CN112194779A - Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof - Google Patents
Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof Download PDFInfo
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- 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
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The invention discloses a single-component epoxy resin composition containing a latent imidazole curing accelerator, and a preparation method and application thereof, and belongs to the technical field of modification and application of epoxy resin. The single-component epoxy resin composition comprises epoxy matrix resin, a curing agent and a curing accelerator; the curing accelerator is a phthalic anhydride imidazole derivative, can effectively improve the room-temperature storage stability of the single-component epoxy resin composition, can enable the system to quickly generate a curing reaction at high temperature, and enables a cured product of the single-component epoxy resin composition to have higher glass transition temperature, so that the single-component epoxy resin composition has a good application prospect in the fields of epoxy resin adhesives, coatings, copper clad laminates, composite materials, electronic packaging materials and the like; meanwhile, the preparation method is simple and safe, and can be widely popularized and applied.
Description
Technical Field
The invention relates to a single-component epoxy resin composition containing a latent imidazole curing accelerator and application thereof, belonging to the technical field of epoxy resin modification and application.
Background
The epoxy resin is an important polymer or semi-polymer material, the molecular structure of which contains two or more than two epoxy groups, and the epoxy resin is cured and crosslinked under the action of certain chemical reagents or physical conditions such as temperature, humidity, irradiation and the like to form a three-dimensional network-shaped cured product. The uncured epoxy resin is a thermoplastic oligomer, is a brittle solid or a viscous liquid, has no practical application value, and can improve the comprehensive performance only by reacting with a curing agent under certain conditions to form a thermosetting resin. The epoxy resin has the advantages of good mechanical property, thermal stability, easy processability, chemical corrosion resistance, low thermal expansion coefficient and the like, so that the epoxy resin is widely applied to the fields of aerospace, automobile parts, biological materials, composite materials, electronic packaging, adhesives, coatings and the like, and becomes an important material which cannot be replaced in the production and life of the current society.
Epoxy matrix resins can be classified into glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, alicyclic epoxy resins, and the like according to their chemical structures. When the epoxy matrix resin and the curing agent are subjected to crosslinking reaction, the reaction is completed only at a very high temperature due to high activation energy, a large amount of energy is wasted, and the production process requirement and the production cost are increased, so that a curing accelerator is often added into an epoxy resin curing system to reduce the activation energy of the reaction, improve the reaction rate and shorten the reaction time. There are many commonly used curing accelerators including tertiary amines and salts thereof, acetylacetone metal salts, triphenylphosphine and salts thereof, organic carboxylates, aryl isocyanic acids, imidazole and salts thereof, and the like. Imidazole is a five-membered heterocyclic ring with two nitrogen atoms, one nitrogen atom forms secondary amine, and the other nitrogen atom forms tertiary amine, so that imidazole not only can open an epoxy group through the catalytic action of the tertiary amine but also can open a ring through the addition reaction of the secondary amine, and the structure of imidazole can be modified by various means to adjust the reactivity of the imidazole derivative; meanwhile, imidazole can be used together with a curing agent, and has the advantages of low toxicity, small using amount, quick curing, high thermal deformation temperature of a cured product, mild curing conditions and the like. However, for the common unmodified imidazole curing accelerator, because two nitrogen atoms of pyrrole nitrogen and pyridine nitrogen on an imidazole ring have high initiating activity, when the imidazole ring is directly added into epoxy matrix resin and a curing agent, a system can be quickly gelled, and a curing and crosslinking reaction occurs; if the epoxy resin and the imidazole are stored separately and prepared as they are, the storage cost and the time cost for mixing materials are increased, the production efficiency is reduced, and the practical application and the production requirement are influenced. Therefore, how to combine the epoxy resin, the curing agent and the imidazole curing accelerator into a one-component system and make the system have excellent storage stability at room temperature has been a problem of great research significance and application value.
The retrieval of the prior scientific and technological literature shows that the modification of imidazole is generally carried out by methods such as imidazole salification, microcapsule coating, metal complexing and the like, and then the modified product is directly added into a single-component epoxy resin system to improve the storage stability at room temperature, so that the related research and report are relatively extensive at present. However, the modified imidazole accelerator is often incompatible or poorly compatible with epoxy matrix resin and/or curing agent, and has problems of poor stability of a mixed system, reduction of thermal stability and glass transition temperature of the cured resin due to introduction of a flexible segment, increase of electric conductivity due to introduction of a metal element, and the like, and has direct consequences of uneven curing of a product, low glass transition temperature of a cured product, poor mechanical properties, reduction of dielectric properties, and the like. The invention patent of the publication No. CN107428914B discloses an epoxy resin composition, wherein a reaction product of a carbodiimide compound and an imidazole compound is used as a latent curing accelerator, so that the storage stability and the operability are improved while the characteristics of a cured resin are not reduced, but the preparation steps of the curing accelerator are still complicated, and the curing accelerator is not suitable for popularization and application in mass production.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides the single-component epoxy resin composition containing the latent imidazole curing accelerator, wherein the latent imidazole curing accelerator has good compatibility with epoxy resin, the room-temperature storage stability of the single-component epoxy resin composition can be effectively improved, the curing reaction of a system can be rapidly carried out at high temperature, and a cured substance of the single-component epoxy resin composition has higher glass transition temperature; in addition, the preparation method is simple and safe, and can be widely popularized and applied.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention discloses a one-component epoxy resin composition containing a latent imidazole curing accelerator, which comprises epoxy matrix resin, a curing agent and a curing accelerator; wherein the molar ratio of the reaction groups of the epoxy matrix resin and the curing agent is (0.5-1.5): 1; the addition amount of the curing accelerator is 0.5-15 wt% of the epoxy matrix resin, and the preferred amount of the curing accelerator is 1-10 wt%; the curing accelerator is phthalic anhydride imidazole derivative, and the chemical structure of the curing accelerator is shown as the following formula 1:
in the formula 1, R1Is hydrogen atom, methyl, ethyl, phenyl, amino, iodine atom, chlorine atom or bromine atom; r2And R3Each independently is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a carboxyl group, a cyano group, an aldehyde group, a hydroxymethyl group, a chlorine atom or a bromine atom; r4And R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Is a hydrogen atom or a methyl group;
the epoxy matrix resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic epoxy resin;
the curing agent is one or the combination of more than two of anhydride, polybasic aromatic amine, dicyandiamide and polyhydric phenol.
Further, the glycidyl ether type epoxy resin may be bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, o-cresol novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetramethylbiphenyl type epoxy resin, biphenol type epoxy resin, dicyclopentadienyl type epoxy resin; the glycidyl ester epoxy resin can be diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalate, diglycidyl methyltetrahydrophthalate, diglycidyl endomethyltetrahydrophthalate and diglycidyl adipate; the glycidyl amine epoxy resin can be triglycidyl isocyanurate, triglycidyl para-aminophenol, tetraglycidyl diaminodiphenylmethane, diisopropylidenylidene tetraglycidyl amine, tetramethylisopropylidenylidene tetraglycidyl amine, N, N, N ', N ' -tetraepoxypropyl-4, 4-diaminodiphenylmethane, 4 ' -diaminodiphenyl ether tetraglycidyl amine; the alicyclic epoxy resin may be 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, dicyclopentadiene diepoxide, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester. The invention is not limited in scope by the examples described above. Preferred epoxy resins of the present invention are bisphenol a type epoxy resins, o-cresol novolac type epoxy resins, tetramethyl biphenyl type epoxy resins, dicyclopentadienyl diphenyl type epoxy resins and triglycidyl isocyanurate.
Further, the acid anhydride can be tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, nadic anhydride, maleic anhydride; the polyaromatic amine can be m-phenylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone; the polyhydric phenol may be novolac resin, o-cresol novolac resin, dicyclopentadiene novolac resin, terpene novolac resin, phenol-aralkyl type resin having phenylene structure, phenol-aralkyl type resin having biphenylene structure, naphthol novolac resin. The invention is not limited in scope by the examples described above. Preferred curing agents of the present invention are methylhexahydrophthalic anhydride, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfone, dicyandiamide, and novolac resins.
The second aspect of the invention discloses a preparation method of a single-component epoxy resin composition containing a latent imidazole curing accelerator, which is characterized by comprising the steps of synthesizing the curing accelerator and preparing the single-component epoxy resin composition;
the curing accelerator is a latent curing accelerator, and is prepared by nucleophilic substitution reaction of chlorinated trimellitic anhydride or a derivative thereof and imidazole or a derivative thereof, but the invention is not limited to the above, for example, the latent curing accelerator is prepared by reaction of chlorinated trimellitic anhydride and imidazole, and the preparation method comprises the following steps:
s1, dissolving trimellitic anhydride chloride in an organic solvent under an ice bath condition, and fully mixing to completely dissolve the trimellitic anhydride chloride;
s2, dissolving imidazole and an acid binding agent in an organic solvent, and fully stirring to completely dissolve the imidazole and the acid binding agent;
s3, dropwise adding the solution prepared in the step S2 into the solution prepared in the step S1, and reacting at the temperature of 30-150 ℃ for 2-24 hours;
the single-component epoxy resin composition is prepared by melting and blending epoxy resin, a curing agent and a curing accelerator according to the proportion and then cooling to room temperature.
Further, the molar concentration ratio of the chlorinated trimellitic anhydride to the imidazole is 5: 1-1: 5;
the molar concentration ratio of the imidazole to the acid-binding agent is 10: 1-1: 10, and the optimal concentration ratio is 5: 1-1: 5; the acid-binding agent can be one or more of pyridine, 4-dimethylaminopyridine, triethylamine, N-diisopropylethylamine, triethanolamine and tetrabutylammonium bromide;
the organic solvent in steps S1 and S2 is one or a combination of two or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, cyclohexane, tetrahydrofuran, and dichloromethane, but the present invention is not limited to the above-mentioned range, and tetrahydrofuran is preferred in the present invention.
The third aspect of the invention discloses a cured product of a one-component epoxy resin composition containing a latent imidazole curing accelerator, which is prepared by curing the one-component epoxy resin composition containing the latent imidazole curing accelerator.
The single-component epoxy resin composition containing the latent imidazole curing agent is suitable for the fields of epoxy resin adhesives, coatings, copper-clad plates, composite materials and electronic packaging materials.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) the phthalic anhydride imidazole derivative has an anhydride group, can participate in epoxy resin curing, and improves the compatibility of the imidazole curing accelerator and epoxy matrix resin;
(2) the activity of pyrrole nitrogen on imidazole rings is effectively inhibited at room temperature, so that the single-component epoxy resin composition has good room-temperature storage stability, and the system can quickly generate a curing reaction at high temperature;
(3) the cured product has higher glass transition temperature, so that the epoxy resin composition has wide application prospect in the fields of epoxy resin adhesives, coatings, copper-clad plates, composite materials, electronic packaging materials and the like;
(4) the preparation method is simple and safe, has mild reaction conditions, and can be widely popularized and applied.
Drawings
FIG. 1 is a schematic for the preparation of latent cure accelerator 2MI-T of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of latent cure accelerator 2MI-T of the present invention;
FIG. 3 is a non-isothermal DSC curing profile of the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 4 is a graph showing curing conversion rate versus temperature for the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a graph showing gel times of the one-pack epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention on a hot stage at 175 ℃;
FIG. 6 is a DSC chart of cured products of the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
The following examples will further illustrate the invention in conjunction with the accompanying drawings. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments. The following examples are conducted under conditions not specified, usually in accordance with conventional conditions or conditions recommended by the manufacturer.
The raw materials used in the examples of the present invention are shown in table 1 below, but not limited thereto:
TABLE 1
| Name of raw materials | Molecular formula | CAS number/model number | Suppliers of goods |
| Chlorinated trimellitic anhydride | C18H10ClO11 | 1204-28-0 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| 2-methylimidazole (2MI) | C4H6N2 | 693-98-1 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Triethylamine | C6H15N | 121-44-8 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetrahydrofuran (THF) | C4H8O | 109-99-9 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetramethylbenzene type epoxy resin | / | YX-4000 | Yukka Shell Co Ltd |
| Phenol novolac resin (hydroxyl equivalent is 102g/eq) | / | PF-8011 | SHANDONG SHENGQUAN NEW MATERIAL Co.,Ltd. |
| Bisphenol A epoxy resin | / | E51 | China petrochemical Baslin division |
| Methyl hexahydrophthalic anhydride | C9H12O3 | 25550-51-0 | Polynt chemical Co Ltd |
Examples 1 to 6
The raw materials and the amounts used in the embodiments 1 to 6 of the present invention are shown in the following table 2:
TABLE 2
In Table 2, latent curing accelerator 2MI-T was prepared as follows: according to the preparation route of latent curing accelerator 2MI-T shown in FIG. 1, 4.64g (22mmol) of chlorinated trimellitic anhydride was added to a single-neck flask, and 40mL of tetrahydrofuran was added and dissolved in ice bath to obtain a chlorinated trimellitic anhydride solution; adding 1.64g (20mmol) of 2-methylimidazole and 2.23g (22mmol) of triethylamine into a beaker, and adding 40mL of tetrahydrofuran for complete dissolution to obtain a mixed solution of 2-methylimidazole and triethylamine; dropwise adding the mixed solution of 2-methylimidazole and triethylamine into a trimellitic anhydride chloride solution, and stirring and reacting for 12 hours at room temperature; filtering after the reaction is finished, carrying out rotary evaporation on the filtrate, washing with water, filtering and drying to obtain the latent curing accelerator 2 MI-T; as shown in fig. 2, the nuclear magnetic hydrogen spectrum of latent curing accelerator 2MI-T is shown, in which the chemical shifts δ of methyl group on imidazole group are 2.45(s, 3H), the chemical shifts δ of hydrogen atoms at three and four positions on imidazole ring are 7.54(dd, 2H), the chemical shifts δ of hydrogen atoms on benzene ring are 8.01(d, 1H), 8.23(d, 1H) and 8.74(s, 1H), respectively, and the chemical shift δ of deuterium reagent DMSO-d6 is 2.51 (m).
In Table 2, the latent cure accelerator EMI-T was prepared by the following method: adding 4.64g (22mmol) of chlorinated trimellitic anhydride into a single-neck flask, adding 40mL of tetrahydrofuran, and dissolving under an ice bath condition to obtain a chlorinated trimellitic anhydride solution; adding 2.20g (20mmol) of 2-ethyl-4-methylimidazole and 2.23g (22mmol) of triethylamine into a beaker, and adding 40mL of tetrahydrofuran for complete dissolution to obtain a mixed solution of 2-ethyl-4-methylimidazole and triethylamine; dropwise adding the mixed solution of 2-ethyl-4-methylimidazole and triethylamine into a chlorinated trimellitic anhydride solution, and stirring and reacting for 12 hours at room temperature; and (3) filtering after the reaction is finished, carrying out rotary evaporation on the filtrate, washing with water, filtering and drying to obtain the latent curing accelerator EMI-T.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 1 to 4 comprises the following specific steps: according to the mixture ratio shown in Table 2, the tetramethyl biphenyl type epoxy resin (YX-4000), the linear phenolic resin (PF-8011) and the latent curing accelerator 2MI-T are melted and blended for 2min at 120 ℃, and are uniformly mixed and cooled to room temperature, so that the single-component epoxy resin composition of the embodiment 1-4 is obtained.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 5 comprises the following specific steps: according to the mixture ratio shown in table 2, bisphenol a type epoxy resin (E51), methylhexahydrophthalic anhydride and latent curing accelerator 2MI-T were mixed uniformly at room temperature using a high-speed homogenizer to obtain the one-component epoxy resin composition of example 5.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 6 comprises the following specific steps: according to the mixture ratio shown in Table 2, the tetramethyl biphenyl type epoxy resin (YX-4000), the linear phenolic resin (PF-8011) and the latent curing accelerator EMI-T are melted and blended for 2min at 120 ℃, and after being uniformly mixed, the mixture is cooled to room temperature, so that the single-component epoxy resin composition of the embodiment 6 is obtained.
Comparative examples 1 to 2
The raw materials and the amounts used in comparative examples 1 to 2 are shown in table 3 below:
TABLE 3
The preparation method of the one-component epoxy resin composition of comparative example 1 specifically includes the steps of: according to the compounding ratio shown in Table 3, a tetramethylbiphenyl type epoxy resin (YX-4000), a phenol novolac resin (PF-8011) and an unmodified curing accelerator, 2-methylimidazole (2MI), were melt-mixed at 110 ℃ for 30 seconds and then cooled to room temperature, thereby obtaining a one-component epoxy resin composition of comparative example 1.
The preparation method of the one-component epoxy resin composition of comparative example 2 specifically includes the steps of: according to the compounding ratio shown in Table 3, a tetramethylbiphenyl type epoxy resin (YX-4000), a phenol novolac resin (PF-8011) and an unmodified curing accelerator, 2-ethyl-4-methylimidazole (EMI), were melt-mixed at 110 ℃ for 30 seconds and then cooled to room temperature, to obtain a one-component epoxy resin composition of comparative example 2.
Performance testing
The one-component epoxy resin compositions prepared in example 1 and comparative examples 1 and 2 and cured products thereof were subjected to curing behavior test using Differential Scanning Calorimetry (DSC).
The test conditions were: the sampling amount of each sample is about 5mg, and the heating rate is 10 ℃ for min-1In N at2And testing in the atmosphere, wherein the protective gas flow is 50mL/min, and the purge gas flow is 70 mL/min.
As shown in fig. 3, which is a non-isothermal DSC curing graph of the one-part epoxy resin compositions of example 1, comparative example 1, and comparative example 2, it can be seen that the curing behavior of the one-part epoxy resin composition of example 1 to which 2MI-T is added shows a significant latency, and curing hardly occurs at a temperature lower than 160 ℃, compared to unmodified curing accelerator 2MI and EMI added to comparative example 1 and comparative example 2, and thus has excellent room-temperature storage stability; whereas example 1 shows a narrower exothermic peak when the temperature is higher than 160 c, and it is shown that it has excellent high-temperature curing activity by the relationship of the conversion rate and the temperature of fig. 4.
FIG. 5 shows the gel times of the one-pack epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 on a hot stage at 175 ℃. It can be seen that the one-pack epoxy resin composition of example 1 has a longer gel time but less than 100s compared to comparative examples 1 and 2, indicating that the latent curing accelerator of the present invention enables a resin system to be rapidly cured at a high temperature.
As shown in fig. 6, which is a DSC graph of the cured products of the one-component epoxy resin compositions of example 1, comparative example 1, and comparative example 2, it can be seen that the cured product of the one-component epoxy resin composition of example 1 containing a latent imidazole derivative has a glass transition temperature similar to that of the 2MI (comparative example 1) and EMI (comparative example 2) systems, indicating that the phthalic anhydride imidazole derivative as a curing accelerator does not have a significant negative influence on the glass transition temperature of the epoxy cured product, and the cured product has a high glass transition temperature.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. All equivalent changes, simplifications and modifications which do not depart from the spirit and scope of the invention are intended to be covered by the scope of the invention.
Claims (10)
1. A single-component epoxy resin composition containing a latent imidazole curing accelerator is characterized by comprising epoxy matrix resin, a curing agent and a curing accelerator; wherein the molar ratio of the reaction groups of the epoxy matrix resin and the curing agent is (0.5-1.5): 1; the addition amount of the curing accelerator is 0.5-15 wt% of the epoxy matrix resin; the curing accelerator is phthalic anhydride imidazole derivative, and the chemical structure of the curing accelerator is shown as the following formula 1:
in the formula 1, R1Is one of hydrogen atom, methyl, ethyl, phenyl, amino, iodine atom, chlorine atom or bromine atom; r2And R3Each independently is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a carboxyl group,One of cyano, aldehyde group, hydroxymethyl, chlorine atom or bromine atom; r4And R5Each independently is one of a hydrogen atom, a methyl group or an ethyl group; r6Is a hydrogen atom or a methyl group;
the epoxy matrix resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic epoxy resin;
the curing agent is one or the combination of more than two of anhydride, polybasic aromatic amine, dicyandiamide and polyhydric phenol.
2. The one-component epoxy resin composition containing the latent imidazole-based curing accelerator as claimed in claim 1, wherein the amount of the curing accelerator added is 1 to 10 wt% of the epoxy resin in the one-component epoxy resin composition.
3. The one-component epoxy resin composition containing the latent imidazole-based curing accelerator according to claim 1, wherein the epoxy matrix resin is one or a combination of two or more of bisphenol a-type epoxy resin, o-cresol novolac-type epoxy resin, tetramethyl biphenyl-type epoxy resin, dicyclopentadiene diphenol-type epoxy resin, and triglycidyl isocyanurate.
4. The one-pack epoxy resin composition containing a latent imidazole-based curing accelerator according to claim 1, wherein the curing agent is one or a combination of two or more of methylhexahydrophthalic anhydride, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfone, dicyandiamide, and phenol novolac.
5. The preparation method of the one-component epoxy resin composition containing the latent imidazole-based curing accelerator according to any one of claims 1 to 4, which is characterized by comprising the steps of synthesizing the curing accelerator and preparing the one-component epoxy resin composition;
the curing accelerator is prepared by carrying out nucleophilic substitution reaction on chlorinated trimellitic anhydride or a derivative thereof and imidazole or a derivative thereof;
the single-component epoxy resin composition is prepared by mixing epoxy resin, a curing agent and a curing accelerator according to the proportion shown in claim 1, melting, blending and cooling to room temperature.
6. The preparation method of the one-component epoxy resin composition containing the latent imidazole-based curing accelerator according to claim 5, wherein the curing accelerator is prepared by nucleophilic substitution reaction of chlorinated trimellitic anhydride and imidazole, and comprises the following steps:
s1, dissolving trimellitic anhydride chloride in an organic solvent under an ice bath condition, and fully mixing to completely dissolve the trimellitic anhydride chloride;
s2, dissolving imidazole and an acid binding agent in an organic solvent, and fully stirring to completely dissolve the imidazole and the acid binding agent;
s3, dropwise adding the solution prepared in the step S2 into the solution prepared in the step S1, and reacting at the temperature of 30-150 ℃ for 2-24 hours to obtain the curing accelerator.
7. The preparation method of the one-component epoxy resin composition containing the latent imidazole-based curing accelerator according to claim 6, wherein the molar concentration ratio of the chlorinated trimellitic anhydride to the imidazole is 5:1 to 1: 5; the molar concentration ratio of the imidazole to the acid-binding agent is 10: 1-1: 10.
8. The preparation method of the one-component epoxy resin composition containing the latent imidazole-based curing accelerator according to claim 6, wherein the acid-binding agent is one or a combination of two or more of pyridine, 4-dimethylaminopyridine, triethylamine, N-diisopropylethylamine, triethanolamine and tetrabutylammonium bromide;
the organic solvent in the steps S1 and S2 is one or more of methanol, toluene, acetonitrile, absolute ethyl alcohol, N-dimethylformamide, cyclohexane, tetrahydrofuran and dichloromethane.
9. A cured product of a single-component epoxy resin composition containing a latent imidazole curing accelerator, which is characterized by being prepared by curing the single-component epoxy resin composition containing the latent imidazole curing accelerator according to any one of claims 1 to 4.
10. The application of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the fields of epoxy resin adhesives, coatings, copper-clad plates, composite materials and electronic packaging materials according to any one of claims 1 to 4.
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| CN112574534A (en) * | 2021-01-12 | 2021-03-30 | 陕西理工大学 | Medium-temperature curing latent epoxy resin curing agent |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin and preparation method and application thereof |
| CN114957619A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy flame-retardant composite material containing imidazole curing accelerator and preparation method thereof |
| CN115160229A (en) * | 2022-05-31 | 2022-10-11 | 上海大学 | Modified imidazole latent epoxy resin curing agent and preparation method thereof |
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| CN112574534A (en) * | 2021-01-12 | 2021-03-30 | 陕西理工大学 | Medium-temperature curing latent epoxy resin curing agent |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin and preparation method and application thereof |
| CN113563564B (en) * | 2021-06-22 | 2022-07-22 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin, and preparation method and application thereof |
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| CN115160229A (en) * | 2022-05-31 | 2022-10-11 | 上海大学 | Modified imidazole latent epoxy resin curing agent and preparation method thereof |
| CN117004172A (en) * | 2023-08-14 | 2023-11-07 | 江苏耀鸿电子有限公司 | Preparation method of high-toughness phenolic resin glue solution for copper-clad plate |
| CN117004172B (en) * | 2023-08-14 | 2024-01-23 | 江苏耀鸿电子有限公司 | Preparation method of high-toughness phenolic resin glue solution for copper-clad plate |
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