CN110551275A - Flexible imidazole epoxy adduct curing agent and preparation method thereof - Google Patents
Flexible imidazole epoxy adduct curing agent and preparation method thereof Download PDFInfo
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- CN110551275A CN110551275A CN201910834825.6A CN201910834825A CN110551275A CN 110551275 A CN110551275 A CN 110551275A CN 201910834825 A CN201910834825 A CN 201910834825A CN 110551275 A CN110551275 A CN 110551275A
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- imidazole
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- epoxy adduct
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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
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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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
- C08G59/56—Amines together with other curing agents
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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
- C08G59/62—Alcohols or phenols
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a flexible imidazole epoxy adduct curing agent and a preparation method thereof, wherein the curing agent is beige to dark yellow solid powder, and has a softening point of 75 ℃ of ~ ℃, the preparation method comprises the steps of dissolving an imidazole compound and polyhydric alcohol at a certain temperature, slowly dripping bisphenol A epoxy resin for 2 hours, reacting for 0.5 ~ hours at the temperature, separating a solvent from a product, and drying and crushing the product to obtain the powdery flexible imidazole epoxy adduct curing agent.
Description
Technical Field
The invention relates to the technical field of epoxy resin curing agents, in particular to a flexible imidazole epoxy adduct curing agent and a preparation method thereof.
Background
Epoxy resin is widely applied to various fields of national economy due to excellent adhesive property, electrical insulation property, corrosion resistance and mechanical property. In the application of epoxy resin, the curing agent plays an essential important role, wherein imidazole and derivatives thereof are an important class of epoxy resin curing agents. With the development of the electronic industry in recent years, the dosage of the imidazole epoxy resin curing agent accounts for more than 90 percent of the total production.
Imidazole is a five-membered ring containing two nitrogen atoms, one of which constitutes a secondary amine and the other of which constitutes a tertiary amine, and can cure epoxy resins by the addition reaction of active hydrogen of the secondary amine group to the epoxy resin and by the tertiary nitrogen atom as an anionic polymerization type curing agent like a tertiary amine. Imidazole compounds are mostly high-melting-point crystals, have the characteristics of volatility and moisture absorption, are difficult to mix with liquid epoxy resin, and have the problem of short storage time. The imidazole/epoxy adduct curing agent can be used as a low-temperature curing agent alone or as a curing accelerator in combination with other curing agents. It has the characteristics of low curing temperature, short curing time, long operable time, high glass transition temperature of a cured product and the like, and has the defect of large curing heat release. In order to reduce the curing heat release greatly and increase the toughness of a cured product, a flexible group is introduced into the main chain of the imidazole/epoxy adduct so as to improve the toughness of the cured product, solve the defects of the existing imidazole/epoxy adduct and improve the comprehensive performance of the imidazole/epoxy adduct.
Disclosure of Invention
The invention aims to solve the problem that the imidazole/epoxy adduct and an epoxy resin condensate have large heat release, introduce a flexible group into the main chain of the imidazole/epoxy adduct, and develop a flexible imidazole epoxy adduct curing agent and a preparation method thereof so as to improve the toughness of the condensate, solve the defects of the existing imidazole/epoxy adduct and improve the comprehensive performance of the condensate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flexible imidazole epoxy adduct curing agent is characterized by being beige to dark yellow powder with a softening point of 75 ℃ of ~ 140 ℃.
A preparation method of a flexible imidazole epoxy adduct curing agent is characterized by comprising the steps of adding an imidazole compound, polyol (the molar ratio of the imidazole compound to the polyol is 1:0.01 ~ 0.55.55) and a solvent into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condensation pipe and a nitrogen inlet and outlet, stirring and heating to 40 ℃ ~ 120 ℃ under the protection of nitrogen until the mixture is dissolved, slowly adding bisphenol A epoxy resin (the molar ratio of the imidazole compound to the bisphenol A epoxy resin is 1:0.5 ~ 1.5.5) dropwise within 2 hours, reacting for 0.5 ~ 8 hours at the temperature, cooling the reaction system to room temperature, separating the solvent from a product, cleaning the product with ethanol or water for three times, then carrying out vacuum drying at 50 ℃ and ~ 100 ℃, and crushing to obtain a beige-deep yellow powder flexible imidazole epoxy adduct curing agent.
The imidazole compound is one or more of 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-methylimidazole.
the polyol is one or more of diethylene glycol, polyether polyol, polyester polyol or polycarbonate polyol.
the solvent is one or more of chloroform, dichloromethane, toluene, xylene, N,N -dimethylformamide, N,N -dimethylacetamide, N -methylpyrrolidone, dimethyl sulfoxide, sulfolane and water, and the using amount of the solvent is 4 ~ 10 times of the mass of all the reactants.
The epoxy resin is any one of liquid bisphenol A type epoxy resin E51, NPEL-128, CYD-128 or WRS-618, and has the epoxy equivalent of 184-194 and the viscosity of 10000 ~ 18000 cps.
compared with the prior art, the invention has the following characteristics and effective effects:
1. The invention utilizes flexible groups introduced into the main chain of imidazole/epoxy adduct to synthesize a flexible imidazole epoxy adduct curing agent, and the method comprises the following steps: dissolving imidazole compounds and polyhydric alcohol at a certain temperature, then dropwise adding bisphenol A epoxy resin, reacting for a certain time, separating the solvent and the product, drying and crushing the product to obtain the powdery flexible imidazole epoxy adduct curing agent.
2. The synthetic method of the flexible imidazole epoxy adduct curing agent has the characteristics of simple process and good product stability.
3. The flexible imidazole epoxy adduct curing agent is a flexible epoxy curing agent, and is suitable for the fields of composite materials, casting materials, electronic and electric appliance materials, adhesives, epoxy coatings, epoxy pouring sealants and the like; the preparation process of the product is simple and convenient, the operation is easy, and the practicability is strong.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be noted that these examples are provided for illustrative purposes only and are not to be construed as limiting the scope of the present invention, and that those skilled in the art will be able to make insubstantial modifications and adaptations of the invention in view of the above teachings.
Example 1:
Adding 0.2 mol of 2-methylimidazole, 0.002 mol of polypropylene glycol 600 and 360 g of water into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condenser pipe and a nitrogen inlet and outlet, heating to 40 ℃ under the protection of nitrogen, stirring until the mixture is dissolved, slowly adding 0.27 mol of bisphenol A epoxy resin E51 dropwise within 2 hours, reacting for 4 hours at the temperature, cooling the reaction system to room temperature, separating water from a product, washing the product with ethanol for three times, then drying in vacuum at 50 ℃, and crushing to obtain a beige powder with a softening point of 82 ℃.
Example 2:
Adding 0.2 mol of 2-phenylimidazole, 0.005 mol of polycaprolactone polyol 1000 and 660 g of xylene into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condenser pipe and a nitrogen inlet and outlet, stirring and heating to 120 ℃ under the protection of nitrogen until the mixture is dissolved, slowly adding 0.28 mol of bisphenol A epoxy resin NPEL-128 dropwise within 2 hours, reacting for 5 hours at the temperature, cooling the reaction system to room temperature, separating the xylene from the product, washing the product with ethanol for three times, drying the product in vacuum at 80 ℃, and crushing the product to obtain dark yellow powder with a softening point of 130 ℃.
Example 3:
Adding 0.2 mol of 2-ethyl-4-methylimidazole, 0.01 mol of polycarbonate 1000 and 600 g of N -methylpyrrolidone into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condenser tube and a nitrogen inlet and outlet, stirring and heating to 100 ℃ under the protection of nitrogen till dissolving, slowly adding 0.16 mol of bisphenol A epoxy resin NPEL-128 dropwise into the reaction kettle for 2 hours, reacting for 3 hours at the temperature, cooling the reaction system to room temperature, separating N -methylpyrrolidone from the product, washing the product with water for three times, drying in vacuum at 80 ℃, and crushing to obtain dark yellow powder with a softening point of 100 ℃.
Example 4:
Adding 0.2 mol of 2-phenylimidazole, 0.1 mol of 1-cyanoethyl-2-methylimidazole, 0.01 mol of diethylene glycol and 700 g of xylene into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condenser tube and a nitrogen inlet and outlet, stirring while heating to 115 ℃ under the protection of nitrogen, stirring until the diethylene glycol is dissolved, slowly adding 0.3 mol of bisphenol A epoxy resin NPEL-128 dropwise over 2 hours, reacting for 2 hours at the temperature, cooling the reaction system to room temperature, separating the xylene from a product, washing the product with ethanol for three times, drying in vacuum at 90 ℃, and crushing to obtain dark yellow powder with a softening point of 118 ℃.
the prepared flexible imidazole epoxy curing agent and bisphenol A epoxy resin NPEL-128 are cured for 40 minutes and 60 minutes at 120 ℃, and the properties of the obtained cured product are shown in Table 1.
TABLE 1 Properties of cured products of Flexible imidazole-based epoxy hardeners obtained in examples 1 to 4
The above examples are only for illustrating the present invention and not for limiting the technical solutions described in the present invention, and any person skilled in the art can easily make component changes or substitutions after the present invention is disclosed, and all technical solutions and modifications without departing from the scope and spirit of the present invention should be covered by the claims of the present invention.
Claims (6)
1. The flexible imidazole epoxy adduct curing agent is characterized by being beige to dark yellow powder with a softening point of 75 ℃ of ~ 140 ℃.
2. A preparation method of a flexible imidazole epoxy adduct curing agent is characterized by comprising the steps of adding an imidazole compound, polyol (the molar ratio of the imidazole compound to the polyol is 1:0.01 ~ 0.55.55) and a solvent into a detachable reaction kettle provided with a stirrer, a dropping funnel, a condensation pipe and a nitrogen inlet and outlet, stirring and heating to 40 ℃ ~ 120 ℃ under the protection of nitrogen until the mixture is dissolved, slowly adding bisphenol A epoxy resin (the molar ratio of the imidazole compound to the bisphenol A epoxy resin is 1:0.5 ~ 1.5.5) dropwise within 2 hours, reacting for 0.5 ~ 8 hours at the temperature, cooling the reaction system to room temperature, separating the solvent from a product, cleaning the product with ethanol or water for three times, then carrying out vacuum drying at 50 ℃ and ~ 100 ℃, and crushing to obtain a beige-deep yellow powder flexible imidazole epoxy adduct curing agent.
3. The method for preparing the flexible imidazole based epoxy adduct curing agent according to claim 2, which is characterized in that: the imidazole compound is one or more of 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and 1-cyanoethyl-2-methylimidazole.
4. The method for preparing the flexible imidazole based epoxy adduct curing agent according to claim 2, which is characterized in that: the polyol is one or more of diethylene glycol, polyether polyol, polyester polyol or polycarbonate polyol.
5. The preparation method of the flexible imidazole based epoxy adduct curing agent as claimed in claim 2, wherein the solvent is one or more of chloroform, dichloromethane, toluene, xylene, N,N -dimethylformamide, N,N -dimethylacetamide, N -methylpyrrolidone, dimethyl sulfoxide, sulfolane and water, and the amount of the solvent is 4 ~ 10 times of the mass of all reactants.
6. The preparation method of the flexible imidazole based epoxy adduct curing agent as claimed in claim 2, wherein the epoxy resin is any one of liquid bisphenol A type epoxy resin E51, NPEL-128, CYD-128 or WRS-618, and the epoxy equivalent is 184-194, and the viscosity is 10000 ~ 18000 cps.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851914A (en) * | 2021-01-11 | 2021-05-28 | 安徽工业大学 | Composite modified 2-methylimidazole curing agent and preparation method thereof |
| CN114369405A (en) * | 2022-01-19 | 2022-04-19 | 安徽朗凯奇防水科技股份有限公司 | Epoxy crack sealer and preparation method thereof |
| CN116253684A (en) * | 2023-02-17 | 2023-06-13 | 天津工业大学 | 2-heptadecyl imidazole and synthetic method thereof |
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| EP0086102A2 (en) * | 1982-02-08 | 1983-08-17 | INTEREZ, Inc.(a Delaware corporation) | Poyol/imidazole curing agents for epoxy resins |
| US4417010A (en) * | 1982-02-08 | 1983-11-22 | Celanese Corporation | Polyol/imidazole curing agents for epoxy resins |
| US20030187155A1 (en) * | 2000-11-16 | 2003-10-02 | Schile Richard D. | Epoxy hardeners for low temperature curing |
| CN102276797A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof |
| CN102504205A (en) * | 2011-11-10 | 2012-06-20 | 湖南神力铃胶粘剂制造有限公司 | Preparation method for epoxy hardener resistant to boiling water boiling |
| CN110156572A (en) * | 2019-05-24 | 2019-08-23 | 陕西生益科技有限公司 | A kind of preparation method of epoxy curing agent |
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2019
- 2019-09-05 CN CN201910834825.6A patent/CN110551275B/en active Active
Patent Citations (6)
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| EP0086102A2 (en) * | 1982-02-08 | 1983-08-17 | INTEREZ, Inc.(a Delaware corporation) | Poyol/imidazole curing agents for epoxy resins |
| US4417010A (en) * | 1982-02-08 | 1983-11-22 | Celanese Corporation | Polyol/imidazole curing agents for epoxy resins |
| US20030187155A1 (en) * | 2000-11-16 | 2003-10-02 | Schile Richard D. | Epoxy hardeners for low temperature curing |
| CN102276797A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Epoxy resin composition with excellent temperature cycle performance and preparation method thereof |
| CN102504205A (en) * | 2011-11-10 | 2012-06-20 | 湖南神力铃胶粘剂制造有限公司 | Preparation method for epoxy hardener resistant to boiling water boiling |
| CN110156572A (en) * | 2019-05-24 | 2019-08-23 | 陕西生益科技有限公司 | A kind of preparation method of epoxy curing agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851914A (en) * | 2021-01-11 | 2021-05-28 | 安徽工业大学 | Composite modified 2-methylimidazole curing agent and preparation method thereof |
| CN114369405A (en) * | 2022-01-19 | 2022-04-19 | 安徽朗凯奇防水科技股份有限公司 | Epoxy crack sealer and preparation method thereof |
| CN116253684A (en) * | 2023-02-17 | 2023-06-13 | 天津工业大学 | 2-heptadecyl imidazole and synthetic method thereof |
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| CN110551275B (en) | 2022-04-12 |
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