CN114015398B - Heat-resistant epoxy adhesive for metal bonding and preparation method thereof - Google Patents

Heat-resistant epoxy adhesive for metal bonding and preparation method thereof Download PDF

Info

Publication number
CN114015398B
CN114015398B CN202111405792.7A CN202111405792A CN114015398B CN 114015398 B CN114015398 B CN 114015398B CN 202111405792 A CN202111405792 A CN 202111405792A CN 114015398 B CN114015398 B CN 114015398B
Authority
CN
China
Prior art keywords
parts
component
epoxy resin
preparation
curing agent
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.)
Active
Application number
CN202111405792.7A
Other languages
Chinese (zh)
Other versions
CN114015398A (en
Inventor
葛凡
孙岳
李艳飞
马苗
顾鸣杰
董立
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Rongtai Technical Industry Co ltd
Original Assignee
Zhejiang Rongtai Technical Industry Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Rongtai Technical Industry Co ltd filed Critical Zhejiang Rongtai Technical Industry Co ltd
Priority to CN202111405792.7A priority Critical patent/CN114015398B/en
Publication of CN114015398A publication Critical patent/CN114015398A/en
Application granted granted Critical
Publication of CN114015398B publication Critical patent/CN114015398B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

Abstract

The application relates to the technical field of preparation of epoxy adhesives for metal bonding, in particular to a heat-resistant epoxy adhesive for metal bonding and a preparation method thereof. The heat-resistant epoxy adhesive for metal bonding comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1-2:1, a step of; the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin and 0.5-100 parts of inorganic filling powder; the component B is prepared from the following raw materials in parts by weight: 30-120 parts of polyamide curing agent and 0.5-100 parts of inorganic filling powder. The epoxy adhesive prepared by the application has good heat resistance, toughness and bonding strength.

Description

Heat-resistant epoxy adhesive for metal bonding and preparation method thereof
Technical Field
The application relates to the technical field of preparation of epoxy adhesives for metal bonding, in particular to a heat-resistant epoxy adhesive for metal bonding and a preparation method thereof.
Background
The heat-resistant epoxy adhesive is mainly used for bonding metals on automobiles, such as bonding stainless steel-stainless steel, aluminum-aluminum, carbon steel-carbon steel, silicon steel sheet-silicon steel sheet and the like. When the heat-resistant epoxy adhesive is applied to metal bonding on automobiles, the heat resistance of the heat-resistant epoxy adhesive is required to be high.
Currently, methods of improving the heat resistance of epoxy adhesives in the related art generally include increasing the crosslink density of the cured product and increasing the proportion of rigid structures. For example, the use of a polyfunctional epoxy resin such as novolac epoxy, AG80, etc. can increase the crosslink density of the cured product, thereby improving the heat resistance of the epoxy adhesive. The introduction of alicyclic or aromatic ring structures, such as alicyclic epoxy resins, aromatic curing agents, alicyclic curing agents, etc., can increase the proportion of rigid structures in the cured product molecules, thereby improving heat resistance.
With respect to the above related art, the applicant found that the following drawbacks exist: the solutions proposed in the related art cause problems of increased brittleness and decreased adhesive strength of the cured product, affecting the performance thereof.
Disclosure of Invention
In order to solve the problems of increased brittleness and reduced bonding strength of a cured product and influence on the service performance of the cured product in the related art, the application provides a heat-resistant epoxy adhesive for metal bonding and a preparation method thereof.
In a first aspect, the application provides a heat-resistant epoxy adhesive for metal bonding, which is realized by the following technical scheme:
the heat-resistant epoxy adhesive for metal bonding comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1-2:1, a step of; the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin and 0.5-100 parts of inorganic filling powder; the component B is prepared from the following raw materials in parts by weight: 30-120 parts of polyamide curing agent and 0.5-100 parts of inorganic filling powder.
Through adopting above-mentioned technical scheme, this application introduces the imide structure into the epoxy molecule through the chemical bond, utilizes the good heat resistance of imide structure to improve the heat resistance of condensate on the one hand, has on the other hand improved the toughness of condensate through the molecular chain that has prolonged epoxy, simultaneously because the introduction of imide structure for holistic polarity promotes to help improving holistic bonding strength, promote metal bonding effect. The adhesive prepared in the application has good bonding effect on metal materials and good heat resistance and heat stability. The tensile shear strength of the stainless steel-stainless steel can reach 18-25Mpa, the tensile shear strength of the carbon steel-carbon steel can reach 23-30Mpa, the tensile shear strength of aluminum-aluminum can reach 27-33MPa, the tensile shear strength is not reduced after the aluminum-aluminum alloy is soaked in engine oil at 160 ℃ for 500 hours, and the tensile shear strength is not lower than 90% of the initial strength after 1000 hours.
Preferably, the polyimide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 5-20 parts of compound containing imide bonds.
By adopting the technical scheme, the usage amount of the compound containing the imide bond is optimized, and the stability of the prepared polyimide modified epoxy resin is ensured, so that the bonding strength and the heat resistance of the heat-resistant epoxy adhesive are ensured.
Preferably, the epoxy value of the epoxy resin is 0.105eq/100g-0.600eq/100g; the compound containing imide bond is one or more of N, N '-4,4' -diphenylmethane bismaleimide, maleimide, N-phenylmaleimide, phthalimide and butyrimide.
By adopting the technical scheme, the bonding strength, toughness and heat resistance of the heat-resistant epoxy adhesive can be ensured.
Preferably, the preparation method of the imide modified epoxy resin comprises the following steps: uniformly mixing epoxy resin and a compound containing imide bonds according to a proportion, stirring at 80-100 ℃ until the epoxy resin and the compound containing imide bonds are completely dissolved into transparent liquid, then raising the temperature to 120-150 ℃ for reaction for 2-4 hours, cooling, and discharging to obtain the imide modified epoxy resin.
By adopting the technical scheme, the imide modified epoxy resin can be prepared conveniently and at low cost. The imide structure is introduced into the epoxy resin molecule through chemical bond, on one hand, the heat resistance of the cured product is improved by utilizing the excellent heat resistance of the imide structure, and on the other hand, the toughness of the cured product is improved by prolonging the molecular chain of the epoxy resin, and meanwhile, the imide structure has a certain polarity, so that the bonding strength is improved.
Preferably, the inorganic filling powder comprises the following raw materials in parts by weight: 0.5-5 parts of thixotropic powder and 0-95 parts of filler.
By adopting the technical scheme, the dosage of thixotropic powder and filler is optimized, and the thixotropic property and heat resistance of the heat-resistant epoxy adhesive are ensured.
Preferably, the filler is one or a combination of more of heavy calcium carbonate, light calcium carbonate, barium sulfate and activated alumina; the thixotropic powder is one or a combination of more of fumed silica, silica micropowder and bentonite.
By adopting the technical scheme, the heat-resistant stability and rheological property of the heat-resistant epoxy adhesive prepared by the application are ensured.
Preferably, the filler is light calcium carbonate, barium sulfate, t-zirconia and ceria; the mass ratio of the light calcium carbonate to the barium sulfate to the t-zirconia to the ceria is 3:6:0.96:0.04.
By adopting the technical scheme, the t-zirconia and the ceria are introduced into the filler system, so that the overall upper heat resistance limit, heat resistance stability and toughness can be improved, and the filler system is better suitable for the bonding environment of metals.
Preferably, the polyamide curing agent is one of a D0140 polyamide curing agent, a 9140 polyamide curing agent, a G0553 polyamide curing agent and a Dow chemical DOW polyamide curing agent.
By adopting the technical scheme, the polyamide curing agent is optimized, so that the heat resistance, the heat resistance stability and the bonding strength of the whole polyamide curing agent can be improved.
In a second aspect, the present application provides a method for preparing a heat-resistant epoxy adhesive for metal adhesion, which is implemented by the following technical scheme:
a preparation method of a heat-resistant epoxy adhesive for metal bonding comprises the following steps:
step one, A, B component preparation;
and (3) preparation of the component A: mixing the imide modified epoxy resin and the inorganic powder according to the proportion, dispersing for 5-10min at 500-3000r/min, uniformly mixing, and stirring for 0.5-2 hours at the temperature of 80-100 ℃ and the vacuum degree of 0.07-0.13 MPa to obtain a component A;
and (3) preparation of a component B: mixing polyamide curing agent and inorganic powder according to a proportion, dispersing for 5-10min at 500-3000r/min, uniformly mixing, stirring for 0.5-2 hours at 80-100 ℃ and vacuum degree of 0.07-0.13 MPa to obtain component B;
and step two, adding the component B into the component A, dispersing for 5-10min at 500-3000r/min, and uniformly mixing to obtain a finished product.
By adopting the technical scheme, the preparation method is relatively simple, is convenient for industrial production, and reduces the use cost. The heat-resistant epoxy adhesive prepared by the method has good bonding effect on metal materials and good heat resistance and heat stability.
In summary, the present application has the following advantages:
1. the heat-resistant epoxy adhesive prepared in the application has a good bonding effect on metal materials and has good heat resistance and heat resistance stability.
2. The preparation method provided by the application has the advantages of relatively simple operation flow and convenience for industrial production, so that the production cost and the use cost of consumers are reduced.
Detailed Description
The present application is described in further detail below with reference to examples.
Raw materials
Figure GDA0004103258020000031
Figure GDA0004103258020000041
Examples
Example 1
A heat-resistant epoxy adhesive for metal adhesion is prepared from a component A and a component B in a mass ratio of 2:1. The component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin, 99.5 parts of light calcium carbonate and 0.5 part of fumed silica. The component B is prepared from the following raw materials in parts by weight: 50 parts of D0140 polyamide curing agent of Shanghai Junjiang New Material Co., ltd., 49.5 parts of light calcium carbonate and 0.5 part of fumed silica.
The imide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 10 parts of compound containing imide bonds. The epoxy resin is epoxy resin E51, and the compound containing imide bond is N, N '-4,4' -diphenylmethane bismaleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 30g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
A preparation method of a heat-resistant epoxy adhesive for metal bonding comprises the following steps:
step one, A, B component preparation;
and (3) preparation of the component A: mixing 200g of imide modified epoxy resin, 199g of light calcium carbonate and 1.0g of fumed silica in proportion for 1min at 200rpm, adjusting the rotating speed to 2000r/min, dispersing for 10min, and stirring for 1.5 hours at the temperature of 100 ℃ and the vacuum degree of 0.08MPa to obtain a component A;
and (3) preparation of a component B: premixing 100g of polyamide curing agent, 99g of light calcium carbonate and 1g of fumed silica for 1min at 200rpm, adjusting the rotating speed to 2000r/min, dispersing for 10min, and stirring for 1.5 hours at the temperature of 100 ℃ and the vacuum degree of 0.08MPa to obtain a component B;
and step two, adding the component B into the component A, premixing for 1min at 200rpm, dispersing for 5min at 2000r/min, and uniformly mixing to obtain the heat-resistant epoxy adhesive. When in use, the heat-resistant epoxy adhesive is coated on the interface of the bonded materials, and the bonding can be completed after curing for 4.0 hours at 80 ℃. When in use, the heat-resistant epoxy adhesive is coated on the interface of the bonded materials, and the bonding can be completed after curing for 12.0 hours at 25 ℃.
Example 2
Example 2 differs from example 1 in that:
a heat-resistant epoxy adhesive for metal bonding is prepared from a component A and a component B in a mass ratio of 1:1. The component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin, 49.5 parts of light calcium carbonate and 0.5 part of fumed silica. The component B is prepared from the following raw materials in parts by weight: 50 parts of D0140 polyamide curing agent of Shanghai Junjiang New Material Co., ltd., 99.5 parts of light calcium carbonate and 0.5 part of fumed silica.
A preparation method of a heat-resistant epoxy adhesive for metal bonding comprises the following steps:
step one, A, B component preparation;
and (3) preparation of the component A: mixing 200g of imide modified epoxy resin, 99g of light calcium carbonate and 1.0g of fumed silica in proportion for 1min at 200rpm, adjusting the rotating speed to 2000r/min, dispersing for 10min, and stirring for 1.5 hours at 100 ℃ and the vacuum degree of 0.08MPa to obtain a component A;
and (3) preparation of a component B: premixing 100g of polyamide curing agent, 199g of light calcium carbonate and 1g of fumed silica for 1min at 200rpm, adjusting the rotating speed to 2000r/min, dispersing for 10min, and stirring for 1.5 hours at the temperature of 100 ℃ and the vacuum degree of 0.08MPa to obtain a component B;
and step two, adding the component B into the component A, premixing for 1min at 200rpm, dispersing for 5min at 2000r/min, and uniformly mixing to obtain the heat-resistant epoxy adhesive.
Example 3
Example 3 differs from example 1 in that: the compound containing an imide bond is maleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 30g of maleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the maleimide is completely dissolved into transparent liquid, then the temperature is raised to 135 ℃ for reaction for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 4
Example 4 differs from example 1 in that: the compound containing imide bond is N-phenyl maleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 30g of N-phenyl maleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 5
Example 5 differs from example 1 in that: the compound containing imide bond is phthalimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 30g of phthalimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 6
Example 6 differs from example 1 in that: the compound containing imide bond is butyrimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 30g of butyryimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the temperature is raised to 135 ℃ for reaction for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 7
Example 7 differs from example 1 in that: the imide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 5 parts of compound containing imide bonds. The epoxy resin is epoxy resin E51, and the compound containing imide bond is N, N '-4,4' -diphenylmethane bismaleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 15g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 8
Example 8 differs from example 1 in that: the imide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 20 parts of compound containing imide bonds. The epoxy resin is epoxy resin E51, and the compound containing imide bond is N, N '-4,4' -diphenylmethane bismaleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 60g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 9
Example 9 differs from example 1 in that: the epoxy resin is epoxy resin E44.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E44 and 60g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Example 10
Example 10 differs from example 1 in that: the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin, 20 parts of heavy calcium carbonate, 40 parts of light calcium carbonate, 39 parts of barium sulfate and 0.5 part of fumed silica. The component B is prepared from the following raw materials in parts by weight: 50 parts of polyamide curing agent, 25 parts of light calcium carbonate, 5 parts of heavy calcium carbonate, 19 parts of barium sulfate and 0.5 part of fumed silica.
Example 11
Example 11 differs from example 1 in that: the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin, 10 parts of heavy calcium carbonate, 35 parts of light calcium carbonate, 15 parts of activated alumina, 39 parts of barium sulfate and 0.5 part of fumed silica. The component B is prepared from the following raw materials in parts by weight: 50 parts of polyamide curing agent, 17 parts of light calcium carbonate, 13 parts of activated alumina, 19 parts of barium sulfate and 0.5 part of fumed silica.
Example 12
Example 12 differs from example 1 in that: the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin and 39.7 parts of inorganic powder. The component B is prepared from the following raw materials in parts by weight: 80 parts of polyamide curing agent and 29.3 parts of inorganic powder.
Preparation of inorganic powder: 150g of light calcium carbonate, 300g of barium sulfate, 15g of fumed silica, 5g of silica micropowder and 50g of t-zirconia in preparation example 1 are uniformly mixed to obtain an inorganic filler. Preparation of t-zirconia: uniformly mixing purchased zirconia and ceria according to a mass ratio of 96:4, then placing the mixture at a temperature of 1250 ℃ for high-temperature treatment for 8.0h, and naturally cooling the mixture to normal temperature to obtain t-phase zirconia.
Example 13
Example 13 differs from example 1 in that: the polyamide curing agent is 9115 polyamide curing agent of the new materials limited by Guangdong, and the ratio of 9115 polyamide curing agent to epoxy resin is 2:1.
Example 14
Example 14 differs from example 1 in that: the polyamide curing agent was a G0553 polyamide curing agent from Guogu chemical Co., ltd, and the ratio of the G0553 polyamide curing agent to the epoxy resin was 2:1.
Comparative example
Comparative example 1 differs from example 1 in that:
the epoxy resin in comparative example 1 was an unmodified epoxy resin E51.
Comparative example 2 differs from example 1 in that:
the epoxy resin in comparative example 2 was unmodified epoxy resin E44.
Comparative example 3
Comparative example 3 differs from example 1 in that:
the imide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 2 parts of compound containing imide bonds. The epoxy resin is epoxy resin E51, and the compound containing imide bond is N, N '-4,4' -diphenylmethane bismaleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 6g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin.
Comparative example 4
Comparative example 4 differs from example 1 in that:
the polyimide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin E51 and 30 parts of N, N '-4,4' -diphenylmethane bismaleimide.
The preparation method of the imide modified epoxy resin comprises the following steps: 300g of epoxy resin E51 and 90g of N, N '-4,4' -diphenylmethane bismaleimide are mixed for 2min at 200rpm, stirred at 100 ℃ until the mixture is completely dissolved into transparent liquid, then the mixture is heated to 135 ℃ to react for 3.0 hours, cooled to room temperature, and discharged to obtain the imide modified epoxy resin. And (3) injection: the preparation process comprises the following steps: 30 parts of the resin containing the imide bond compound had poor stability, and thus did not participate in the performance test.
Performance test
Detection method/test method
1. The tensile shear strength detection method comprises the following steps: measurement of GB/T7124-2008 adhesive tensile shear Strength (rigid Material vs rigid Material).
2. And (3) detection of heat resistance: detecting tensile shear strength after soaking in 160 ℃ engine oil for 500 hours; the tensile shear strength was measured after soaking in 160℃engine oil for 1000 hours. The tensile shear strength detection method comprises the following steps: measurement of GB/T7124-2008 adhesive tensile shear Strength (rigid Material vs rigid Material).
3. The method for detecting toughness of the cured product comprises the following steps: and the elongation at break is the determination method, and the tensile property of the GB/T1040-2018 plastic is measured.
Data analysis
Table 1 shows the tensile shear strength (stainless steel-stainless steel) test parameters for examples 1-14 and comparative examples 1-3
Figure GDA0004103258020000081
Figure GDA0004103258020000091
Table 2 shows the tensile shear strength (carbon steel-carbon steel) test parameters for examples 1-14 and comparative examples 1-3
Figure GDA0004103258020000092
Table 3 shows the tensile shear strength (aluminum-aluminum) test parameters for examples 1-14 and comparative examples 1-3
Figure GDA0004103258020000093
Figure GDA0004103258020000101
Table 4 shows the toughness test parameters for examples 1-14 and comparative examples 1-3
Project Elongation at break
Example 1 20.9％
Example 2 22.5％
Example 3 19.1％
Implementation of the embodimentsExample 4 18.6％
Example 5 19.4％
Example 6 18.0％
Example 7 17.3％
Example 8 22.1％
Example 9 21.5％
Example 10 21.2％
Example 11 19.8％
Example 12 24.1％
Example 13 20.7％
Example 14 20.3％
Comparative example 1 14.0％
Comparative example 2 15.4％
Comparative example 3 17.3％
As can be seen from the combination of examples 1 to 14 and comparative examples 1 to 4 and the combination of Table 3, the heat-resistant epoxy adhesives prepared in examples 1 to 14 were close to each other in tensile shear strength at normal temperature and tensile shear strength after soaking in 160℃engine oil for 500 hours, and therefore, the mass ratio of the A component to the B component was 1 to 14: the heat-resistant epoxy adhesive prepared in the step 1 has good heat resistance and bonding strength. The heat-resistant epoxy adhesive prepared in examples 1-14 has a tensile shear strength of not less than 90% of the tensile shear strength at normal temperature after being immersed in engine oil at 160 ℃ for 1000 hours, and therefore, the mass ratio of the component A to the component B is 1-2: the heat-resistant epoxy adhesive prepared in the step 1 has good heat resistance and bonding strength. The elongation at break of the heat-resistant epoxy adhesive prepared in the examples 1-2 is 20.9-22.5%, and the toughness of a cured product of the epoxy adhesive prepared in the application is improved.
It can be seen from the combination of examples 1 to 14 and comparative examples 1 to 4 and the combination of tables 1 to 3 that the heat-resistant epoxy adhesive prepared in example 1 has a tensile shear strength at normal temperature and a tensile shear strength after being immersed in 160℃engine oil for 500 hours, which are both greater than those of the heat-resistant epoxy adhesive prepared in comparative example 1 and the heat-resistant epoxy adhesive prepared in comparative example 1, and the tensile shear strength after being immersed in 160℃engine oil for 500 hours, which is not lower than 90% of the tensile shear strength at normal temperature after being immersed in 160℃engine oil. Therefore, the epoxy adhesive prepared by adopting the imide modified epoxy resin has good heat resistance, toughness and bonding strength.
It can be seen from the combination of examples 1 to 14 and comparative examples 1 to 4 and tables 1 to 3 that the adhesive prepared in the present application has a good adhesion effect on metal materials (stainless steel-stainless steel, carbon steel-carbon steel, aluminum-aluminum) and has good heat resistance and heat stability. The tensile shear strength of the stainless steel-stainless steel can reach 18-25Mpa, the tensile shear strength of the carbon steel-carbon steel can reach 23-30Mpa, the tensile shear strength of aluminum-aluminum can reach 27-33MPa, the tensile shear strength is hardly reduced after the aluminum-aluminum alloy is soaked in engine oil at 160 ℃ for 500 hours, and the tensile shear strength is not lower than 90% of the initial strength after 1000 hours.
It can be seen from the combination of examples 1 to 14 and comparative examples 1 to 4 and the combination of Table 4 that the epoxy adhesives prepared using the imide-modified epoxy resin not only have good heat-resistant adhesive strength, but also improve the toughness of the whole.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (6)

1. A heat-resistant epoxy adhesive for metal bonding is characterized in that: comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (1-2): 1, a step of; the component A is prepared from the following raw materials in parts by weight: 100 parts of imide modified epoxy resin and 0.5-100 parts of inorganic filling powder; the component B is prepared from the following raw materials in parts by weight: 30-120 parts of polyamide curing agent and 0.5-100 parts of inorganic filling powder;
the imide modified epoxy resin is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin and 5-20 parts of compound containing imide bonds; the epoxy value of the epoxy resin is 0.105eq/100g-0.600eq/100g; the compound containing imide bond is one or more of N, N '-4,4' -diphenylmethane bismaleimide, maleimide, N-phenylmaleimide, phthalimide and butyrimide;
the preparation method of the imide modified epoxy resin comprises the following steps: uniformly mixing epoxy resin and a compound containing imide bonds according to a proportion, stirring at 80-100 ℃ until the epoxy resin and the compound containing imide bonds are completely dissolved into transparent liquid, then raising the temperature to 120-150 ℃ for reaction for 2-4 hours, cooling, and discharging to obtain the imide modified epoxy resin.
2. A heat resistant epoxy adhesive for metal bonding as defined in claim 1, wherein: the inorganic filling powder consists of the following raw materials in parts by weight: 0.5-5 parts of thixotropic powder and 0-95 parts of filler.
3. A heat resistant epoxy adhesive for metal bonding as defined in claim 2, wherein: the filler is one or a combination of a plurality of heavy calcium carbonate, light calcium carbonate, barium sulfate, silicon micropowder and active alumina; the thixotropic powder is one or a combination of more of fumed silica and bentonite.
4. A heat resistant epoxy adhesive for metal bonding according to claim 3, wherein: the filler is light calcium carbonate, barium sulfate, t-zirconia and ceria; the mass ratio of the light calcium carbonate to the barium sulfate to the t-zirconia to the ceria is 3:6:0.96:0.04.
5. A heat resistant epoxy adhesive for metal bonding as defined in claim 1, wherein: the polyamide curing agent is one of D0140 polyamide curing agent, 9140 polyamide curing agent, G0553 polyamide curing agent and Dow chemical DOW polyamide curing agent.
6. A method for preparing the heat-resistant epoxy adhesive for metal bonding according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
step one, A, B component preparation;
and (3) preparation of the component A: mixing the imide modified epoxy resin and the inorganic powder according to the proportion, dispersing for 5-10min at 500-3000r/min, uniformly mixing, and stirring for 0.5-2 hours at the temperature of 80-100 ℃ and the vacuum degree of 0.07-0.13 MPa to obtain a component A;
and (3) preparation of a component B: mixing polyamide curing agent and inorganic powder according to a proportion, dispersing for 5-10min at 500-3000r/min, uniformly mixing, stirring for 0.5-2 hours at 80-100 ℃ and vacuum degree of 0.07-0.13 MPa to obtain component B;
and step two, adding the component B into the component A, dispersing for 5-10min at 500-3000r/min, and uniformly mixing to obtain a finished product.
CN202111405792.7A 2021-11-24 2021-11-24 Heat-resistant epoxy adhesive for metal bonding and preparation method thereof Active CN114015398B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111405792.7A CN114015398B (en) 2021-11-24 2021-11-24 Heat-resistant epoxy adhesive for metal bonding and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111405792.7A CN114015398B (en) 2021-11-24 2021-11-24 Heat-resistant epoxy adhesive for metal bonding and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114015398A CN114015398A (en) 2022-02-08
CN114015398B true CN114015398B (en) 2023-07-14

Family

ID=80066189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111405792.7A Active CN114015398B (en) 2021-11-24 2021-11-24 Heat-resistant epoxy adhesive for metal bonding and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114015398B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011297B (en) * 2022-07-15 2023-01-20 北京新风航天装备有限公司 Adhesive for ceramic material and preparation method thereof
CN116285574A (en) * 2023-03-09 2023-06-23 湖南驰邦新材料有限公司 Bi-component marking paint and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1233768C (en) * 2004-03-10 2005-12-28 四川大学 Epoxy resin adhesive containing dimalea mic and preparation process thereof
CN108753231A (en) * 2018-06-27 2018-11-06 上海德联化工有限公司 A kind of vehicle body polyamide modified epoxy resin structural adhesive and preparation method thereof
CN111087958A (en) * 2019-12-20 2020-05-01 北京高盟新材料股份有限公司 Room-temperature fast-curing epoxy adhesive and preparation method thereof
CN111040701A (en) * 2019-12-28 2020-04-21 西安元创化工科技股份有限公司 High-temperature-resistant and high-toughness epoxy resin adhesive and preparation method thereof
CN112480865B (en) * 2020-12-10 2022-09-27 上海佰奥聚新材料科技有限公司 New energy automobile coil high-temperature-resistant adhesive

Also Published As

Publication number Publication date
CN114015398A (en) 2022-02-08

Similar Documents

Publication Publication Date Title
CN114015398B (en) Heat-resistant epoxy adhesive for metal bonding and preparation method thereof
CN106751516B (en) A kind of toughening, heat-resisting modified epoxy and preparation method thereof
EP2736999B1 (en) Flexible bismaleimide, benzoxazine, epoxy-anhydride adduct hybrid adhesive
JP6378346B2 (en) Conductive die attach films for large die semiconductor packages and compositions useful for their preparation
CA2553251A1 (en) Epoxy adhesive composition
CN110734728A (en) modified epoxy structural adhesive for plastic part bonding and preparation method thereof
Kar et al. Synthesis and evaluation of liquid amine‐terminated polybutadiene rubber and its role in epoxy toughening
Yong et al. The effects of polyamic acid on curing behavior, thermal stability, and mechanical properties of epoxy/DDS system
Gaw et al. Adhesion behaviour of polyamic acid cured epoxy
CN109705312A (en) One kind is based on difunctional POSS high-temperature-resistant epoxy resin and its preparation and application
Filippi et al. Reactive compatibilizer precursors for LDPE/PA6 blends, 4
US6331226B1 (en) LCP bonding method
EP2986685A1 (en) Adhesive compositions, manufacture and use thereof
Dodiuk et al. Room temperature curing epoxy adhesives for elevated temperature service
CN109554069B (en) Nylon crystal reinforced epoxy resin coating and preparation method thereof
CN112322244A (en) High-temperature-resistant adhesive and preparation method thereof
JP4112863B2 (en) Adhesive composition
Pascal et al. Approach to improving the toughness of TGMDA/DDS epoxy resin by blending with thermoplastic polymer powders
JPH04311718A (en) Epoxy resin-modified product and epoxy resin composition
JPS648675B2 (en)
CN115216253B (en) Structural adhesive special for surgical gown and preparation method thereof
JPH09151274A (en) Production of thermoplastic resin composite material and thermoplastic resin composite material
CN116375977A (en) MOF modified epoxy resin, adhesive and preparation method thereof
JPH0582848B2 (en)
KR100241494B1 (en) Silicone-containing polyimide resin composition

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
GR01 Patent grant
GR01 Patent grant