alicyclic has good dynamic properties of repairability, detachability and reprocessability and molding, and also has a mechanochromic property, and the wave band of mechanochromic is 643 nm.
Claims (1)
1. The invention provides a method for regulating and controlling aromatic dithioepoxy mechanotropic wave band by changing molecular structure; the preparation method comprises the following steps of preparing the aromatic disulfide epoxy polymer with different structures and mechanochromism by changing the types of epoxy resin, and completely curing 50-100 parts by weight of different types of epoxy resin and 20-80 parts by weight of epoxy curing agent at high temperature to obtain the aromatic disulfide epoxy polymer with different structures, wherein the epoxy polymer has good repairable, detachable and reprocessed dynamic properties, and more importantly, the mechanochromism wave band can realize the regulation and control of 20 nm;
the epoxy curing agent is an aromatic amino compound containing dynamic disulfide bonds;
the epoxy resin comprises aliphatic epoxy resin, such as 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether and the like; alicyclic-containing epoxy resins such as hydrogenated bisphenol a epoxy resin, 1, 2-cyclohexanedicarboxylic acid diglycidyl ether, and the like; aromatic epoxy resins such as bisphenol a epoxy resin, triglycidyl p-aminophenol and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210612118.4A CN114989563B (en) | 2022-06-01 | 2022-06-01 | Method for regulating and controlling aromatic disulfide epoxy electrochromic wave band |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210612118.4A CN114989563B (en) | 2022-06-01 | 2022-06-01 | Method for regulating and controlling aromatic disulfide epoxy electrochromic wave band |
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| CN114989563A true CN114989563A (en) | 2022-09-02 |
| CN114989563B CN114989563B (en) | 2023-09-19 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2949679A1 (en) * | 2014-05-26 | 2015-12-02 | Fundación Cidetec | Thermomechanically reprocessable epoxy composites and processes for their manufacturing |
| WO2018050189A1 (en) * | 2016-09-14 | 2018-03-22 | Aarhus Universitet | Cleavable epoxy compositions based on amine- and disulfide-containing additives |
| CN110564109A (en) * | 2019-10-14 | 2019-12-13 | 中国工程物理研究院化工材料研究所 | Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled |
| CN111040110A (en) * | 2019-01-01 | 2020-04-21 | 翁秋梅 | Force-induced response dynamic polymer and application thereof |
| CN113429741A (en) * | 2021-06-28 | 2021-09-24 | 北京化工大学 | Difunctional epoxy resin composite material and preparation method thereof |
| CN114349934A (en) * | 2021-12-23 | 2022-04-15 | 西南科技大学 | Preparation and disassembly of double-dynamic covalent bond 'parallel interlocking' thermosetting polymer |
| CN114350116A (en) * | 2022-03-01 | 2022-04-15 | 江苏富琪森新材料有限公司 | Epoxy thermosetting resin and preparation method thereof |
-
2022
- 2022-06-01 CN CN202210612118.4A patent/CN114989563B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2949679A1 (en) * | 2014-05-26 | 2015-12-02 | Fundación Cidetec | Thermomechanically reprocessable epoxy composites and processes for their manufacturing |
| WO2018050189A1 (en) * | 2016-09-14 | 2018-03-22 | Aarhus Universitet | Cleavable epoxy compositions based on amine- and disulfide-containing additives |
| CN111040110A (en) * | 2019-01-01 | 2020-04-21 | 翁秋梅 | Force-induced response dynamic polymer and application thereof |
| CN110564109A (en) * | 2019-10-14 | 2019-12-13 | 中国工程物理研究院化工材料研究所 | Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled |
| CN113429741A (en) * | 2021-06-28 | 2021-09-24 | 北京化工大学 | Difunctional epoxy resin composite material and preparation method thereof |
| CN114349934A (en) * | 2021-12-23 | 2022-04-15 | 西南科技大学 | Preparation and disassembly of double-dynamic covalent bond 'parallel interlocking' thermosetting polymer |
| CN114350116A (en) * | 2022-03-01 | 2022-04-15 | 江苏富琪森新材料有限公司 | Epoxy thermosetting resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZI-JIAN LI 等: "Investigation on Self-healing Property of Epoxy Resins Based on Disulfide Dynamic Links", vol. 38, no. 9, pages 932 - 940, XP037202663, DOI: 10.1007/s10118-020-2406-x * |
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