CN116444768A - High-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin - Google Patents
High-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin Download PDFInfo
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- CN116444768A CN116444768A CN202310419866.5A CN202310419866A CN116444768A CN 116444768 A CN116444768 A CN 116444768A CN 202310419866 A CN202310419866 A CN 202310419866A CN 116444768 A CN116444768 A CN 116444768A
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- 229920005989 resin Polymers 0.000 title claims abstract description 80
- 239000011347 resin Substances 0.000 title claims abstract description 80
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims abstract description 25
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000008439 repair process Effects 0.000 description 11
- 238000011084 recovery Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
Classifications
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrer resin which comprises the following raw materials in parts by mole: e-51 bisphenol A epoxy resin (DGEBA), 3 '-dithiodipropionic acid (DTDPA), 2-methyl hexahydrophthalic anhydride (MHHPA) and Triethanolamine (TEOA), wherein the triethanolamine is a transesterification catalyst, and the 3,3' -dithiodipropionic acid and the 2-methyl hexahydrophthalic anhydride are used as curing agents.
Description
Technical Field
The invention relates to the technical field of resin, in particular to a high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin.
Background
The epoxy resin material is an important thermosetting resin, has good arc resistance, heat resistance, low corrosion resistance, electrical insulation and the like, has excellent physical and mechanical and electrical insulation properties, adhesion performance with various materials and flexibility of using process thereof which are not possessed by other thermosetting plastics, so that the epoxy resin material can be prepared into coating, composite material, casting material, adhesive, molding material and injection molding material, can be widely applied in various fields of national economy, is widely applied to power transmission lines and power equipment in recent years, is mainly cured by using an epoxy resin curing agent in epoxy resin preparation, and has simple curing process and excellent electrical insulation performance;
however, the resin crosslinked network after the epoxy resin curing agent 2-methyl hexahydrophthalic anhydride (MHHPA) is cured is irreversible in permanent crosslinking, and the resin cannot be recycled and reprocessed after being damaged, so that the preparation of the high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin is needed.
Disclosure of Invention
The invention provides a high-efficiency damage self-repairing degradable double dynamic crosslinking Virimer resin, which can effectively solve the problems that in the background art, a resin crosslinking network is irreversible in permanent crosslinking after an epoxy resin curing agent 2-methyl hexahydrophthalic anhydride (MHHPA) is cured, and the resin cannot be recycled and reprocessed after the resin is damaged.
In order to achieve the above purpose, the present invention provides the following technical solutions: the high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrer resin comprises the following raw materials in parts by mole:
e-51 bisphenol A epoxy resin (DGEBA);
3,3' -dithiodipropionic acid (DTDPA);
2-methyl hexahydrophthalic anhydride (MHHPA);
triethanolamine (TEOA);
wherein, triethanolamine is an ester exchange catalyst;
3,3' -dithiodipropionic acid and 2-methyl hexahydrophthalic anhydride are used as curing agents.
According to the technical scheme, the 3,3' -dithiodipropionic acid accounts for 10-50% of the curing agent.
The preparation method of the high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrer resin comprises the following steps:
s1, weighing E-51 resin with a corresponding proportion, adding the E-51 resin into a container, weighing a curing agent DTDPA with a certain proportion, adding the DTDPA into the container, and completely dissolving the DTDPA at 150 ℃;
s2, cooling to 80 ℃, adding a weighed curing agent MHHPA in a certain proportion, and finally adding an ester exchange catalyst TEOA with the mole fraction of epoxy groups of 5%;
s3, stirring for 6-8 min in a water bath kettle at the constant temperature of 80 ℃ to prepare resin prepolymer glue solution;
s4, performing vacuum defoaming treatment for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
s5, slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
s6, solidifying for 2 hours at the temperature of 110 ℃, solidifying for 2 hours at the temperature of 130 ℃, solidifying for 3 hours at the temperature of 150 ℃, naturally cooling and demoulding.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention mixes the carboxylic acid curing agent DTDPA containing dynamic disulfide bond with the traditional anhydride curing agent MHHPA, and prepares and synthesizes the degradable double dynamic crosslinking Vitrimer resin with excellent dynamic characteristic, high-efficiency damage self-repairing characteristic under the catalysis of the transesterification catalyst TEOA.
2. According to the preparation method of the Virimer resin, the proportion of the curing agents DTDPA and MHHPA can be flexibly adjusted along with the requirements of different crosslinking network structures of the resin, so that novel dual-dynamic crosslinking Virimer resin with different dynamic crosslinking structures is constructed, and the preparation method is applied to different scene requirements.
3. The damage repair efficiency of the dual dynamic cross-linked Virimer resin condensate is better than that of a single ester exchange resin system, when the DTDPA content in the curing agent is increased from 0% to 50%, the surface scratch repair rate of the prepared Virimer resin condensate is improved from 70% to 93%, and in addition, the prepared resin system can realize repair of various damage forms such as fracture adhesion, electric tree damage repair and the like.
4. According to the resin disclosed by the invention, the degradation rate of a resin cured product is greatly accelerated along with the increase of the content of the DTDPA, and when the content of the DTDPA is 50%, the resin matrix can be completely degraded in an ethylene glycol solution under the airtight condition at 190 ℃, so that the high-value copper winding in the resin matrix is recycled without damage.
In summary, the transesterification catalyst triethanolamine is introduced into a traditional resin crosslinking network, and meanwhile, a dual-dynamic crosslinking Virimer resin based on transesterification and dynamic disulfide bonds is constructed by blending a curing agent DTDPA containing dynamic disulfide bonds with a traditional curing agent MHHPA, so that the stress relaxation time constant of a resin system is obviously reduced along with the increase of the DTDPA, the dynamic characteristic of the resin system is obviously enhanced, the repair rate of the surface scratches of the prepared Virimer resin cured product is improved, the degradation speed of the resin system is obviously accelerated under the condition of glycol solution, the resin matrix is completely degraded, the defects of poor dynamic characteristic, irrecoverable damage and undegradable damage of the traditional epoxy resin are effectively improved, the damage to a certain extent can be repaired, the service life of equipment is prolonged, the decommissioning recovery treatment of a later period is facilitated, the lossless recovery of high-value materials is realized, and the solid waste pollution is reduced.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is a schematic illustration of the chemical reaction principle of the Virimer resin of the present invention;
FIG. 2 is a schematic illustration of the process for preparing a dual dynamic cross-linked Vitrer resin of the present invention;
FIG. 3 is a graph of stress relaxation of Vicarrier resins of different DTDPA content in accordance with the present invention;
FIG. 4 is a graph of the repair rate of scratches on the surface of the Virimer resin according to the present invention as a function of the amount of different DTDPA;
FIG. 5 is a graph of degradation rate versus DTDPA content in ethylene glycol for a resin system of the present invention;
fig. 6 is a diagram of an experimental view of degradation recovery of a cast winding of a simulated dry-type transformer according to the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, with the understanding that, the preferred embodiments described herein are presented for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1:
as shown in fig. 1-2, the invention provides a technical scheme, namely a high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin, which comprises the following raw materials in parts by mole:
e-51 bisphenol A epoxy resin (DGEBA);
3,3' -dithiodipropionic acid (DTDPA);
2-methyl hexahydrophthalic anhydride (MHHPA);
triethanolamine (TEOA);
wherein, triethanolamine is a transesterification catalyst, and 3,3' -dithiodipropionic acid and 2-methyl hexahydrophthalic anhydride are curing agents.
As can be seen from fig. 1, the reversible network topology gives the macroscopic resin dynamic properties after the two reversible dynamic structures are introduced into the resin cross-linked network.
The method for preparing the high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrer resin comprises the following steps:
weighing a certain amount of E-51 resin, adding the E-51 resin into a container, weighing DTDPA with the molar ratio of a curing agent of 10%, adding the DTDPA into the container, and completely dissolving the DTDPA at 150 ℃;
cooling to 80 ℃, adding weighed 90% of curing agent MHHPA, and finally adding transesterification catalyst TEOA with the mole fraction of epoxy groups of 5%;
stirring in a water bath kettle at a constant temperature of 80 ℃ for 6-8 min to obtain resin prepolymer glue solution;
vacuum defoaming treatment is carried out for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
curing for 2h at 110 ℃, curing for 2h at 130 ℃ and curing for 3h at 150 ℃, naturally cooling and demolding to obtain the degradable double dynamic covalent bond crosslinked Vitrimer resin cured product with certain damage repairing capability.
Example 2: weighing a certain amount of E-51 resin, adding the E-51 resin into a container, weighing DTDPA with the molar ratio of a curing agent of 30%, adding the DTDPA into the container, and completely dissolving the DTDPA at 150 ℃;
cooling to 80 ℃, adding the weighed 70% of curing agent MHHPA, and finally adding the transesterification catalyst TEOA with the mole fraction of epoxy groups of 5%;
stirring in a water bath kettle at a constant temperature of 80 ℃ for 6-8 min to obtain resin prepolymer glue solution;
vacuum defoaming treatment is carried out for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
curing for 2h at 110 ℃, curing for 2h at 130 ℃ and curing for 3h at 150 ℃, naturally cooling and demolding to obtain the degradable double dynamic covalent bond crosslinked Vitrimer resin cured product with certain damage repairing capability.
Example 3: weighing a certain amount of E-51 resin, adding the E-51 resin into a container, weighing DTDPA with the molar ratio of a curing agent of 50%, adding the DTDPA into the container, and completely dissolving the DTDPA at 150 ℃;
cooling to 80 ℃, adding weighed 50% of curing agent MHHPA, and finally adding transesterification catalyst TEOA with the mole fraction of epoxy groups of 5%;
stirring in a water bath kettle at a constant temperature of 80 ℃ for 6-8 min to obtain resin prepolymer glue solution;
vacuum defoaming treatment is carried out for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
curing for 2h at 110 ℃, curing for 2h at 130 ℃ and curing for 3h at 150 ℃, naturally cooling and demolding to obtain the degradable double dynamic covalent bond crosslinked Vitrimer resin cured product with certain damage repairing capability.
Comparative example 1: weighing E-51 resin with corresponding proportion, adding into a container, weighing curing agent MHHPA with mass fraction of 80wt%, and adding into the container;
finally adding an ester exchange catalyst TEOA with the mole fraction of epoxy groups of 5%;
stirring in a water bath kettle at a constant temperature of 80 ℃ for 6-8 min to obtain resin glue solution;
vacuum defoaming treatment is carried out for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
curing at 110 ℃ for 2 hours, 130 ℃ for 2 hours, 150 ℃ for 3 hours, naturally cooling, and demolding to obtain the single transesterification Virimer resin condensate.
According to the contents of comparative example 1 and examples 1 to 3, the following curing agent ratio table was prepared:
the resins prepared in comparative example 1 and examples 1-3 above were tested as follows:
1. stress relaxation performance test: and (3) carrying out tensile loading at 180 ℃, then, over time, keeping the total deformation amount to be 1%, measuring the reduction value of stress over time, normalizing the stress, drawing a stress relaxation curve, and carrying out related test by adopting a tensile mode of a dynamic mechanical analyzer (TA DMA 850) stress relaxation test.
2. Surface scratch damage repair test: and (3) respectively carrying out surface scratches with the same depth and width on the surface of the solidified object sample by using a surgical knife, observing the surface scratches by using an optical microscope, recording the original appearance and width of the scratches, placing the sample in a 190 ℃ drying oven for 5min, taking out, and then observing the related data after repairing the surface scratches again by using the optical microscope.
3. Degradation recovery test: placing a copper wire into a pouring mold to simulate a dry-type transformer winding, adopting the resin preparation and pouring process to prepare a dry-type transformer device, placing the simulation device into ethylene glycol solution, carrying out degradation recovery experiments under the airtight condition of 190 ℃, recording the change of the residual mass ratio of the resin along with degradation time, and observing the detail of the appearance before and after the recovery of the surface of the winding by adopting a scanning electron microscope (SEM, JSM-IT500, JEOR).
As shown in FIG. 3, the stress relaxation test results show that the stress relaxation test data of the Virimer resin system with different DTDPA (draw-down) ratio contents in the curing agent under the condition of 180 ℃ show that as the DTDPA ratio content increases, the stress relaxation time constant of the resin system is obviously reduced, so that the dynamic characteristic of the resin system is obviously enhanced, and when the molar ratio content of the DTDPA curing agent is 50%, the stress relaxation time of a cured product is only 489s.
As shown in fig. 4, the surface scratch damage repair test results show that the relationship between the surface scratch damage repair rates of the Vitrimer resin with different DTDPA ratios in the curing agent shows that when the DTDPA ratio in the curing agent is increased from 0% to 50%, the surface scratch repair rate of the prepared Vitrimer resin cured product is improved from 70% to 93%.
When the DTDPA content is 50%, the damage repair efficiency of the surface scratch for 5min is as high as 93%, and the prepared dual dynamic cross-linked Virimer resin still keeps good comprehensive electrical properties;
when the DTDPA content is 50%, the breakdown voltage is 37.82kV/mm, the leakage current is 38.04 mu A, the dielectric loss tangent value is 0.35%, and the basic requirement of the electrical material is met.
The degradation recovery test result is shown in figure 5, and the relation between different DTDPA (draw-down) ratio contents in the Vitrer resin system and degradation rate in the ethylene glycol solution can be shown that the degradation speed of the resin system is obviously accelerated under the airtight high-temperature condition in the ethylene glycol solution along with the increase of the DTDPA ratio content of the curing agent, and the complete degradation of the resin matrix can be realized in 5.5 hours when the molar ratio content of the DTDPA curing agent is 50%;
as shown in fig. 6, the degradation recovery experiments of the casting windings of the simulated dry-type transformer with different DTDPA duty ratios can show that the degradability of the resin is obviously enhanced along with the increase of the DTDPA duty ratio content containing dynamic disulfide bonds, and the casting device of the simulated dry-type transformer can recover the high-value copper windings in the resin matrix without damage after 6 hours at 190 ℃, and the recovery mode greatly reduces solid waste pollution compared with the traditional incineration landfill.
Finally, it should be noted that: the foregoing is merely a preferred example of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrer resin is characterized in that: comprises the following raw materials in parts by mole:
e-51 bisphenol A epoxy resin (DGEBA);
3,3' -dithiodipropionic acid (DTDPA);
2-methyl hexahydrophthalic anhydride (MHHPA);
triethanolamine (TEOA);
wherein, triethanolamine is an ester exchange catalyst;
3,3' -dithiodipropionic acid and 2-methyl hexahydrophthalic anhydride are used as curing agents.
2. The high efficiency damage self-repairing degradable double dynamic cross-linked Vitrimer resin of claim 1, wherein the 3,3' -dithiodipropionic acid in the curing agent is 10-50%.
3. The method for preparing the high-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin according to any one of claims 1 to 2, which comprises the following steps:
s1, weighing a proportion of E-51 resin, adding the weighed proportion of curing agent DTDPA into a container, and completely dissolving the DTDPA at 150 ℃;
s2, cooling to 80 ℃, adding a weighed proportion of curing agent MHHPA, and finally adding an ester exchange catalyst TEOA with the mole fraction of epoxy groups of 5%;
s3, stirring for 6-8 min in a water bath kettle at the constant temperature of 80 ℃ to prepare resin prepolymer glue solution;
s4, performing vacuum defoaming treatment for 15min in a vacuum drying oven with the temperature environment of 80 ℃;
s5, slowly pouring the mixed solution into a stainless steel die which is preheated and coated with a release agent, and then carrying out constant-temperature vacuum defoaming treatment for 15min;
s6, solidifying for 2 hours at the temperature of 110 ℃, solidifying for 2 hours at the temperature of 130 ℃, solidifying for 3 hours at the temperature of 150 ℃, naturally cooling and demoulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310419866.5A CN116444768A (en) | 2023-04-19 | 2023-04-19 | High-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310419866.5A CN116444768A (en) | 2023-04-19 | 2023-04-19 | High-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116444768A true CN116444768A (en) | 2023-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310419866.5A Pending CN116444768A (en) | 2023-04-19 | 2023-04-19 | High-efficiency damage self-repairing degradable double dynamic crosslinking Vitrimer resin |
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| Country | Link |
|---|---|
| CN (1) | CN116444768A (en) |
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- 2023-04-19 CN CN202310419866.5A patent/CN116444768A/en active Pending
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