CN115572369B - Single-component epoxy resin with ester bond/imine bond dual dynamic crosslinking network, epoxy cured product and application - Google Patents
Single-component epoxy resin with ester bond/imine bond dual dynamic crosslinking network, epoxy cured product and application Download PDFInfo
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- CN115572369B CN115572369B CN202211302546.3A CN202211302546A CN115572369B CN 115572369 B CN115572369 B CN 115572369B CN 202211302546 A CN202211302546 A CN 202211302546A CN 115572369 B CN115572369 B CN 115572369B
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- 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
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- 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
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- 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
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Abstract
The invention discloses a single-component epoxy resin with an ester bond/imine bond dual dynamic crosslinking network, an epoxy cured product and application thereof. The single-component epoxy resin comprises the following components in parts by weight: 100 parts of carbonyl/aldehyde group-containing monofunctional glycidyl ester, 5-150 parts of amino acid latent curing agent, 0-10 parts of curing reaction accelerator, 0-50 parts of epoxy reactive diluent and 0-400 parts of solvent. The invention also provides an epoxy condensate formed by curing the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network. The single-component epoxy resin with good storage performance can be used in the fields of single-component adhesives, coatings, prepregs, electronic packaging and the like, and in addition, the cured epoxy resin obtained after curing has an ester bond/imine bond dual dynamic crosslinking network and has good reworkability.
Description
Technical Field
The invention relates to a single-component epoxy resin, in particular to a single-component epoxy resin with an ester bond/imine bond dual dynamic crosslinking network, a corresponding epoxy cured product and application thereof, and belongs to the technical field of polymers.
Background
The single-component epoxy resin is formed by matching the latent curing agent with the epoxy resin, and compared with the double-component epoxy resin, the single-component epoxy resin used in production and life has the advantages of improving the working efficiency, reducing the environmental pollution, stabilizing the product quality and the like, and is suitable for modern large-scale production. The epoxy resin is originally of a linear structure, has excellent thermal property, mechanical property, solvent resistance and weather resistance due to an insoluble and infusible permanent three-dimensional crosslinked network after being cured, and is widely applied to the fields of coating, adhesives, composite materials, electronic packaging and the like. However, also because of its permanent three-dimensional crosslinked structure, cured epoxy resins are difficult to recycle, causing huge economic losses and environmental pollution, and the introduction of dynamic covalent bonds into the crosslinked network is an important direction to solve this problem. However, up to now, no patent report has been made on a reworkable one-component epoxy resin.
Disclosure of Invention
The invention mainly aims to provide a single-component epoxy resin with an ester bond/imine bond dual dynamic crosslinking network and a preparation method thereof, so as to overcome the defects and problems in the prior art.
The invention also aims at providing a corresponding epoxy condensate and application.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a single-component epoxy resin with an ester bond/imine bond dual dynamic crosslinking network, which comprises the following components in parts by weight: 100 parts of carbonyl/aldehyde group-containing monofunctional glycidyl ester, 5-150 parts of amino acid latent curing agent, 0-10 parts of curing reaction accelerator, 0-50 parts of epoxy reactive diluent and 0-400 parts of solvent.
In some embodiments, the carbonyl/aldehyde group-containing monofunctional glycidyl ester has a structure as shown in formula I:
wherein R comprises CH 3 Or H.
The embodiment of the invention also provides a preparation method of the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network, which comprises the following steps:
1) Mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, and uniformly stirring to obtain a mixed system;
2) And (3) extracting the solvent in the mixed system to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
The embodiment of the invention also provides an epoxy condensate which is formed by curing the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
The embodiment of the invention also provides a preparation method of the epoxy condensate, which comprises the following steps:
and heating the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network to 90-150 ℃ for curing reaction for 1-8 h, and then performing post curing for 1-6 h at 160-200 ℃ to obtain an epoxy cured product.
The embodiment of the invention also provides application of the single-component epoxy resin or epoxy condensate with the ester bond/imine bond dual dynamic cross-linking network in the fields of preparation of single-component adhesives, coatings, prepregs or electronic packaging and the like.
Compared with the prior art, the invention has at least the following advantages:
1) According to the invention, the amino acid curing agent is matched with the monofunctional epoxy resin containing carbonyl/aldehyde groups to obtain the single-component epoxy resin with good storage performance, and the system has the advantages of abundant and easily obtained raw material sources and simple preparation;
2) The single-component epoxy resin provided by the invention is convenient to operate, has stable product quality, can be used for large-scale product manufacture, and has great commercial value;
3) The single-component epoxy resin condensate provided by the invention has good reworkability due to the double dynamic crosslinking network of ester bond/imine bond, and is beneficial to sustainable utilization and development of resources.
Detailed Description
As described above, in view of the drawbacks of the prior art, the present inventors have long studied and have made a great deal of practical use to propose the technical solution of the present invention. The present invention will be more fully understood from the following detailed description, of which detailed embodiments are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The technical scheme, the implementation process, the principle and the like are further explained as follows.
One aspect of the embodiment of the invention provides a single-component epoxy resin with an ester bond/imine bond dual dynamic crosslinking network, which comprises the following components in parts by weight: 100 parts of carbonyl/aldehyde group-containing monofunctional glycidyl ester, 5-150 parts of amino acid latent curing agent, 0-10 parts of curing reaction accelerator, 0-50 parts of epoxy reactive diluent and 0-400 parts of solvent.
In some embodiments, the carbonyl/aldehyde group-containing monofunctional glycidyl ester has a structure as shown in formula I:
wherein R comprises CH 3 Or H, etc.
In some embodiments, the amino acid latent curing agent includes any one or a combination of two or more of glycine, lysine, alanine, serine, tyrosine, tryptophan, cysteine, phenylalanine, glutamic acid, arginine, aspartic acid, histidine, leucine, isoleucine, valine, threonine, 11-aminoundecanoic acid, and the like, but is not limited thereto.
In some embodiments, the curing reaction accelerator includes any one or a combination of two or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2,4, 6-tris (dimethylaminomethyl) phenol trioleate, triethylamine, triethanolamine, triphenylphosphine, N- (5-chloro-2-hydroxyphenyl) -N ', N' -dimethylurea, N- (2-hydroxy-5-nitrobenzene) -N ', N' -dimethylurea, chromium naphthenate-diethylenetriamine, nickel naphthenate-diethylenetriamine, manganese octoate-N-methylethanolamine, 2-mercaptobenzothiazole, benzoyl peroxide, 2-phenylimidazoline, N-diglycidyl aniline, and the like, but is not limited thereto.
In some embodiments, the epoxy reactive diluent includes any one or a combination of two or more of butyl glycidyl ether, glycidyl acrylate, glycidyl oleate, and the like, but is not limited thereto.
Further, the solvent may be any one or a combination of two or more of water, methanol, ethanol, diethyl ether, n-butanol, isobutanol, and the like, but is not limited thereto.
The mechanism of the invention is as follows: the amino acid latent curing agent is a novel latent epoxy resin curing agent with two curing groups of amino and carboxyl, and because the amino acid has the two curing groups of amino and carboxyl at the same time to form zwitterions, the curing agent has low curing reaction activity, can obtain single-component epoxy resin with good storage performance after being matched with carbonyl/aldehyde-containing single-functionality epoxy resin, can be used in the fields of single-component adhesives, coatings, prepregs, electronic packaging and the like, and can react with glycidyl ester containing aldehyde groups to obtain an ester bond/imine bond dual dynamic crosslinking network, so that the epoxy resin curing agent has good repeatable processing performance.
The invention also provides a preparation method of the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network, which comprises the following steps:
1) Mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, and uniformly stirring to obtain a mixed system;
2) And (3) extracting the solvent in the mixed system to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
In some embodiments, the method of making comprises: the carbonyl/aldehyde group-containing monofunctional glycidyl ester is matched with an amino acid latent curing agent, a curing reaction accelerator, an epoxy reactive diluent and a solvent for pre-curing, the solvent is removed after the system is uniform to obtain single-component epoxy resin, and the single-component epoxy resin is further heated for curing to obtain the epoxy resin cured product capable of being repeatedly processed.
Further, step 1) includes: mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, heating to 60-110 ℃, preferably 70-90 ℃, and stirring for 1-8 hours, preferably 2-3 hours to obtain a mixed system.
Further, step 2) includes: the solvent in the mixed system is pumped out for 0.5 to 4 hours, preferably 0.5 to 2 hours at the temperature of 40 to 120 ℃, preferably 70 to 90 ℃ to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
In another aspect, the present invention provides an epoxy cured product formed by curing the aforementioned one-component epoxy resin having an ester bond/imine bond dual dynamic cross-linked network. The single-component epoxy resin with the ester bond/imine bond dual-dynamic cross-linking network is obtained by matching an amino acid latent curing agent with carbonyl/aldehyde group-containing monofunctional glycidyl ester, and the cured single-component epoxy resin cured product has the ester bond/imine bond dual-dynamic cross-linking network and can be reprocessed through hot pressing treatment.
Further, the single-component epoxy resin with the ester bond/imine bond double dynamic crosslinking network can be subjected to hot pressing for 0.5-2 hours at the temperature of 150-200 ℃ and the pressure of 5-15 MPa, so that the repeated processing can be realized.
Another aspect of the embodiment of the present invention also provides a method for preparing an epoxy cured product, which includes:
and (3) heating the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network to 90-150 ℃ for curing for 1-8 hours, preferably 120-140 ℃ for curing reaction for 1-2 hours, and then performing post curing in a vacuum oven at 160-200 ℃ for 1-6 hours, preferably 180-200 ℃ for 2-4 hours to obtain an epoxy cured product.
In a preferred embodiment of the present invention, the method for preparing the one-component epoxy resin and the epoxy cured product comprises the steps of:
1) Mixing the aldehyde group-containing monofunctional glycidyl ester with an amino acid type latent epoxy resin curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, heating to 60-110 ℃, preferably 70-90 ℃, and stirring for 1-8 hours, preferably 2-3 hours;
2) The solvent in the system is pumped out for 0.5 to 4 hours, preferably 0.5 to 2 hours at the temperature of 40 to 120 ℃ and preferably 70 to 90 ℃ by a vacuum oven, and the solvent is pumped out to obtain the single-component epoxy resin;
3) And (2) heating the single-component epoxy resin obtained in the step (2) to 90-150 ℃ for curing reaction, preferably 120-140 ℃, and performing post-curing in a vacuum oven at 160-200 ℃, preferably 180-200 ℃.
The invention also provides application of the single-component epoxy resin or the epoxy condensate with the ester bond/imine bond dual dynamic cross-linked network in the fields of preparing single-component adhesives, coatings, prepregs or electronic packages and the like.
In conclusion, the single-component epoxy resin cured product obtained by the invention has good reworkability due to the double dynamic crosslinking network of ester bonds/imine bonds, and is beneficial to sustainable utilization and development of resources.
The technical scheme of the invention will be further described through the following specific examples. It should be apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and do not limit the scope of the present invention. It should be noted that the examples described below are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
1. Synthesis of aldehyde group-containing monofunctional glycidyl ester 1
10g of succinic semialdehyde, 15g of epichlorohydrin and 0.25g of tetrabutylammonium bromide were added to a round-bottomed flask, and the mixture was stirred for 10 minutes and reacted at 105℃for 0.5 hour. But to 50 c, 9g of 50wt% aqueous sodium hydroxide solution was added and maintained at 50 c for 3 hours. After the reaction is completed, extracting and rotary evaporating to obtain aldehyde group-containing monofunctional glycidyl ester 1, wherein the structural formula is as follows:
2. synthesis of carbonyl-containing monofunctional glycidyl esters 2
10g of levulinic acid, 15g of epichlorohydrin and 0.25g of tetrabutylammonium bromide are added into a round-bottomed flask, mixed and stirred for 10min, and reacted for 0.5h at 105 ℃. But to 50 c, 9g of 50wt% aqueous sodium hydroxide solution was added and maintained at 50 c for 3 hours. After the reaction is completed, extracting and rotary evaporating to obtain carbonyl-containing monofunctional glycidyl ester 2, wherein the structural formula is as follows:
example 1
Mixing 20g of aldehyde group-containing monofunctional glycidyl ester 1 and 10g of lysine, adding 1g of triethylamine, 20g of ethanol and 5g of water, heating to 90 ℃, stirring for 1h, and removing the solvent in the system at 70 ℃ by using a vacuum oven for 1h to obtain the single-component epoxy resin. And then heating to 120 ℃ for curing reaction for 2 hours, and then performing post-curing in a vacuum oven at 180 ℃ for 4 hours to obtain the epoxy resin cured product.
The storage period of the single-component epoxy resin is 32 days, the tensile strength of the epoxy resin condensate is 87MPa, the tensile modulus is 2000MPa, the elongation at break is 7%, the glass transition temperature is 110 ℃, and the epoxy resin condensate can be repeatedly processed after hot pressing treatment for 30min at 180 ℃.
Example 2
Mixing 20g of carbonyl-containing monofunctional glycidyl ester 2 and 10g of glutamic acid, adding 2g of imidazole, 20g of ethanol, 20g of methanol and 10g of water, heating to 100 ℃, stirring for 2 hours, and removing the solvent in the system at 90 ℃ by using a vacuum oven for 2 hours to obtain the single-component epoxy resin. And then heating to 140 ℃ to carry out a curing reaction for 1h, and then carrying out post-curing in a vacuum oven at 200 ℃ for 1h to obtain an epoxy resin cured product.
The single-component epoxy resin has a storage period of 26 days, the tensile strength of an epoxy resin cured product is 96MPa, the tensile modulus is 2200MPa, the elongation at break is 6%, the glass transition temperature is 105 ℃, the single-component epoxy resin can be repeatedly processed by hot pressing for 30min at 180 ℃, and the single-component epoxy resin can be repeatedly processed by hot pressing for 30min at 180 ℃ under the pressure of 10 MPa.
Example 3
10g of aldehyde-containing monofunctional glycidyl ester 1 and 10g of carbonyl-containing monofunctional glycidyl ester 2,5g of glycine and 5g of tyrosine are mixed, 2g of 2-methylimidazole and 50g of ethanol are added, the temperature is raised to 60 ℃, stirring is carried out for 6 hours, a vacuum oven is used for removing the solvent in the system at 60 ℃ for 1 hour, and the single-component epoxy resin is obtained. Heating to 100 ℃ for curing reaction for 6 hours, then performing post curing in a vacuum oven at 180 ℃ for 2 hours to obtain an epoxy resin cured product, and performing hot pressing treatment for 30 minutes at 160 ℃ under 15MPa for repeated processing.
Example 4
10g of aldehyde group-containing monofunctional glycidyl ester 1 and 10g of carbonyl group-containing monofunctional glycidyl ester 2,5g of cysteine are mixed, 40g of n-butanol or 40g of isobutanol are heated to 110 ℃, stirred for 3 hours, and the solvent in the system is removed by a vacuum oven at 100 ℃ for 2 hours, so that the single-component epoxy resin is obtained. Heating to 120 ℃ for curing reaction for 2 hours, then performing post curing in a vacuum oven at 180 ℃ for 3 hours to obtain an epoxy resin cured product, and performing hot pressing treatment for 1 hour at 200 ℃ under 5MPa for repeated processing.
Example 5
5g of aldehyde group-containing monofunctional glycidyl ester 1 and 15g of carbonyl group-containing monofunctional glycidyl ester 2,3g of lysine, 3g of glutamic acid and 3g of leucine are mixed, 20g of ethanol is added, the temperature is raised to 70 ℃, stirring is carried out for 1h, a vacuum oven is used for removing the solvent in the system at 70 ℃ for 1h, and the single-component epoxy resin is obtained. Heating to 130 ℃ for curing reaction for 1h, then performing post curing in a vacuum oven at 180 ℃ for 4h to obtain an epoxy resin cured product, and performing hot pressing treatment for 2h at 160 ℃ under 5MPa for repeated processing.
Example 6
15g of aldehyde group-containing monofunctional glycidyl ester 1 and 5g of carbonyl group-containing monofunctional glycidyl ester 2,2g of alanine, 2g of serine, 2g of aspartic acid and 2g of threonine are mixed, 70g of ethanol and 10g of water are added, the temperature is raised to 60 ℃, stirring is carried out for 8 hours, a vacuum oven is used for removing the solvent in the system at 90 ℃ for 2 hours, and the single-component epoxy resin is obtained. Heating to 120 ℃ for curing reaction for 2 hours, then performing post curing in a vacuum oven at 180 ℃ for 2 hours to obtain an epoxy resin cured product, and performing hot pressing treatment for 1 hour at 180 ℃ under 5MPa for repeated processing.
Example 7
20g of aldehyde group-containing monofunctional glycidyl ester 1, 10g of 11-aminoundecanoic acid, 10g of threonine and 10g of glutamic acid are mixed, 5g of glycidyl acrylate and 10g of ethanol are added, the temperature is raised to 90 ℃, stirring is carried out for 8 hours, a vacuum oven is used for removing the solvent in the system at 40 ℃ for 4 hours, and the single-component epoxy resin is obtained. Then heating to 90 ℃ for curing reaction for 8 hours, then performing post curing in a vacuum oven at 200 ℃ for 1 hour to obtain an epoxy resin cured product, and performing hot pressing treatment for 30 minutes at 160 ℃ under 15MPa for repeated processing.
Example 8
20g of carbonyl-containing monofunctional glycidyl ester 2 and 1g of glycine 20g are mixed, 10g of butyl glycidyl ether and 20g of water are added, the temperature is raised to 90 ℃, stirring is carried out for 6 hours, a vacuum oven is used for removing the solvent in the system at 120 ℃ for 0.5 hour, and the single-component epoxy resin is obtained. Then heating to 150 ℃ for curing reaction for 1h, then performing post curing in a vacuum oven at 160 ℃ for 6h to obtain an epoxy resin cured product, and performing hot pressing treatment for 30min at 160 ℃ under 5MPa for repeated processing.
Example 9
10g of aldehyde group-containing monofunctional glycidyl ester 1 and 10g of carbonyl group-containing monofunctional glycidyl ester 2, 10g of glycine and 20g of glutamic acid are mixed, 1g of 2-methylimidazole is added, the temperature is raised to 60 ℃, and stirring is carried out for 8 hours, so that the one-component epoxy resin is obtained. And heating to 140 ℃ for curing reaction for 2 hours, then performing post curing in a vacuum oven at 190 ℃ for 3 hours to obtain an epoxy resin cured product, and performing hot pressing treatment for 2 hours at 170 ℃ under 5MPa for repeated processing.
Comparative example 1
20g of bisphenol A type epoxy resin (DER 331, available from Dow chemical), 10g of lysine were mixed, 1g of triethylamine 20g of ethanol, 5g of water were added, the temperature was raised to 90℃and stirring was carried out for 1 hour, and the solvent in the system was removed at 70℃for 1 hour by a vacuum oven, to obtain a pre-cured epoxy resin composition. And heating to 120 ℃ to carry out curing reaction, and then carrying out post-curing in a vacuum oven at 180 ℃ to obtain the epoxy resin cured product. The single-component epoxy resin has a storage period of 30 days, the tensile strength of the epoxy resin cured product is 78MPa, the tensile modulus is 1900MPa, the elongation at break is 7%, the glass transition temperature is 97 ℃, and the epoxy resin cured product cannot be remolded after hot pressing treatment for 2 hours under the pressure of 15MPa at the temperature of 200 ℃.
As is clear from a comparison between example 1 and comparative example 1, the one-component epoxy resin cured product of the present invention has improved tensile strength, tensile modulus and glass transition temperature, and can be repeatedly reworked by a certain hot press treatment.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (14)
1. The single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network is characterized by comprising the following components in parts by weight: 100 parts of carbonyl/aldehyde group-containing monofunctional glycidyl ester, 5-150 parts of amino acid latent curing agent, 0-10 parts of curing reaction accelerator, 0-50 parts of epoxy reactive diluent and 0-400 parts of solvent;
the carbonyl/aldehyde group-containing monofunctional glycidyl ester has a structure shown in a formula I:
；
wherein R is CH 3 Or H.
2. The one-component epoxy resin with an ester/imine bond dual dynamic cross-linked network according to claim 1, characterized in that: the amino acid latent curing agent is selected from any one or more than two of glycine, lysine, alanine, serine, tyrosine, tryptophan, cysteine, phenylalanine, glutamic acid, arginine, aspartic acid, histidine, leucine, isoleucine, valine, threonine and 11-aminoundecanoic acid.
3. The one-component epoxy resin with an ester/imine bond dual dynamic cross-linked network according to claim 1, characterized in that: the curing reaction accelerator is selected from any one or more than two of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2,4, 6-tri (dimethylaminomethyl) phenol trioleate, triethylamine, triethanolamine, triphenylphosphine, N- (5-chloro-2-hydroxyphenyl) -N ', N' -dimethylurea, N- (2-hydroxy-5-nitrobenzene) -N ', N' -dimethylurea, chromium naphthenate-diethylenetriamine, nickel naphthenate-diethylenetriamine, manganese octoate-N-methylethanolamine, 2-mercaptobenzothiazole, benzoyl peroxide, 2-phenylimidazoline and N-diglycidyl aniline.
4. The one-component epoxy resin with an ester/imine bond dual dynamic cross-linked network according to claim 1, characterized in that: the epoxy reactive diluent is selected from any one or more than two of butyl glycidyl ether, glycidyl acrylate and glycidyl oleate.
5. The one-component epoxy resin with an ester/imine bond dual dynamic cross-linked network according to claim 1, characterized in that: the solvent is selected from any one or more than two of water, methanol, ethanol, diethyl ether, n-butanol and isobutanol.
6. The method for preparing a one-component epoxy resin having an ester bond/imine bond dual dynamic cross-linked network according to any one of claims 1 to 5, comprising:
1) Mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, and uniformly stirring to obtain a mixed system;
2) And (3) extracting the solvent in the mixed system to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
7. The method of claim 6, wherein step 1) comprises: mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, heating to 60-110 ℃, and stirring for 1-8 h to obtain a mixed system.
8. The method of claim 7, wherein step 1) comprises: mixing carbonyl/aldehyde group-containing monofunctional glycidyl ester with an amino acid latent curing agent, adding an epoxy reactive diluent, a curing reaction accelerator and a solvent, heating to 70-90 ℃, and stirring for 2-3 h to obtain a mixed system.
9. The method of claim 6, wherein step 2) comprises: and (3) pumping out the solvent in the mixed system for 0.5-4 h at the temperature of 40-120 ℃ to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
10. The method of claim 9, wherein step 2) comprises: and (3) extracting the solvent in the mixed system for 0.5-2 h at 70-90 ℃ to obtain the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network.
11. An epoxy cured product formed by curing the one-component epoxy resin having the ester bond/imine bond dual dynamic cross-linked network according to any one of claims 1 to 5.
12. A method for producing an epoxy cured product, comprising:
heating the single-component epoxy resin with the ester bond/imine bond dual dynamic cross-linking network as claimed in any one of claims 1 to 5 to 90 to 150 ℃ for curing for 1 to 8 hours, and then performing post curing in a vacuum oven at 160 to 200 ℃ for 1 to 6 hours to obtain an epoxy cured product.
13. The method for producing an epoxy cured product according to claim 12, comprising:
and heating the single-component epoxy resin with the ester bond/imine bond dual dynamic crosslinking network to 120-140 ℃ for curing reaction for 1-2 h, and then performing post-curing for 2-4 h at 180-200 ℃ to obtain an epoxy cured product.
14. Use of the one-component epoxy resin with an ester/imine bond dual dynamic cross-linked network according to any one of claims 1 to 5 or the epoxy cured product according to claim 11 for the preparation of one-component adhesives, coatings, prepregs or electronic packaging.
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| CN111187190A (en) * | 2020-01-10 | 2020-05-22 | 华南理工大学 | Epoxy resin based on vanillin and amino acid and preparation method and application thereof |
| CN115197173A (en) * | 2022-07-19 | 2022-10-18 | 南京工业大学 | Bio-based epoxy resin and preparation method thereof |
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| CN109180909A (en) * | 2018-09-04 | 2019-01-11 | 中国林业科学研究院林产化学工业研究所 | Biology base flexible-epoxy and preparation method thereof |
| CN109320918B (en) * | 2018-11-07 | 2021-01-29 | 中国科学院宁波材料技术与工程研究所 | Recyclable carbon fiber reinforced epoxy resin composite material, and preparation method and application thereof |
| CN113667099B (en) * | 2021-07-19 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Single-component epoxy resin based on amino acid type curing agent |
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| CN115197173A (en) * | 2022-07-19 | 2022-10-18 | 南京工业大学 | Bio-based epoxy resin and preparation method thereof |
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