CN110790903A - Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof - Google Patents
Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof Download PDFInfo
- Publication number
- CN110790903A CN110790903A CN201911234013.4A CN201911234013A CN110790903A CN 110790903 A CN110790903 A CN 110790903A CN 201911234013 A CN201911234013 A CN 201911234013A CN 110790903 A CN110790903 A CN 110790903A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- curing accelerator
- intramolecular hydrogen
- hydrogen bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a single-component epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator and a preparation method thereof, belonging to the technical field of latent curing accelerators for epoxy resins. The single-component epoxy resin composition comprises epoxy matrix resin, a curing agent and a curing accelerator, wherein the curing accelerator is a benzimidazole derivative with an intramolecular hydrogen bond. The benzimidazole derivative enables the single-component epoxy resin composition to have good room-temperature storage stability; under high temperature, the intramolecular hydrogen bond of the benzimidazole derivative is broken, the alkali catalytic activity is released instantly, the curing exothermic peak is narrower, the epoxy resin composition system is rapidly catalyzed to be crosslinked and cured, and the curing crosslinking reaction is rapidly carried out under high temperature, so that the obtained epoxy cured material has higher glass transition temperature and thermal stability. The epoxy resin composition has good application prospect in the fields of epoxy adhesives, coatings, composite materials, copper clad laminates, electronic packaging materials and the like.
Description
Technical Field
The invention belongs to the technical field of latent curing accelerators for epoxy resins, and particularly relates to a single-component epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator and a preparation method thereof.
Background
Epoxy resins are a broad class of compounds that contain two or more epoxy groups in one molecule and are capable of forming three-dimensional crosslinked network-like cured products in the presence of suitable chemical reagents. The epoxy matrix resin and the curing agent are often subjected to a crosslinking reaction due to high activation energy, and the reaction needs to be carried out at a high temperature or even cannot be carried out, so that the curing crosslinking reaction of the epoxy resin often needs to be carried out by adding a curing accelerator to improve the reaction speed and shorten the reaction time. There are many kinds of 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. The imidazole contains secondary amine groups and tertiary amine groups in a molecular structure, so that active hydrogen on the secondary amine groups can participate in addition reaction on epoxy groups, and the imidazole can be used together with a curing agent, and has the advantages of small using amount, high curing speed, high thermal deformation temperature of a cured product, mild curing conditions and the like.
However, as for a common imidazole curing accelerator, because two nitrogen atoms of pyrrole nitrogen and pyridine nitrogen on an imidazole ring have high initiating activity, when imidazole is directly added into epoxy matrix resin and a curing agent, a system can be quickly crosslinked and cured; if imidazole, epoxy matrix resin and curing agent are stored separately and mixed when needed, the storage cost and the time cost of mixing materials are increased, the production efficiency is reduced, and the actual application and the production requirements are influenced. Therefore, how to mix epoxy resin, curing agent and imidazole accelerator into a single-component system and ensure certain storage stability becomes an important subject with research significance and application value.
In the prior art, imidazole is modified by imidazole salification, microcapsule coating, metal complexation and the like, and the modified substance is used as a latent curing accelerator for a single-component epoxy resin system so as to improve the storage stability. However, the modified imidazole curing accelerator has the problems of poor compatibility with epoxy matrix resin, poor stability of a mixed system, poor latency, introduction of metal elements to increase conductivity and the like, and directly causes the problems of uneven curing of a cured product, reduction of glass transition temperature, reduction of mechanical properties, thermal stability and dielectric properties and the like.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a single-component epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator and prepared by the same and a preparation method thereof, so that the imidazole curing accelerator has better compatibility with epoxy resin, high-temperature catalytic activity can be released instantly, the epoxy resin single-component system can be rapidly catalyzed to be cured, and the single-component epoxy resin composition can have good storage stability at the temperature below middle and high temperature (140-160 ℃).
As a first aspect of the present invention, there is provided a one-pack epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator, comprising an epoxy matrix resin, a curing agent, and a curing accelerator which is a benzimidazole derivative having an intramolecular hydrogen bond and having a chemical structure shown below:
wherein R is1And R4Is a hydrogen atom (H); r2And R3Is a hydrogen atom (H), a methyl group (CH)3) Methoxy (CH)3O), fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or nitro group (NO)2)，R2And R3May be the same or different from each other; r5Is a hydrogen atom (H) or a methyl group (CH)3)；R6And R7Is a hydrogen atom (H), a methyl group (CH)3) Methoxy (CH)3O), fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or nitro group (NO)2)；R6And R7May be the same or different from each other; r8Is a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl) or a methoxy group (CH)3O)。
The molar ratio of the epoxy groups of the epoxy matrix resin to the reactive groups of the curing agent is 0.8-1.3;
the addition amount of the curing accelerator is 0.5-5 wt% of epoxy matrix resin in the epoxy resin composition.
As a second aspect of the present invention, there is provided a method for preparing a one-pack epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator, comprising the steps of:
s1: preparation of curing accelerator containing intramolecular hydrogen bond type imidazole
S1-1: at room temperature, adding sodium bisulfite and o-hydroxybenzaldehyde or derivatives thereof in an amount of 1: 1-10: 1 by mass ratio, preferably 1: 1-3: 1, adding the mixture into an organic solvent, and fully mixing and dissolving the mixture;
s1-2: dripping solution of o-phenylenediamine or derivatives thereof into the mixture to perform Schiff base reaction and oxidation reaction to obtain solution of imidazole derivatives with intramolecular hydrogen bonds;
s1-3, pouring the product in the S1-2 into ice water, standing for a period of time, performing suction filtration, washing with deionized water for multiple times, and drying in an oven to obtain a target product, namely the imidazole derivative with intramolecular hydrogen bonds;
s2: preparation of one-component epoxy resin composition
And melting and blending the epoxy resin, the curing agent and the curing accelerator prepared in S1 at a certain temperature, uniformly mixing, and cooling to room temperature to obtain the single-component epoxy resin composition.
The organic solvent in S1-1 is one or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, cyclohexane, and dichloromethane, but the present invention is not limited to the above-mentioned range, and absolute ethanol is preferred in the present invention.
The solvent of the solution of o-phenylenediamine or its derivative in S1-2 is one or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, dimethyl sulfoxide, cyclohexane and dichloromethane, but the present invention is not limited to the above-mentioned range, and N, N-dimethylformamide is preferred in the present invention.
The reaction temperature of the Schiff base reaction and the oxidation reaction can be 40-200 ℃, the optimal temperature of the Schiff base reaction and the oxidation reaction is 60-120 ℃, and the reaction time is 4-8 h.
And the standing time in the S1-3 is 1-2 h.
The melt blending temperature in the S2 is 110-150 ℃.
It is understood that 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 glycidyl ether epoxy resin can be bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, o-cresol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, tetramethyl biphenyl epoxy resin, biphenyl phenol epoxy resin, and dicyclopentadiene biphenyl 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, diisopropylidenylidenylidenylidenylidenylidenylidenylidenephlycidylamine, tetramethylisopropylidenylidenylidenylidenylidenylidenylidenediallylamine, N, N, N ', N ' -tetraglycidyl-4, 4-diaminodiphenylmethane, 4 ' -diaminodiphenylether 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-epoxycyclohexanecarboxylate) 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.
It is understood that the curing agent is one or more of an acid anhydride, a polyaromatic amine, dicyandiamide, a polyphenol. The anhydride can be tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, eleostearic acid anhydride, nadic anhydride, and 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 a phenylene structure, phenol-aralkyl type resin having a 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.
Compared with the prior art, the invention has the beneficial effects that:
1. the intramolecular hydrogen bond-containing imidazole curing accelerator has good compatibility with epoxy matrix resin, intramolecular hydrogen bonds at low temperature, the activity of pyridine nitrogen is sealed, alkalinity is effectively inhibited, and the single-component epoxy resin composition has good room-temperature storage stability;
2. at the temperature of about 160 ℃, the intramolecular hydrogen bond of the imidazole derivative is broken, the base catalytic activity is released instantly, the exothermic peak of curing is narrower, and the epoxy resin composition system is rapidly catalyzed to crosslink and cure;
3. the obtained epoxy resin condensate has higher glass transition temperature and thermal stability, and has good application prospect in the fields of epoxy adhesives, coatings, composite materials, copper clad laminates, electronic packaging materials and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a reaction scheme of a curing accelerator according to example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a curing accelerator in example 1 of the present invention;
FIG. 3 is a Fourier transform infrared spectrum of a curing accelerator according to example 1 of the present invention;
FIG. 4 is a graph (a) of non-isothermal DSC curing and a graph (b) of conversion of the one-component epoxy resin compositions of example 2, comparative example 1 and comparative example 2 of the present invention, with a temperature rise rate of 10 ℃/min;
FIG. 5 is a non-isothermal DSC plot of the cured products of the one-component epoxy resin compositions of example 2, comparative example 1 and comparative example 2 of the present invention with a temperature rise rate of 10 ℃/min;
FIG. 6 is a TGA graph of the cured products of the one-component epoxy resin compositions of example 2, comparative example 1 and comparative example 2 of the present invention under a nitrogen atmosphere at a temperature rising rate of 20 ℃/min.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is further illustrated by the following examples and figures. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
(1) Preparation of latent curing accelerators
150mL of absolute ethanol was added to a three-necked flask, and 2.04g (0.018mol) of salicylaldehyde and 2.08g (0.020mol) of sodium bisulfite were added thereto, and the mixture was stirred at room temperature for 4 hours.
2.16g (0.020mol) of o-phenylenediamine was added to 75ml of N, N-Dimethylformamide (DMF), and the mixture was dissolved completely by magnetic stirring, and the DMF solution of o-phenylenediamine was added dropwise to a three-necked flask at 80 ℃ and reacted for 4 hours by magnetic stirring. After the reaction is finished, pouring the product into ice water, standing for 1H, performing suction filtration, washing with deionized water, and drying in an oven to obtain a target product 2- (2-hydroxyphenyl) -1H-benzimidazole (HPBI); the reaction scheme is shown in FIG. 1.
FIG. 2 shows the nuclear magnetic hydrogen spectrum of 2- (2-hydroxyphenyl) -1H-benzimidazole (HPBI). Chemical shifts δ of hydrogen on hydroxy group 13.18(br,2H), chemical shifts δ of hydrogen on carbon 4-position 8.03(d,1H), chemical shifts δ of hydrogen on carbon 6-position 7.70(d,2H), chemical shifts δ of hydrogen on carbon 3-position 7.39(m,1H), chemical shifts δ of hydrogen on carbon 5-position 7.30(d,2H), and chemical shifts δ of hydrogen on carbon 2-position 7.04(m, 2H). The chemical shift δ of water was 3.34(s), and the chemical shift δ of deuterated DMSO was 2.51 (m).
As shown in FIG. 3, a Fourier transform infrared spectrum of 2- (2-hydroxyphenyl) -1H-benzimidazole (HPBI). 3233cm-1Absorption peak at position (3046 cm) is ascribed to the hydroxyl group on HPBI-1The absorption peaks at (A) correspond to N-H on the imidazole ring and 1591 and 1497cm-1The absorption peak at (A) corresponds to the structure of C ═ C on the benzene ring, 1419cm-1The absorption peak at (B) corresponds to C ═ N stretching vibration at the imidazole ring, 1318cm-1The absorption peak at (A) corresponds to C-N at 1256cm on the imidazole ring-1The absorption peak at (A) corresponds to C-O on the imidazole ring, 736cm-1The absorption peak at (a) corresponds to the out-of-plane bending vibration of C-H on the benzene ring. And can be seen at 2714--1A broad peak appears at the position, which is a characteristic absorption peak of the hydrogen bond in the molecule.
In conclusion, according to the comprehensive analysis of the nuclear magnetic hydrogen spectrum in fig. 2 and the fourier infrared spectrum in fig. 3, the imidazole derivative containing the intramolecular hydrogen bond as the curing accelerator can be determined to be prepared.
(2) Preparation of one-component epoxy resin composition
50g of tetramethyl biphenyl type epoxy resin (YX4000 with epoxy equivalent of 185g/eq), 30g of curing agent novolac phenolic resin (with hydroxyl equivalent of 106g/eq) and 0.25g of curing accelerator HPBI are melted and blended at 110 ℃, and the single-component epoxy resin composition is obtained after uniform mixing and cooling to room temperature.
Example 2
(1) Preparation of latent curing accelerators
The preparation method is the same as example 1.
(2) Preparation of one-component epoxy resin composition
50g of tetramethyl biphenyl type epoxy resin (YX4000 with epoxy equivalent of 185g/eq), 30g of curing agent novolac phenolic resin (with hydroxyl equivalent of 106g/eq) and 1.5g of curing accelerator HPBI are melted and blended at 110 ℃, and the single-component epoxy resin composition is obtained after uniform mixing and cooling to room temperature.
Comparative example 1
50g of tetramethyl biphenyl type epoxy resin (YX4000 with epoxy equivalent of 185g/eq), 30g of curing agent novolac phenolic resin (with hydroxyl equivalent of 106g/eq) and 1.5g of curing accelerator 2-methylimidazole (2MI) are melted and blended at 110 ℃, and the single-component epoxy resin composition is obtained after uniform mixing and cooling to room temperature.
Comparative example 2
50g of tetramethyl biphenyl type epoxy resin (YX4000 with the epoxy equivalent of 185g/eq), 30g of curing agent novolac phenolic resin (with the hydroxyl equivalent of 106g/eq) and 1.5g of curing accelerator triphenylphosphine (PPh3) are melted and blended at 110 ℃, mixed uniformly and cooled to room temperature to obtain the single-component epoxy resin composition.
As can be seen from fig. 4, the one-pack epoxy resin composition system containing the intramolecular hydrogen bonding imidazole accelerator HPBI in example 2 exhibited a significant latency in curing behavior and hardly cured before 160 ℃ compared to the one-pack epoxy resin composition system containing 2MI in comparative example 1 and the one-pack epoxy resin composition system containing PPh3 in comparative example 2; and when the temperature is higher than 160 ℃, the one-component epoxy resin composition in the example 2 shows a narrower exothermic peak and a faster curing reaction conversion rate, which shows that the one-component epoxy resin composition has excellent high-temperature curing activity. The HPBI has an intramolecular hydrogen bond at low temperature, so that the activity of pyridine nitrogen is sealed, the alkalinity is effectively inhibited, and the single-component epoxy resin composition has good low-temperature storage stability; at high temperature, the intramolecular hydrogen bonds of the imidazole derivative are broken, and the base catalytic activity is released again, so that the epoxy resin composition can be quickly crosslinked and cured.
As can be seen from FIG. 5, example 2 compares comparative example 1 with the pairThe cured product of the one-component epoxy resin composition containing the intramolecular hydrogen bond type imidazole accelerator HPBI of example 2, ratio 2, had a higher glass transition temperature (T)g) And is about 124 deg.c. The secondary amino and hydroxyl in the HPBI structure can participate in epoxy resin curing at high temperature, and the introduction of the benzene ring and imidazole ring structure increases the molecular chain rigidity of a crosslinking network, so that the T of a cured product is improvedg。
As can be seen from fig. 6, the cured product of the one-component epoxy resin composition of example 2 containing the intramolecular hydrogen bond type imidazole accelerator HPBI had a higher initial thermal decomposition temperature, that is, had more excellent thermal stability, than those of comparative examples 1 and 2. The secondary amino and hydroxyl in the HPBI structure can participate in epoxy resin curing at high temperature, and the introduction of the benzene ring and imidazole ring structure improves the thermal stability of a cured product.
It is to be understood that the foregoing is only exemplary of the present invention and is not intended to limit the scope of the invention, which is defined by the appended claims and their equivalents, which include all modifications of the equivalent compositions and equivalents, which fall within the true spirit and scope of the invention.
Claims (10)
1. A one-component epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator, which comprises an epoxy matrix resin, a curing agent and a curing accelerator, and is characterized in that the curing accelerator is a benzimidazole derivative with an intramolecular hydrogen bond, and the chemical structure of the benzimidazole derivative is as follows:
wherein R is1And R4Is a hydrogen atom (H); r2And R3Is a hydrogen atom (H), a methyl group (CH)3) Methoxy (CH)3O), fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or nitro group (NO)2)，R2And R3May be the same or different from each other; r5Is a hydrogen atom (H) or a methyl group (CH)3)；R6And R7Is a hydrogen atom (H), a methyl group (CH)3) Methoxy (CH)3O), fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or nitro group (NO)2)，R6And R7May be the same or different from each other; r8Is a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl) or a methoxy group (CH)3O)。
2. The one-pack epoxy resin composition containing an intramolecular hydrogen bonding type imidazole curing accelerator according to claim 1, wherein the molar ratio between the epoxy group of the epoxy matrix resin and the reactive group of the curing agent is 0.8 to 1.3; the addition amount of the curing accelerator is 0.5-5 wt% of epoxy matrix resin in the epoxy resin composition.
3. A method for producing the one-pack epoxy resin composition containing an intramolecular hydrogen bonding type imidazole curing accelerator according to claim 1, comprising the steps of:
s1: preparation of curing accelerator containing intramolecular hydrogen bond type imidazole
S1-1: adding sodium bisulfite and o-hydroxybenzaldehyde or derivatives thereof into an organic solvent according to the mass ratio of 1: 1-10: 1 at room temperature, and fully mixing and dissolving;
s1-2: dripping solution of o-phenylenediamine or derivatives thereof into the mixture to perform Schiff base reaction and oxidation reaction to obtain solution of imidazole derivatives with intramolecular hydrogen bonds;
s1-3, pouring the product in the S1-2 into ice water, standing for a period of time, performing suction filtration, washing with deionized water for multiple times, and drying in an oven to obtain a target product, namely the imidazole derivative with intramolecular hydrogen bonds;
s2: preparation of one-component epoxy resin composition
And melting and blending the epoxy resin, the curing agent and the curing accelerator prepared in S1 at a certain temperature, uniformly mixing, and cooling to room temperature to obtain the single-component epoxy resin composition.
4. The method for preparing a one-pack epoxy resin composition containing an intramolecular hydrogen bonding type imidazole curing accelerator according to claim 3, wherein the organic solvent in S1-1 is a mixture of one or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, cyclohexane and dichloromethane.
5. The method of claim 3, wherein the solvent of the solution of o-phenylenediamine or its derivative in S1-2 is a mixture of one or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, dimethylsulfoxide, cyclohexane, and dichloromethane.
6. The method for preparing a one-component epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator according to claim 3, wherein the reaction temperature of the Schiff base reaction and the oxidation reaction is 40 to 200 ℃ and the reaction time is 4 to 8 hours.
7. The method for preparing a one-component epoxy resin composition containing an intramolecular hydrogen bonding imidazole curing accelerator according to claim 3, wherein the standing time in S1-3 is 1 to 2 hours.
8. The method for preparing a one-pack epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator according to claim 3, wherein the melt blending temperature in S2 is 110 to 150 ℃.
9. The one-pack epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator according to claim 1 or 3, wherein the epoxy matrix resin is one or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and alicyclic type epoxy resin.
10. The one-pack epoxy resin composition containing an intramolecular hydrogen bond type imidazole curing accelerator according to claim 1 or 3, wherein the curing agent is one or more of acid anhydride, polyaromatic amine, dicyandiamide, polyphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234013.4A CN110790903A (en) | 2019-12-05 | 2019-12-05 | Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234013.4A CN110790903A (en) | 2019-12-05 | 2019-12-05 | Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110790903A true CN110790903A (en) | 2020-02-14 |
Family
ID=69447693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911234013.4A Pending CN110790903A (en) | 2019-12-05 | 2019-12-05 | Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790903A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102236259A (en) * | 2010-04-28 | 2011-11-09 | Jsr株式会社 | Radiation sensitivity resin composition for display element, interlayer insulation film, protective film and spacer and forming method thereof |
| CN104516196A (en) * | 2013-10-02 | 2015-04-15 | Jsr株式会社 | Hardenable composition, hardened film and forming method thereof, and compound |
| CN106432584A (en) * | 2016-09-18 | 2017-02-22 | 江南大学 | Synthesis of imidazole latent epoxy curing accelerator having toughening effect and application of accelerator in epoxy modification |
-
2019
- 2019-12-05 CN CN201911234013.4A patent/CN110790903A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102236259A (en) * | 2010-04-28 | 2011-11-09 | Jsr株式会社 | Radiation sensitivity resin composition for display element, interlayer insulation film, protective film and spacer and forming method thereof |
| CN104516196A (en) * | 2013-10-02 | 2015-04-15 | Jsr株式会社 | Hardenable composition, hardened film and forming method thereof, and compound |
| CN106432584A (en) * | 2016-09-18 | 2017-02-22 | 江南大学 | Synthesis of imidazole latent epoxy curing accelerator having toughening effect and application of accelerator in epoxy modification |
Non-Patent Citations (1)
| Title |
|---|
| STARCHAK, V. G. ET AL.: ""Effectiveness of arylbenzimidazole derivatives in powdered protective epoxy paint compounds"", 《PROTECTION OF METALS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI820204B (en) | Maleimide resin, curable resin composition and cured product | |
| JP5348740B2 (en) | Epoxy resin, epoxy resin composition, and cured product thereof | |
| CN112334512B (en) | Maleimide resin, curable resin composition, and cured product thereof | |
| CN112194779A (en) | Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof | |
| KR101143131B1 (en) | Epoxy compound, preparation method thereof, and use thereof | |
| JPWO2019244694A1 (en) | Curable compound | |
| JP5127164B2 (en) | Modified epoxy resin, epoxy resin composition, and cured product thereof | |
| JP5196625B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| CA1222521A (en) | Triglycidyl compounds of aminophenols | |
| EP3248996A1 (en) | Aromatic amine resin, and epoxy resin composition and cured product thereof | |
| JP4655490B2 (en) | Epoxy resin composition and cured product thereof | |
| WO2015093461A1 (en) | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof | |
| JPWO2018123806A1 (en) | Alkenyl group-containing resin, curable resin composition and cured product thereof | |
| JP2010163540A (en) | Epoxy resin composition and cured material of the same | |
| JP2003301031A (en) | Phenolic resin, epoxy resin and method for preparation thereof, and resin composition | |
| JP2008195843A (en) | Phenolic resin, epoxy resin, epoxy resin composition, and cured product of the same | |
| CN110790903A (en) | Single-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof | |
| KR102099795B1 (en) | Compound having anhydrosugar alcohol core and method for preparing the same | |
| TWI754743B (en) | Methallyl-containing resin, curable resin composition and cured product thereof | |
| JP2010006897A (en) | Polyhydric phenol resin, epoxy resin composition, and its cured product | |
| JP5093904B2 (en) | Epoxy resin and production method thereof | |
| JP4142155B2 (en) | Epoxy resin and method for producing the same | |
| WO2022075324A1 (en) | Curable compound product | |
| TWI802196B (en) | Resin composition and resin film | |
| JP5579300B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200214 |