CN111909359A - Curing agent and preparation method and application thereof - Google Patents
Curing agent and preparation method and application thereof Download PDFInfo
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- CN111909359A CN111909359A CN202010690678.2A CN202010690678A CN111909359A CN 111909359 A CN111909359 A CN 111909359A CN 202010690678 A CN202010690678 A CN 202010690678A CN 111909359 A CN111909359 A CN 111909359A
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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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
- C08G59/5086—Triazines; Melamines; Guanamines
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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 curing agent and a preparation method and application thereof. The curing agent has degradability and different numbers of curing active groups, and can realize the adjustment of the crosslinking density and performance of a cured product. The cured product obtained by mixing and curing the curing agent containing 4-6 primary amine groups and the epoxy prepolymer has adjustable crosslinking density and high mechanical strength, and the Young modulus can reach 2893MPa and the maximum stress can reach 95MPa according to a standard test method GB/T2567-2008, so that the cured product can replace the traditional curing agent.
Description
Technical Field
The invention belongs to the technical field of curing agents, and particularly relates to a curing agent and a preparation method and application thereof.
Background
The epoxy resin has excellent mechanical property, electrical insulation property, bonding property and the like, so the epoxy resin is widely applied to the fields of composite materials, casting parts, electronic and electric appliances and the like, and is one of the most widely applied and researched thermosetting resin varieties. But the waste epoxy resin products are treated as garbage due to the difficult degradability of the epoxy resin products, thereby causing serious environmental pollution. Therefore, the research on the degradable epoxy resin has important theoretical and practical significance.
At present, the research on the degradable epoxy resin is mainly used for synthesizing the degradable epoxy curing agent and preparing the degradable epoxy prepolymer. Or introducing cleavable ketal and acetal groups into the curing agent, or directly synthesizing hexahydrotriazine derivatives with epoxy groups, but these methods have complicated synthetic processes, a large amount of by-products, and the cured products thereof cannot be completely decomposed.
Manchurian Qi, a Ningbo material, reports an amine curing agent with 3 hydrazide groups and a hexahydrotriazine ring structure, and an epoxy cured product prepared by the amine curing agent has better mechanical property and degradation property. Although the synthetic method of the curing agent is simpler, the crosslinking density of a cured product is not adjustable, and compared with the traditional curing agent such as DDM, the curing agent has low crosslinking density and poor mechanical property.
Disclosure of Invention
The invention aims to provide a curing agent with degradability and different numbers of curing active groups, and a preparation method and application thereof, so as to adjust the crosslinking density and performance of a cured product. The method comprises the steps of synthesizing hexahydrotriazine derivatives containing different numbers of nitric acid groups, reducing to obtain curing agents with different numbers of primary amine groups, and curing by adopting different curing agents and epoxy prepolymer to achieve the purpose of controlling the crosslinking density of a cured product. The curing agent can simultaneously endow the epoxy cured material with high mechanical strength and acid degradation characteristic.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
a curing agent having the general formula of formula I,
wherein A, B is at least one of aliphatic alkylene, aryl, aliphatic cyclic alkyl and heterocycle independently; r1、R2、R3、R4、R5、R6At least 4 of which are-NH2The others are independently selected from-H, -CH3At least one of-OH.
Preferably, I is selected from the group consisting of:
in a second aspect of the present invention, there is provided:
the preparation method of the curing agent comprises the following steps:
(1) adding into a solvent a
Reacting with formaldehyde to obtain secondary diamine containing nitric acid groups;
(2) adding secondary diamine, formaldehyde and
dropwise adding an acid solution, reacting, and purifying to obtain an intermediate product of hexahydrotriazine ring;
(3) and carrying out amination reaction on the intermediate product of the hexahydrotriazine ring to obtain the epoxy resin curing agent.
Preferably, the above
And the above
In, X1、X2At least one is a nitrate group, the others are selected from-H, -CH3At least one of-OH.
Preferably, the above
Is at least one selected from p-nitroaniline, p-nitrobenzylamine, 4-nitronaphthylamine, 3, 5-dinitroaniline, 2-amido-5-nitropyridine and 2-amido-5-nitropyrimidine.
Preferably, the above
Is selected from p-nitroaniline, p-nitrobenzylamine, 4-nitronaphthylamine,At least one of 3-nitro-5-methylaniline, 3, 5-dinitroaniline, 2-aminoethanol, 2-nitroacetamine, 3-nitropropylamine, 4-nitropropylamine, 2-amino-5-nitropyridine and 2-amino-5-nitropyrimidine.
Preferably, the step (1) is a step of
And the molar ratio of formaldehyde is 1: 1 to 3.
Preferably, the reaction temperature in the step (1) is 25-60 ℃, and the reaction time is 1-8 hours.
Preferably, the secondary diamine, formaldehyde, or a mixture thereof in the step (2),
The molar ratio of (1) - (3) to (0-2).
Preferably, in the step (1), the solvent a is at least one selected from the group consisting of water, methanol, ethanol, acetonitrile, and tetrahydrofuran.
Preferably, the solvent b in the step (2) is at least one selected from the group consisting of water, methanol, ethanol, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
Preferably, in the step (2), the acidic solution is at least one selected from hydrochloric acid, formic acid, acetic acid and sulfuric acid.
Preferably, the reaction temperature in the step (2) is 60-120 ℃, and the reaction time is 3-24 hours.
Preferably, the amination reaction in the step (3) is one selected from catalytic hydrogenation reductive amination and metal electron transfer reductive amination.
Preferably, the reducing agent system for catalytic hydrogenation reductive amination is at least one selected from the group consisting of a palladium carbon-hydrazine hydrate reduction system, a palladium carbon-hydrogen reduction system, a raney nickel-hydrazine hydrate reduction system, a raney nickel-hydrogen reduction system, and a palladium carbon-ammonium formate reduction system.
Preferably, the reducing agent system for the electron transfer reductive amination of the metal is at least one selected from the group consisting of an iron-ammonium chloride reduction system, an iron-hydrochloric acid reduction system, a zinc-ammonium chloride reduction system, a zinc-hydrochloric acid reduction system, and an indium-ammonium chloride reduction system.
In a third aspect of the present invention, there is provided:
an epoxy resin cured product comprises the following components: the curing agent and the epoxy resin prepolymer.
Preferably, the epoxy resin prepolymer is at least one selected from the group consisting of bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, triglycidyl ether, tetrabromobisphenol a diglycidyl ether, collaphthalenedicarboxylic acid diglycidyl ether, glycidylamine epoxy resins, and aliphatic epoxy resins.
The cured epoxy resin can be degraded in an acidolysis solution.
The concentration of hydrogen ions in the acidolysis solution is 0.1-8 monl/L.
The degradation temperature is 25-120 ℃, and the degradation time is 12 hours-14 days.
The acidolysis solution is an aqueous solution or an organic solution of an acid.
The acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, acetic acid and trifluoroacetic acid;
the organic solution is at least one selected from tetrahydrofuran, dimethyl sulfoxide, methanol, ethanol and acetone.
In a fourth aspect of the present invention, there is provided:
a method for preparing the cured epoxy resin comprises the following steps:
(1) heating and stirring the curing agent and the epoxy resin prepolymer, and vacuumizing to obtain a pre-polymerization liquid;
(2) and pouring the prepolymer into a mold, vacuumizing, curing and cooling to obtain an epoxy resin cured product.
Preferably, the epoxy resin prepolymer is at least one selected from the group consisting of bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, triglycidyl ether, tetrabromobisphenol a diglycidyl ether, phthalic acid diglycidyl ether, glycidyl amine epoxy resins, and aliphatic epoxy resins.
Preferably, the stirring temperature in the step (1) is 30-60 ℃, and the stirring time is 0.5-1 hour.
Preferably, the curing in the step (2) is divided into three temperature stages of 70-90 ℃, 110-130 ℃ and 150-180 ℃, and the curing time of each temperature stage is 1-2 hours.
The invention has the beneficial effects that:
1. the curing agent has curing active groups with different degradability and quantity, and can realize the adjustment of the crosslinking density and the performance of a cured product.
2. According to the invention, a primary amine compound with a nitrate group reacts with formaldehyde to prepare secondary diamine, and then a second primary amine is added to prepare a hexahydrotriazine intermediate product with a specific number of nitrate groups. The degradable curing agent with a specific number of primary amine groups is prepared by reductive amination.
3. The cured material obtained by mixing and curing the curing agent containing 4-6 primary amine groups and the epoxy prepolymer has adjustable crosslinking density and high mechanical strength, the Young modulus tested according to GB/T2410-2008 can reach 2893MPa, the maximum stress can reach 95MPa, and the cured material can replace the traditional curing agent.
4. The cured epoxy resin has good degradability and can be completely decomposed in an acid solution with the hydrogen ion concentration of 0.1-8 mol/L.
5. The curing agent and the epoxy cured product can be applied to the industrial fields of environment-friendly epoxy resin composite materials and the like.
Drawings
FIG. 1 is a scheme showing the synthesis of the curing agent of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
For ease of understanding and comparison, the synthetic scheme for the curing agent is shown in FIG. 1.
Example 1:
a curing agent and a preparation method thereof are as follows: adding 100mL of ethanol, 13.8g of p-nitroaniline and 4.5g of 33 wt% formaldehyde solution into a three-neck flask, stirring for 2 hours at 25 ℃, filtering, washing and drying in vacuum to obtain secondary diamine; 400mL of acetonitrile, 5.76g of secondary diamine, 3.66g of 3, 5-dinitroaniline, 0.2g of formic acid and 3.6g of 33 wt% formaldehyde are added into a flask, and the mixture is reacted for 20 hours at 60 ℃ in a nitrogen atmosphere, cooled, filtered, the filter cake is washed by acetonitrile, dried in vacuum to obtain a crude product, dissolved by chloroform and separated by a column to obtain an intermediate with four nitro groups. A flask was charged with 70mL of ethanol, 100mL of water, 3.02g of intermediate, 6g of indium powder, and 5.7g of ammonium chloride, and the reaction was refluxed for 24 hours under a nitrogen atmosphere. Filtering, extracting with dichloromethane, taking an organic layer, performing rotary evaporation, recrystallizing with ethanol, and performing vacuum drying to obtain the curing agent with the formula II and four primary amine groups.1H-NMR(,CDCl3)：6.45，6.28，5.35，5.26，5.11，2.13。
An epoxy resin condensate and a preparation method thereof are as follows: 3.75g of the prepared curing agent of the formula II and 11.7g of bisphenol A diglycidyl ether are taken, stirred for 0.5h at the temperature of 60 ℃ to prepare a prepolymerization liquid, the prepolymerization liquid is poured into a steel mould, vacuumized to remove bubbles, and cured for 1h at three temperature stages of 70 ℃, 120 ℃ and 160 ℃. And cooling to obtain the degradable epoxy resin condensate.
Example 2:
a curing agent and a preparation method thereof are as follows: adding 100mL of ethanol, 18.3g of 3, 5-dinitroaniline and 4.5g of 33 wt% formaldehyde solution into a three-neck flask, stirring for 4 hours at 40 ℃, filtering, washing and drying in vacuum to obtain secondary diamine; a flask was charged with 400mL of acetonitrile, 7.56g of a secondary diamine, 1.56g of aniline, 0.2g of hydrochloric acid, and 3.6g of a 33 wt% formaldehyde solution, reacted at 80 ℃ for 20 hours under a nitrogen atmosphere, and cooledFiltering, washing, drying to obtain a crude product, dissolving with chloroform, and separating by a column to obtain an intermediate with four nitro groups. 100mL of ethanol, 1g of the intermediate and 0.1g of 10 wt% palladium on carbon were placed in a 250mL flask, and hydrogen was injected into the reaction solution at 40 ℃ to form small bubbles, which were involved in the reaction at a bubble generation rate of 1/sec for 24 hours. The curing agent of formula III with four primary amine groups is obtained.1H-NMR(,CDCl3)：7.23、6.91、6.71、5.35、5.26、5.11、2.23。
An epoxy resin condensate and a preparation method thereof are as follows: 3.75g of the prepared curing agent shown in the formula III and 11.7g of bisphenol F diglycidyl ether are taken, stirred for 1 hour at the temperature of 30 ℃ to prepare a pre-polymerization liquid, the pre-polymerization liquid is poured into a steel mould, vacuumized to remove bubbles, and cured for 1 hour at three temperature stages of 80 ℃, 130 ℃ and 180 ℃. And cooling to obtain the degradable epoxy resin condensate.
Example 3:
a curing agent and a preparation method thereof are as follows: adding 100mL of ethanol, 18.3g of 3, 5-dinitroaniline and 4.5g of 33 wt% formaldehyde solution into a three-neck flask, stirring for 1 hour at 60 ℃, filtering, washing and drying in vacuum to obtain secondary diamine; 400mL of acetonitrile, 7.56g of secondary diamine, 2.80g of 2-amino-5-nitropyrimidine, 0.2g of sulfuric acid and 3.6g of 33 wt% formaldehyde solution are added into a flask, and the mixture reacts for 20 hours at 80 ℃ in a nitrogen atmosphere, is cooled, filtered, washed and dried to obtain a crude product, and then is dissolved by chloroform, and is subjected to column separation to obtain the product with five nitro groups. A flask was charged with 70mL of ethanol, 100mL of water, 3.31g of an intermediate, 6g of zinc powder, and 180mL of a 1mol/L aqueous hydrochloric acid solution was added dropwise from a dropping funnel, and the reaction was completed in 2 hours and refluxed for 24 hours under a nitrogen atmosphere. Filtering, extracting with dichloromethane, collecting organic layer, rotary evaporating, recrystallizing with ethanol, and vacuum drying. The curing agent of formula IV is obtained with five primary amine groups.1H-NMR(,CDCl3)：8.15，5.36、5.26、5.17、5.11、2.67。
An epoxy resin condensate and a preparation method thereof are as follows: 3.92g of the prepared curing agent IV and 11.7g of hydrogenated bisphenol A diglycidyl ether are taken, stirred for 1 hour at the temperature of 40 ℃ to prepare a prepolymerization liquid, the prepolymerization liquid is poured into a steel mould, the steel mould is vacuumized to remove bubbles, and the curing is carried out for 1 hour at three temperature stages of 80 ℃, 120 ℃ and 160 ℃. And cooling to obtain the degradable epoxy resin condensate.
Example 4:
a curing agent and a preparation method thereof are as follows: adding 100mL of ethanol, 18.3g of 3, 5-dinitroaniline and 4.5g of 33 wt% formaldehyde solution into a three-neck flask, stirring for 8 hours at 30 ℃, filtering, washing and drying in vacuum to obtain secondary diamine; a flask was charged with 400mL of acetonitrile, 7.56g of a secondary diamine, 0.2g of acetic acid, and 1.8g of a 33 wt% formaldehyde solution, and reacted at 60 ℃ for 20 hours under a nitrogen atmosphere to obtain an intermediate having six nitro groups. 100mL of ethanol, 1g of intermediate and 0.01g of 10 wt% Raney nickel were put into a flask, and hydrogen gas was injected into the reaction solution at 40 ℃ to form small bubbles to participate in the reaction, wherein the bubble generation rate was 1/sec, and the reaction was carried out for 24 hours. What is obtained is a V curing agent with six primary amine groups.
An epoxy resin condensate and a preparation method thereof are as follows: taking 4.05g of the prepared curing agent shown in the formula V and equal 16g of ethylene glycol diglycidyl ether, stirring for 0.5-1 h at the temperature of 50 ℃ to prepare a pre-polymerization liquid, pouring the pre-polymerization liquid into a steel mould, and curing for 1 hour at three temperature stages of 70 ℃, 110 ℃ and 150 ℃. And cooling to obtain the degradable epoxy resin condensate.
Comparative example 1:
a cured product and a preparation method thereof are as follows: taking 2.97g of curing agent 4, 4' -diaminodiphenylmethane and 11.7g of bisphenol A diglycidyl ether as the raw materials, stirring for 0.5-1 h at the temperature of 60 ℃ to prepare a pre-polymerization liquid, pouring the pre-polymerization liquid into a steel mold, and curing for 1 hour at three temperature stages of 80 ℃, 120 ℃ and 160 ℃. And cooling to obtain the degradable epoxy resin condensate.
Comparative example 2:
a cured product and a preparation method thereof are as follows: taking 7.2g of a curing agent of the formula VI and 11.7g of bisphenol A diglycidyl ether, stirring for 0.5-1 h at the temperature of 60 ℃ to prepare a prepolymerization liquid, pouring the prepolymerization liquid into a steel mold, and curing for 1 hour at three temperature stages of 80 ℃, 120 ℃ and 160 ℃. And cooling to obtain the degradable epoxy resin condensate.
Test example:
the following mechanical property tests were carried out on the cured products obtained in examples 1 to 4 and comparative examples 1 to 2:
test samples were prepared in GB/T2567-2008 for examples 1 to 4 and comparative examples 1 to 2, respectively, and tensile test was conducted at a rate of 10mm/min using an universal tensile machine.
The cured products prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to an acid/alkali degradation performance test:
samples of the cured products of examples 1 to 4 and comparative examples 1 to 2, respectively, were taken, the size of the sample was 10mm by 6mm by 1mm, the sample was completely immersed in 2mol/L hydrochloric acid solution, heated to a specified temperature, stirred at a rate of 200 rpm, and the time for the sample to completely dissolve was recorded.
The results are shown in table 1:
TABLE 1 mechanical Property test results of cured products obtained in examples 1 to 4 and comparative examples 1 to 2
| Name (R) | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Young's modulus/MPa | 2389 | 2417 | 2702 | 2893 | 3211 | 1893 |
| Maximum stress/MPa | 83 | 88 | 94 | 95 | 86 | 74 |
| Elongation at break/%) | 5.7 | 5.7 | 8.3 | 10.0 | 5.8 | 5.7 |
As can be seen from Table 1, examples 1 to 4 have better mechanical properties, and compared with comparative example 2, the mechanical properties are provided more obviously, and the more the number of amine groups in the curing agent is, the larger the Young modulus and the maximum stress is, compared with comparative example 1, the mechanical properties are slightly inferior, but the overall mechanical properties can reach the mechanical property index of the conventional epoxy resin material.
The cured products obtained in examples 1 to 4 and comparative examples 1 to 2 were tested for their degradation performance in a 2mol/L hydrochloric acid solution, and the results are shown in Table 2:
TABLE 2 complete degradation time (unit: hour) of cured products obtained in examples 1 to 4 and comparative examples 1 to 2
| Temperature/. degree.C | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| 30 | 32 | 30 | 32 | 31 | Does not degrade | 32 |
| 50 | 17 | 16 | 16 | 14 | Does not degrade | 18 |
| 70 | 3 | 2.5 | 2.5 | 2 | Does not degrade | 3 |
As can be seen from Table 2, examples 1-4 and comparative example 2 can be completely degraded in 2mol/L hydrochloric acid solution, and the more the number of amine groups in the curing agent is, the higher the crosslinking density of the cured product is, the fewer the crosslinking points are, the less time is required for complete degradation, and the fastest complete degradation can be achieved within 2 hours.
Therefore, the mechanical property test and the acid degradation test are integrated, and the cured product prepared by the curing agent provided by the technical scheme of the invention has good mechanical property and acid degradability, can replace the traditional curing agent, and can be used for preparing the degradable epoxy resin material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A curing agent characterized by: the curing agent has the general formula of formula I,
wherein A, B is at least one of aliphatic alkylene, aryl, aliphatic cyclic alkyl and heterocycle independently; r1、R2、R3、R4、R5、R6At least 4 of which are-NH2The others are independently selected from-H, -CH3At least one of-OH.
2. The curing agent according to claim 1, characterized in that: the formula I is selected from the group consisting of:
3. a method for preparing the curing agent according to claim 1 or 2, wherein: the method comprises the following steps:
(1) adding into a solvent a
Reacting with formaldehyde to obtain secondary diamine containing nitric acid groups;
(2) adding secondary diamine, formaldehyde and
dropwise adding an acid solution, reacting, and purifying to obtain an intermediate product of hexahydrotriazine ring;
(3) and carrying out amination reaction on the intermediate product of the hexahydrotriazine ring to obtain the epoxy resin curing agent.
4. The method for producing a cured epoxy resin according to claim 3, wherein:the above-mentioned
And said
In, X1、X2At least one is a nitrate group, the others are selected from-H, -CH3At least one of-OH.
5. The method for producing the curing agent according to claim 3, wherein: the step (1) is as described above
And the molar ratio of formaldehyde is 1: 1 to 3.
6. The method for producing the curing agent according to claim 3, wherein: the secondary diamine, formaldehyde and the like in the step (2),
The molar ratio of (1) - (3) to (0-2).
7. The method for producing the curing agent according to claim 3, wherein: in the step (1), the solvent a is at least one selected from water, methanol, ethanol, acetonitrile and tetrahydrofuran; preferably, the solvent b in the step (2) is at least one selected from the group consisting of water, methanol, ethanol, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
8. The method for producing a cured epoxy resin according to claim 3, wherein: the amination reaction in the step (3) is selected from one of catalytic hydrogenation reductive amination and metal electron transfer reductive amination.
9. A cured epoxy resin, characterized in that: comprises the following components: the curing agent, epoxy resin prepolymer, or cured product according to claim 1 or 2.
10. A preparation method of an epoxy resin condensate is characterized by comprising the following steps: the method comprises the following steps:
(1) heating and stirring the curing agent of claim 1 or 2 and an epoxy resin prepolymer, and vacuumizing to obtain a pre-polymerization solution;
(2) and pouring the prepolymer into a mold, vacuumizing, curing and cooling to obtain an epoxy resin cured product.
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Cited By (2)
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| CN112898538A (en) * | 2019-12-04 | 2021-06-04 | 万华化学集团股份有限公司 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
| CN114044883A (en) * | 2021-12-08 | 2022-02-15 | 浙江万盛股份有限公司 | Cardanol aldehyde amine epoxy resin curing agent containing purine structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112898538A (en) * | 2019-12-04 | 2021-06-04 | 万华化学集团股份有限公司 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
| CN112898538B (en) * | 2019-12-04 | 2022-04-19 | 万华化学集团股份有限公司 | Thick-coatable modified ketimine curing agent and preparation method and application thereof |
| CN114044883A (en) * | 2021-12-08 | 2022-02-15 | 浙江万盛股份有限公司 | Cardanol aldehyde amine epoxy resin curing agent containing purine structure and preparation method thereof |
| CN114044883B (en) * | 2021-12-08 | 2023-10-03 | 浙江万盛股份有限公司 | Cashew phenol aldehyde amine epoxy resin curing agent containing purine structure and preparation method thereof |
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| CN111909359B (en) | 2022-09-13 |
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