CN116102713A - Multi-arm structure amine epoxy curing agent and preparation method thereof - Google Patents
Multi-arm structure amine epoxy curing agent and preparation method thereof Download PDFInfo
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- CN116102713A CN116102713A CN202211088602.8A CN202211088602A CN116102713A CN 116102713 A CN116102713 A CN 116102713A CN 202211088602 A CN202211088602 A CN 202211088602A CN 116102713 A CN116102713 A CN 116102713A
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- curing agent
- epoxy curing
- amine epoxy
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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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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 an amine epoxy curing agent with a multi-arm structure. It is made up by using (wt%) 30-50% of ternary or above-ternary polyhydric phenol, 40-60% of acrylonitrile, 5-15% of hydrogen and 3-8% of metal catalyst. The preparation method screens out various reaction raw material compositions and specific reaction steps through a large number of experiments, and the prepared multi-arm structure amine epoxy curing agent is matched with epoxy resin for curing, has the advantages of quick drying, high hardness and high gloss, and also has excellent heat resistance and corrosion resistance.
Description
Technical Field
The invention relates to an amine epoxy curing agent with a multi-arm structure and a preparation method thereof.
Background
The double-component system composed of the epoxy resin and the epoxy resin curing agent is widely used in the fields of floor coatings, anticorrosive coatings, adhesives, composite materials and the like due to the characteristics of small curing shrinkage, good cohesiveness, heat resistance, chemical resistance, mechanical properties and electrical properties.
In an epoxy two-component coating or adhesive system, the structural characteristics of the curing agent play a key role in the performance of the epoxy system. Typical amine curing agents contain only two amino groups, such as ethylenediamine, hexamethylenediamine, cyclohexanediamine, 1, 3-cyclohexanediamine, isoparaffinone diamine, m-xylylenediamine, diaminodicyclohexylmethane, and the like, and amine curing agents contain three or more amino groups, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and aminoethylpiperazine, but the number of primary amino groups in these molecules is not more than two.
According to the invention, through a large number of experimental screening, the Michael addition is carried out by using the polyhydric phenol and the acrylonitrile, and then the cyano group in the addition product is reduced to primary amine, so that the amine epoxy curing agent with a multi-arm structure is developed. The product contains three or more primary amino groups, so that the activity is higher, and the curing speed is higher. The cured product has a compact three-dimensional structure after curing, and better heat resistance and corrosion resistance are provided for the cured product.
Disclosure of Invention
The invention aims to: the invention aims to provide an amine epoxy curing agent with a multi-arm structure; the invention also aims at providing a preparation method of the curing agent.
The technical scheme is as follows: in order to achieve the above purpose, the invention adopts the following technical scheme:
the amine epoxy curing agent with the multi-arm structure is prepared from the following raw materials in percentage by mass:
30-50% of ternary or higher polyhydric phenol, 40-60% of acrylonitrile, 5-15% of hydrogen and 3-8% of metal catalyst.
As a preferable scheme, the multi-arm structure amine epoxy curing agent is one or a mixture of more than three-element polyhydric phenols such as trimellitic phenol, phloroglucinol, 1,2,4, 5-benzene tetraphenol, 2,4,6,3',5' -biphenyl pentachenol and benzene hexaphenol.
As a preferable scheme, the multi-arm structure amine epoxy curing agent is one or a mixture of a plurality of nickel, platinum and palladium as metal catalysts.
The invention relates to a preparation method of a multi-arm structure amine epoxy resin curing agent, which comprises the following steps:
1) Adding the ternary or more polyhydric phenols and acrylonitrile into the reaction kettle according to the mass percentage, and uniformly stirring;
2) Heating to 60-90 ℃, and preserving heat for reacting for a period of time;
3) Adding a metered metal catalyst;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) Introducing hydrogen into the reaction kettle until the pressure reaches a certain pressure;
6) Heating to 90-110 ℃, and preserving heat for reacting for a period of time;
7) Filtering to obtain the finished product of the amine epoxy curing agent with the multi-arm structure.
As a preferable scheme, the preparation method of the multi-arm structure amine epoxy resin curing agent comprises the following steps:
1) Adding the ternary or more polyhydric phenols and acrylonitrile into the reaction kettle according to the mass percentage, and uniformly stirring;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) Adding a metered metal catalyst;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) Introducing hydrogen into the reaction kettle until the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) And (5) filtering. Obtaining the finished product of the amine epoxy curing agent with the multi-arm structure.
As an optimal scheme, the preparation method of the multi-arm structure amine epoxy curing agent provided by the invention has the advantage that the optimal molar ratio of phenolic hydroxyl groups to acrylonitrile in the polyhydric phenol is 1:1.
Typical reaction processes of the present invention are shown in the following reaction equations:
the invention mainly improves the defects of the existing amine epoxy curing agent through the following schemes:
1. the invention increases the reactivity of the curing agent and the epoxy resin by increasing the number of primary amino groups in the epoxy curing agent, thus obtaining faster curing speed.
2. The invention uses polyhydric phenol as initial raw material, the final product contains benzene ring core skeleton, and compared with aliphatic amine such as ethylenediamine, diethylenetriamine, hexamethylenediamine, etc., the condensate has better rigidity and heat resistance.
3. The product of the invention has a multi-arm structure, has a more compact structure with the cured product of the epoxy resin, and has better corrosion resistance effect.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention obtains the optimal raw material proportioning composition through a large number of experimental screening, selects the polyhydric phenols with different structures as the initial raw materials, and the prepared multi-arm structure amine epoxy curing agent has the advantages of quick drying, high hardness and high gloss, and also has excellent heat resistance and corrosion resistance.
Detailed Description
The molar ratio of phenolic hydroxyl groups to acrylonitrile in each of the following examples 1 to 3 was 1:1. as for the molar ratio of phloroglucinol to acrylonitrile in example 1, 1/3,1mol of phloroglucinol had 3mol of phenolic hydroxyl groups, i.e., 1/1 in terms of phenolic hydroxyl groups/acrylonitrile molar ratio. Examples 2 and 3 are the same.
Example 1
1. The amine epoxy curing agent with the multi-arm structure is prepared from the following raw materials in percentage by mass:
38% of phloroglucinol, 48% of acrylonitrile, 9% of hydrogen and 5% of metal catalyst.
2. The preparation method of the amine epoxy curing agent with the multi-arm structure comprises the following steps:
1) 380g of phloroglucinol and 480g of acrylonitrile are put into a reaction kettle and stirred uniformly;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) 50g Raney nickel (Raney Ni) was added;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) 90g of hydrogen is introduced into the reaction kettle, and the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) Filtering to obtain the finished product of the amine epoxy curing agent with the multi-arm structure.
Example 2
1. The amine epoxy curing agent with the multi-arm structure is prepared from the following raw materials in percentage by mass: 36% of 1,2,4, 5-benzene tetraphenol, 53% of acrylonitrile, 8% of hydrogen and 3% of metal catalyst.
2. The preparation method of the amine epoxy curing agent with the multi-arm structure comprises the following steps:
1) 360g of 1,2,4, 5-benzene tetraphenol and 530g of acrylonitrile are put into a reaction kettle and stirred uniformly;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) 30g of platinum catalyst was added;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) 80g of hydrogen is introduced into the reaction kettle, and the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) And (5) filtering. Obtaining the finished product of the amine epoxy curing agent with the multi-arm structure.
Example 3
1. The amine epoxy curing agent with the multi-arm structure is prepared from the following raw materials in percentage by mass: 40% of 2,4,6,3',5' -biphenol, 45% of acrylonitrile, 10% of hydrogen and 5% of metal catalyst palladium carbon.
2. The preparation method of the amine epoxy curing agent with the multi-arm structure comprises the following steps:
1) 400g of 2,4,6,3',5' -biphenol and 450g of acrylonitrile are put into a reaction kettle and stirred uniformly;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) Adding 50g of palladium-carbon catalyst;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) Introducing 100g of hydrogen into the reaction kettle, wherein the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) Filtering to obtain the finished product of the amine epoxy curing agent with the multi-arm structure.
Comparative example 1
1. The amount of acrylonitrile used in example 1 was reduced, and the molar ratio of phloroglucinol to acrylonitrile was adjusted to 1:2.5. The material is prepared from the following raw materials in percentage by mass: 42% of phloroglucinol, 44% of acrylonitrile, 9% of hydrogen and 5% of metal catalyst.
2. The preparation method of the amine epoxy curing agent with the multi-arm structure comprises the following steps:
1) 420g of phloroglucinol and 440g of acrylonitrile are put into a reaction kettle and stirred uniformly;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) 50g Raney nickel (Raney Ni) was added;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) 90g of hydrogen is introduced into the reaction kettle, and the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) And (5) filtering. Obtaining the finished product of the amine epoxy curing agent with the multi-arm structure.
Comparative example 2
1. The amount of acrylonitrile used in example 1 was increased and the molar ratio of phloroglucinol to acrylonitrile was adjusted to 1:3.5. The material is prepared from the following raw materials in percentage by mass: 35% of phloroglucinol, 51% of acrylonitrile, 9% of hydrogen and 5% of metal catalyst.
2. The preparation method of the amine epoxy curing agent with the multi-arm structure comprises the following steps:
1) 350g of phloroglucinol and 510g of acrylonitrile are put into a reaction kettle and stirred uniformly;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) 50g Raney nickel (Raney Ni) was added;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) 90g of hydrogen is introduced into the reaction kettle, and the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) And (5) filtering. Obtaining the finished product of the amine epoxy curing agent with the multi-arm structure.
Example 4 Performance test
Epoxy resin (828 manufactured by Jiangsu Sanmu chemical Co., ltd.) was mixed with the epoxy resin curing agents prepared in examples 1 to 3 and comparative examples 1 to 2 in proportion, and then uniformly coated on tin plates to form films with a film thickness of 40. Mu.m. Meanwhile, the diamine curing agent meta-xylylenediamine (MXDA) with good heat resistance and corrosion resistance is compared and tested. The basic properties after curing of the finished products obtained in examples 1 to 3, comparative examples 1 to 2 and m-xylylenediamine (MXDA) were measured as shown in table 1 below.
TABLE 1 Performance test results
The performance detection results show that the multi-arm structure amine epoxy curing agent prepared by the invention is matched with epoxy resin for curing, has the advantages of quick dryness and high hardness, has excellent heat resistance and corrosion resistance, and achieves good technical effects. And it can be seen from comparison that the curing agent synthesized in example 1 has better performance than those obtained in comparative examples 1 and 2, which means that the molar ratio of phloroglucinol to acrylonitrile (molar ratio of phenolic hydroxyl groups to acrylonitrile 1:1) has a great influence on the structure and performance of the reaction product. From the comparison of examples 1 to 3, it can be seen that example 3 has the shortest tack-free time and tack-free time.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. An amine epoxy curing agent with a multi-arm structure is characterized in that: the material is prepared from the following raw materials in percentage by mass:
30-50% of ternary or higher polyhydric phenol, 40-60% of acrylonitrile, 5-15% of hydrogen and 3-8% of metal catalyst.
2. The multi-arm structure amine epoxy curing agent according to claim 1, wherein the ternary or higher polyhydric phenol is one or a mixture of more of trimellitic phenol, phloroglucinol, 1,2,4, 5-benzene tetraphenol, 2,4,6,3',5' -bipentaphenol and benzene hexaphenol.
3. The multi-arm structure amine epoxy curing agent according to claim 1, wherein the metal catalyst is one or a mixture of nickel, platinum and palladium.
4. A method for preparing the amine epoxy curing agent with a multi-arm structure according to any one of claims 1 to 3, which is characterized by comprising the following steps:
1) Adding the ternary or more polyhydric phenols and acrylonitrile into the reaction kettle according to the mass percentage, and uniformly stirring;
2) Heating to 60-90 ℃, and preserving heat for reacting for a period of time;
3) Adding a metered metal catalyst;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) Introducing hydrogen into the reaction kettle until the pressure reaches a certain pressure;
6) Heating to 90-110 ℃, and preserving heat for reacting for a period of time;
7) Filtering to obtain the finished product of the amine epoxy curing agent with the multi-arm structure.
5. The method for preparing the amine epoxy curing agent with the multi-arm structure according to claim 4, which is characterized by comprising the following steps:
1) Adding the ternary or more polyhydric phenols and acrylonitrile into the reaction kettle according to the mass percentage, and uniformly stirring;
2) Heating to 80 ℃, and preserving heat for reaction for 3 hours;
3) Adding a metered metal catalyst;
4) Introducing nitrogen into the reaction kettle, and evacuating air in the kettle;
5) Introducing hydrogen into the reaction kettle until the pressure reaches 2MPa;
6) Heating to 100 ℃, and preserving heat for reaction for 3 hours;
7) Filtering to obtain the finished product of the amine epoxy curing agent with the multi-arm structure.
6. The method for preparing a multi-arm amine epoxy curing agent according to claim 4 or 5, wherein the molar ratio of phenolic hydroxyl groups to acrylonitrile in the polyhydric phenol is 1:1.
7. The amine epoxy curing agent with a multi-arm structure according to claim 1, wherein the amine epoxy curing agent is characterized in that: the material is prepared from the following raw materials in percentage by mass:
38% of phloroglucinol, 48% of acrylonitrile, 9% of hydrogen and 5% of metal catalyst.
8. The amine epoxy curing agent with a multi-arm structure according to claim 1, wherein the amine epoxy curing agent is characterized in that: the material is prepared from the following raw materials in percentage by mass:
36% of 1,2,4, 5-benzene tetraphenol, 53% of acrylonitrile, 8% of hydrogen and 3% of metal catalyst.
9. The amine epoxy curing agent with a multi-arm structure according to claim 1, wherein the amine epoxy curing agent is characterized in that: the material is prepared from the following raw materials in percentage by mass:
40% of 2,4,6,3',5' -biphenol, 45% of acrylonitrile, 10% of hydrogen and 5% of metal catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211088602.8A CN116102713A (en) | 2022-09-07 | 2022-09-07 | Multi-arm structure amine epoxy curing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211088602.8A CN116102713A (en) | 2022-09-07 | 2022-09-07 | Multi-arm structure amine epoxy curing agent and preparation method thereof |
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| CN116102713A true CN116102713A (en) | 2023-05-12 |
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| CN202211088602.8A Pending CN116102713A (en) | 2022-09-07 | 2022-09-07 | Multi-arm structure amine epoxy curing agent and preparation method thereof |
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- 2022-09-07 CN CN202211088602.8A patent/CN116102713A/en active Pending
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