CN111138637A - Anti-aging epoxy resin curing agent and preparation method thereof - Google Patents
Anti-aging epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN111138637A CN111138637A CN201811300453.0A CN201811300453A CN111138637A CN 111138637 A CN111138637 A CN 111138637A CN 201811300453 A CN201811300453 A CN 201811300453A CN 111138637 A CN111138637 A CN 111138637A
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- curing agent
- epoxy resin
- resin curing
- aging
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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
-
- 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
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
-
- 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
- C08G59/60—Amines together with other curing agents with amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention provides an anti-aging epoxy resin curing agent which comprises the following raw materials in parts by mass: 3-8 parts of fatty polyamine, 2-5 parts of cardanol, 1-3 parts of polyamide, 2-4 parts of alumina, 0.5-1 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3-0.5 part of titanium dioxide. The curing agent system of the invention not only has the hardness and chemical corrosion resistance of a fatty amine system, but also has long-term applicability, good toughness and low toxicity of a polyamide system. Can absorb ultraviolet ray well and prevent epoxy resin from ageing. The cardanol structurally contains a carbon pentadecane branch chain with an unsaturated double bond, the surface energy and the viscosity of the system are reduced, the adhesion to a substrate is improved, and the donor system provides excellent hydrophobicity and low permeability. The gamma-glycidoxypropyltrimethoxysilane is used as a filler, can participate in the curing process of a curing agent and epoxy resin, and prevents the corrosion and the damage of acid and alkali.
Description
Technical Field
The invention relates to an anti-aging epoxy resin curing agent and a preparation method thereof, belonging to the field of epoxy resin curing agents.
Background
Epoxy resin has the advantages of good cohesiveness, corrosion resistance, electrical insulation, high strength, small shrinkage and the like, so that the epoxy resin is widely applied to many fields of electronics, electricity, mechanical manufacturing, chemical corrosion, aerospace, ship transportation and the like, and becomes an indispensable basic material in industrial production. However, the epoxy resin-based composite material has poor ultraviolet aging resistance, and the molecular chain of common epoxy resin is damaged by absorbing ultraviolet rays, so that the epoxy resin has poor ultraviolet aging resistance and is easy to pulverize after being cured and molded, and the epoxy resin is limited when being used as a coating or other materials. Therefore, how to improve the ultraviolet aging resistance of the epoxy resin, delay the aging speed of products and prolong the service life of the epoxy resin is an important subject of research in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides an anti-aging epoxy resin curing agent and a preparation method thereof, which endow epoxy resin with anti-aging performance.
The technical scheme for solving the technical problems is as follows: an anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 3-8 parts of fatty polyamine, 2-5 parts of cardanol, 1-3 parts of polyamide, 2-4 parts of alumina, 0.5-1 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3-0.5 part of titanium dioxide.
The invention is further set that the anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 4-6 parts of fatty polyamine, 3-4 parts of cardanol, 2-2.5 parts of polyamide, 2-3 parts of alumina, 0.6-0.8 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3-0.5 part of titanium dioxide.
The invention is further provided that the aliphatic polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, diethylaminopropylene, dihexyltriamine and hexanediamine.
The invention further provides that the aliphatic polyamine is a mixture of diethylenetriamine, diethylaminopropylene and hexamethylene diamine, and the mass ratio of the diethylenetriamine to the diethylaminopropylene to the hexamethylene diamine is 1: (1-2): (1.5-2).
The invention is further provided that the gamma-glycidyl ether oxygen propyl trimethoxy silane is 0.6 to 1.2 parts by mass.
Another technical solution of the present invention for solving the above technical problems is as follows: the preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence and mixing uniformly; (2) adding alumina, and reacting at 50-70 deg.C for 10-30 min; (3) slowly adding 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and uniformly mixing.
The invention is further provided that in the step (1), the mixed solution reacts for 10-30min at 60-70 ℃.
The invention is further set that in the step (3), the mixed solution reacts for 30-60min at the temperature of 53-72 ℃, and then is cooled and filtered to obtain the anti-aging epoxy resin curing agent product.
The invention has the following beneficial effects: the invention uses fatty polyamine, cardanol, polyamide, alumina, titanium dioxide and 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone to form a curing agent system. The curing agent system has the hardness and chemical corrosion resistance of a fatty amine system, and also has long-term applicability, good toughness and low toxicity of a polyamide system. 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone is introduced, so that ultraviolet rays can be well absorbed, and epoxy resin is prevented from aging. The cardanol structurally contains a carbon pentadecane branch chain with an unsaturated double bond, the surface energy and the viscosity of the system are reduced, the adhesion to a substrate is improved, and the donor system provides excellent hydrophobicity and low permeability. The gamma-glycidoxypropyltrimethoxysilane is used as a filler, can participate in the curing process of a curing agent and epoxy resin, and prevents the corrosion and the damage of acid and alkali.
Detailed Description
The technical solutions in the embodiments of the present invention are 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.
Example 1
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 1 part of diethylenetriamine, 2 parts of diethylaminopropylene, 2 parts of hexamethylene diamine, 3 parts of cardanol, 3 parts of polyamide, 2 parts of alumina, 1 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 62 ℃ for 20 min; (2) adding alumina, and reacting at 50 deg.C for 10 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 60 ℃ for 60min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
Example 2
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 2 parts of diethylenetriamine, 2 parts of diethylaminopropylene, 2 parts of hexamethylene diamine, 4 parts of cardanol, 2 parts of polyamide, 2 parts of alumina, 0.9 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 70 ℃ for 30 min; (2) adding alumina, and reacting at 55 deg.C for 20 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 70 ℃ for 30min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
Example 3
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 2 parts of diethylenetriamine, 2 parts of diethylaminopropylene, 3 parts of hexamethylene diamine, 5 parts of cardanol, 1 part of polyamide, 4 parts of alumina, 0.8 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone, 0.6-1.2 parts of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.4 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 65 ℃ for 30 min; (2) adding alumina, and reacting at 65 deg.C for 20 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 68 ℃ for 50min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
Example 4
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 4 parts of ethylenediamine, 2 parts of cardanol, 2.5 parts of polyamide, 4 parts of alumina, 0.7 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone, 0.6-1.2 parts of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.3 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 60 ℃ for 10 min; (2) adding alumina, and reacting at 60 deg.C for 10 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 72 ℃ for 33min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
Example 5
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: diethylenetriamine, 8 parts of triethylene tetramine, 3 parts of cardanol, 1 part of polyamide, 3 parts of alumina, 0.6 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone, 0.6-1.2 parts of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.5 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 64 ℃ for 20 min; (2) adding alumina, and reacting at 50 deg.C for 30 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 55 ℃ for 56min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
Example 6
An anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 3 parts of dihexyl triamine, 5 parts of cardanol, 3 parts of polyamide, 3 parts of alumina, 0.5 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone, 0.6-1.2 parts of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.5 part of titanium dioxide.
The preparation method of the anti-aging epoxy resin curing agent comprises the following steps: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence, uniformly mixing, and reacting the mixed solution at 68 ℃ for 10 min; (2) adding alumina, and reacting at 70 deg.C for 15 min; (3) slowly adding 2-hydroxy-4- (2, 3-epoxy ethane glycidyl ether) -benzophenone, uniformly mixing, reacting the mixed solution at 52 ℃ for 60min, cooling, and filtering to obtain the anti-aging epoxy resin curing agent product.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The anti-aging epoxy resin curing agent is characterized by comprising the following raw materials in parts by mass: 3-8 parts of fatty polyamine, 2-5 parts of cardanol, 1-3 parts of polyamide, 2-4 parts of alumina, 0.5-1 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3-0.5 part of titanium dioxide.
2. The anti-aging epoxy resin curing agent as claimed in claim 1, wherein the anti-aging epoxy resin curing agent comprises the following raw materials in parts by mass: 4-6 parts of fatty polyamine, 3-4 parts of cardanol, 2-2.5 parts of polyamide, 2-3 parts of alumina, 0.6-0.8 part of 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and 0.3-0.5 part of titanium dioxide.
3. The curing agent according to claim 1, wherein the aliphatic polyamine is one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, diethylaminopropylene, dihexyltriamine, and hexanediamine.
4. The curing agent according to claim 1, wherein the aliphatic polyamine is a mixture of diethylenetriamine, diethylaminopropylene and hexamethylenediamine, and the mass ratio of the diethylenetriamine to the diethylaminopropylene to the hexamethylenediamine is 1: (1-2): (1.5-2).
5. The curing agent for anti-aging epoxy resin as claimed in claim 1, further comprising 0.6-1.2 parts by mass of gamma-glycidoxypropyltrimethoxysilane as a raw material.
6. The preparation method of the anti-aging epoxy resin curing agent as claimed in any one of claims 1 to 5, comprising the steps of: (1) adding cardanol and polyamide into the stirred aliphatic polyamine in sequence and mixing uniformly; (2) adding alumina, and reacting at 50-70 deg.C for 10-30 min; (3) slowly adding 2-hydroxy-4- (2, 3-ethylene oxide glycidyl ether) -benzophenone and uniformly mixing.
7. The method for preparing the anti-aging epoxy resin curing agent according to claim 6, wherein in the step (1), the mixed solution is reacted at 60-70 ℃ for 10-30 min.
8. The method for preparing the anti-aging epoxy resin curing agent as claimed in claim 6, wherein in the step (3), the mixed solution is reacted at 53-72 ℃ for 30-60min, cooled and filtered to obtain the anti-aging epoxy resin curing agent product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811300453.0A CN111138637A (en) | 2018-11-02 | 2018-11-02 | Anti-aging epoxy resin curing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811300453.0A CN111138637A (en) | 2018-11-02 | 2018-11-02 | Anti-aging epoxy resin curing agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN111138637A true CN111138637A (en) | 2020-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811300453.0A Pending CN111138637A (en) | 2018-11-02 | 2018-11-02 | Anti-aging epoxy resin curing agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724602A (en) * | 2020-12-28 | 2021-04-30 | 江西瀚泰新材料科技有限公司 | Epoxy resin curing agent and preparation method thereof |
-
2018
- 2018-11-02 CN CN201811300453.0A patent/CN111138637A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724602A (en) * | 2020-12-28 | 2021-04-30 | 江西瀚泰新材料科技有限公司 | Epoxy resin curing agent and preparation method thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200512 |
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| WD01 | Invention patent application deemed withdrawn after publication |