CN114605948B - Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof - Google Patents
Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114605948B CN114605948B CN202210271950.2A CN202210271950A CN114605948B CN 114605948 B CN114605948 B CN 114605948B CN 202210271950 A CN202210271950 A CN 202210271950A CN 114605948 B CN114605948 B CN 114605948B
- Authority
- CN
- China
- Prior art keywords
- temperature
- epoxy resin
- epoxy adhesive
- curing
- low temperature
- 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
Links
- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 43
- 238000013035 low temperature curing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000001723 curing Methods 0.000 claims abstract description 43
- 239000000853 adhesive Substances 0.000 claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims description 57
- 229920000647 polyepoxide Polymers 0.000 claims description 57
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 48
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 21
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 21
- 229940091173 hydantoin Drugs 0.000 claims description 21
- 150000004982 aromatic amines Chemical class 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 16
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 13
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 6
- -1 glycidol amine Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000010998 test method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to the field of high polymer materials and preparation, and particularly discloses a medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and a preparation method thereof. The viscosity of the adhesive is regulated by the filler. The epoxy adhesive can realize medium-low temperature (not more than 110 ℃) curing, and the tensile shear strength is not lower than 6.5MPa at 250 ℃. The epoxy adhesive provided by the invention has the advantages of simple preparation method and mild curing condition, and is suitable for construction operation in various occasions.
Description
Technical Field
The invention relates to an epoxy resin adhesive and a preparation method thereof, in particular to a medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and a preparation method thereof, wherein the medium-low temperature curing high-temperature-resistant high-strength refers to the curing temperature not higher than 110 ℃, and the tensile shear strength at 250 ℃ not lower than 6.5MPa, and belongs to the field of preparation of high polymer materials.
Background
The epoxy resin can generate stronger interaction with the surfaces of various materials due to the existence of polar chemical structures such as epoxy groups, hydroxyl groups, ether bonds and the like in the structure, and is matched with a curing agent for use, so that the epoxy resin is an adhesive with excellent performance and is widely used in the fields of aerospace, electronic packaging and the like.
The epoxy adhesive is limited by a cross-linked network structure after the epoxy resin is cured, the heat-resistant temperature of the common epoxy adhesive is generally below 150 ℃, the epoxy adhesive with excellent partial performance can be used at 170-200 ℃, and the maximum tensile shear strength at 250 ℃ is only about 1-3 MPa.
In addition, the high-temperature-resistant adhesive generally has the technical problems of long gel time, high curing temperature (generally above 120 ℃), long curing time and the like, and severely limits the application of the high-temperature-resistant adhesive in aircraft cementing. With the increasingly severe service thermal environment of the aircraft, the high-temperature resistance requirement on the epoxy adhesive is gradually increased, meanwhile, the manufacturability of the epoxy adhesive is required to be considered, and the current commercial epoxy adhesive cannot meet the requirement.
Disclosure of Invention
Aiming at the problems, the invention provides a medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and a preparation method thereof, wherein the medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive is prepared from a mixture of para-aminophenol epoxy resin, glycidol amine type epoxy resin and glycidyl ether, and an aromatic amine curing agent.
In a first aspect, the present application provides a medium-low temperature cured high-temperature resistant high-strength epoxy adhesive, which adopts the following technical scheme:
the medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following raw materials in parts by mass:
60-80 parts of para-aminophenol epoxy resin, 20-40 parts of glycidol amine type epoxy resin, 3-10 parts of glycidol ether, 25-35 parts of aromatic amine curing agent and 3-10 parts of inorganic filler.
Preferably, the para-aminophenol epoxy resin is a triglycidyl para-aminophenol epoxy resin.
Preferably, the glycidylamine type epoxy resin is a mixture of diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, and the mass percentage of the diaminodiphenyl methane tetraglycidyl amine is 15-40% and the mass percentage of the 1, 3-diglycidyl hydantoin is 60-85% based on 100% of the total mass of the diaminodiphenyl methane tetraglycidyl amine and the 1, 3-diglycidyl hydantoin.
Through the technical scheme, the amino diphenyl methane tetraglycidyl amine effectively improves the compatibility between the amino phenol epoxy resin and the 1, 3-diglycidyl hydantoin epoxy resin, and the heat stability of the adhesive is further improved by the amino diphenyl methane tetraglycidyl amine, the 1, 3-diglycidyl hydantoin epoxy resin and the heterocycle in the structure of the condensate.
Preferably, the glycidyl ether is at least one of trimethylolpropane triglycidyl ether and 1, 4-butanediol diglycidyl ether.
Preferably, the aromatic amine curing agent is a mixture of m-phenylenediamine and diaminodiphenyl methane, and the mass percentage of the m-phenylenediamine is 70-95% and the mass percentage of the diaminodiphenyl methane is 5-30% based on the total mass of the m-phenylenediamine and the diaminodiphenyl methane as 100%.
Through the technical scheme, the curing temperature of the adhesive is reduced, and the thermal stability of the adhesive is improved. Under the selection of the aromatic amine curing agent, the adhesive realizes medium-low temperature (not more than 110 ℃) curing, and the thermal stability is improved.
Preferably, the inorganic filler is fumed silica with a specific surface area of 175-225 m 2 /g。
By limiting the specific surface area of the silicon dioxide, the particle size of the inorganic filler is controlled, and the proper size of the inorganic filler is beneficial to improving the technological performance of the adhesive.
In a second aspect, the present application provides a method for preparing a middle-low temperature cured high-temperature resistant high-strength epoxy adhesive, which adopts the following technical scheme:
a preparation method of a medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following steps:
(1) Uniformly stirring p-aminophenol epoxy resin, glycidol amine type epoxy resin and glycidyl ether at room temperature to obtain an epoxy resin mixed solution;
(2) Preheating an aromatic amine curing agent to obtain a liquid co-solution; rapidly stirring the epoxy resin mixed solution and the liquid co-solvent, and adding an inorganic filler after uniformly mixing to obtain an adhesive;
(3) And (3) curing the adhesive obtained in the step (2).
Preferably, in the step (2), the preheating temperature of the curing agent is 80-90 ℃ and the preheating time is 20-40 min.
Preferably, in the step (3), the curing condition of the adhesive is: 8-24 h at room temperature, 2-4 h at 80 ℃/2-4 h at 100 ℃/6-8 h and 2-4 h at 110 ℃/2-4 h.
In summary, the present application at least includes the following beneficial technical effects:
(1) According to the invention, through the cooperation of the chemical structures of the para-aminophenol epoxy resin and the glycidol amine type epoxy resin, the adhesive is endowed with good thermal stability, so that the adhesive has higher tensile shear strength under the high temperature condition, the curing activity of the adhesive is improved by adding the glycidol ether, the curing at medium and low temperature (not more than 110 ℃) can be realized, and the adhesive has excellent high-temperature bonding performance, and the tensile shear strength at 250 ℃ is not lower than 6.5MPa.
(2) The epoxy adhesive provided by the invention has the advantages of simple preparation method, mild curing condition, low cost and strong process applicability, and is suitable for construction operation in various occasions.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention:
the fumed silica in the examples has a specific surface area of 200.+ -.25 m 2 /g。
Example 1
The medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following components in parts by mass: 60 parts of triglycidyl para-aminophenol epoxy resin, 32 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenyl methane tetraglycidyl amine, 10 parts of trimethylolpropane triglycidyl ether, 28.5 parts of m-phenylenediamine, 1.5 parts of diaminodiphenyl methane and 10 parts of fumed silica.
The preparation method of the middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following specific steps:
(1) Weighing the raw materials according to the mass parts.
(2) After uniformly stirring diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl para-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) placing the mixture of m-phenylenediamine and diaminodiphenyl methane in an oven at 85 ℃ and heating for 30min to obtain the preheated aromatic amine curing agent.
(4) And adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, rapidly stirring to uniformly mix the two, and adding fumed silica to adjust the viscosity to obtain the adhesive.
(5) Curing the adhesive obtained in the step (4) under the following conditions: room temperature 12h,80 ℃/2h,100 ℃/6h,110 ℃/2h.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 18.77MPa, the tensile and shear strength at 210 ℃ is 14.35MPa, the tensile and shear strength at 250 ℃ is 13.53MPa, and the tensile and shear strength at 270 ℃ is 7MPa.
Example 2
The medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following components in parts by mass: 80 parts of triglycidyl para-aminophenol epoxy resin, 17 parts of 1, 3-diglycidyl hydantoin, 3 parts of diaminodiphenyl methane tetraglycidyl amine, 3 parts of trimethylolpropane triglycidyl ether, 24.5 parts of m-phenylenediamine, 10.5 parts of diaminodiphenyl methane and 3 parts of fumed silica.
The preparation method of the middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following specific steps:
(1) Weighing the raw materials according to the mass parts.
(2) After uniformly stirring diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl para-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) placing the mixture of m-phenylenediamine and diaminodiphenyl methane in a baking oven at 90 ℃ and heating for 20min to obtain the preheated aromatic amine curing agent.
(4) And adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, rapidly stirring to uniformly mix the two, and adding fumed silica to adjust the viscosity to obtain the adhesive.
(5) Curing the adhesive obtained in the step (4) under the following conditions: 24h at room temperature, 80 ℃/4h,100 ℃/8h,110 ℃/4h.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 14.97MPa, the tensile and shear strength at 210 ℃ is 13.73MPa, the tensile and shear strength at 250 ℃ is 12.2MPa, and the tensile and shear strength at 270 ℃ is 6.5MPa.
Example 3
The medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following components in parts by mass: 80 parts of triglycidyl para-aminophenol epoxy resin, 12 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenyl methane tetraglycidyl amine, 17.5 parts of m-phenylenediamine, 17.5 parts of diaminodiphenyl methane and 3 parts of fumed silica.
The preparation method of the middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following specific steps:
(1) Weighing the raw materials according to the mass parts.
(2) After uniformly stirring diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl para-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) placing the mixture of m-phenylenediamine and diaminodiphenyl methane in an oven at 80 ℃ and heating for 40min to obtain the preheated aromatic amine curing agent.
(4) And adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, rapidly stirring to uniformly mix the two, and adding fumed silica to adjust the viscosity to obtain the adhesive.
(5) Curing the adhesive obtained in the step (4) under the following conditions: 8h,80 ℃/3h,100 ℃/7h,110 ℃/3h at room temperature.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 13MPa, the tensile and shear strength at 210 ℃ is 12MPa, the tensile and shear strength at 250 ℃ is 10MPa, and the tensile and shear strength at 270 ℃ is 5.5MPa.
Example 4
The medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following components in parts by mass: 60 parts of triglycidyl para-aminophenol epoxy resin, 34 parts of 1, 3-diglycidyl hydantoin, 6 parts of diaminodiphenyl methane tetraglycidyl amine, 10 parts of 1, 4-butanediol diglycidyl ether, 12.5 parts of m-phenylenediamine, 12.5 parts of diaminodiphenyl methane and 6 parts of fumed silica.
The preparation method of the middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following specific steps:
(1) Weighing the raw materials according to the mass parts.
(2) After uniformly stirring diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl para-aminophenol epoxy resin and 1, 4-butanediol diglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) placing the mixture of m-phenylenediamine and diaminodiphenyl methane in a baking oven at 90 ℃ and heating for 20min to obtain the preheated aromatic amine curing agent.
(4) And adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, rapidly stirring to uniformly mix the two, and adding fumed silica to adjust the viscosity to obtain the adhesive.
(5) Curing the adhesive obtained in the step (4) under the following conditions: room temperature 10h,80 ℃/4h,100 ℃/6h,110 ℃/3h.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: 15MPa of room temperature tensile shear strength, 13.5MPa of 210 ℃ tensile shear strength, 9.5MPa of 250 ℃ tensile shear strength and 4.5MPa of 270 ℃ tensile shear strength.
Example 5
The medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following components in parts by mass: 60 parts of triglycidyl para-aminophenol epoxy resin, 32 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenyl methane tetraglycidyl amine, 5 parts of 1, 4-butanediol diglycidyl ether, 5 parts of trimethylolpropane triglycidyl ether, 14 parts of m-phenylenediamine, 14 parts of diaminodiphenyl methane and 5 parts of fumed silica.
The preparation method of the middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive comprises the following specific steps:
(1) Weighing the raw materials according to the mass parts.
(2) After uniformly stirring diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl para-aminophenol epoxy resin, 1, 4-butanediol diglycidyl ether and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) placing the mixture of m-phenylenediamine and diaminodiphenyl methane in a baking oven at 90 ℃ and heating for 20min to obtain the preheated aromatic amine curing agent.
(4) And adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, rapidly stirring to uniformly mix the preheated aromatic amine curing agent and the epoxy resin mixed solution, and adding fumed silica to adjust the viscosity to obtain the adhesive before curing.
(5) Curing the adhesive before curing under the following conditions: 20h,80 ℃/2h,100 ℃/6h,110 ℃/4h at room temperature.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 13MPa, the tensile and shear strength at 210 ℃ is 11.8MPa, the tensile and shear strength at 250 ℃ is 9.2MPa, and the tensile and shear strength at 270 ℃ is 5MPa.
Comparative example 1
The difference from example 1 is that: 1, 3-diglycidyl hydantoin and diaminodiphenylmethane tetraglycidyl amine are replaced by equal mass triglycidyl para-aminophenol epoxy resins.
The adhesive preparation method is different from example 1 in that in step (2): and uniformly mixing triglycidyl para-aminophenol epoxy resin and trimethylolpropane triglycidyl ether to obtain an epoxy resin mixed solution.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 12.10MPa, the tensile and shear strength at 210 ℃ is 7.68MPa, the tensile and shear strength at 250 ℃ is 5.84MPa, and the tensile and shear strength at 270 ℃ is 3.41MPa.
Comparative example 2
The difference from example 1 is that: the triglycidyl para-aminophenol epoxy resin was replaced with 48 parts of 1, 3-diglycidyl hydantoin and 12 parts of diaminodiphenyl methane tetraglycidyl amine.
The adhesive preparation method is different from example 1 in that in step (2): uniformly mixing 1, 3-diglycidyl hydantoin, diaminodiphenylmethane tetraglycidyl amine and trimethylolpropane triglycidyl ether to obtain epoxy resin mixed solution.
The tensile and shear strength test is carried out on the cured adhesive according to the Q/Dq139-94 test method, and the result is that: the tensile and shear strength at room temperature is 14.67MPa, the tensile and shear strength at 210 ℃ is 7.16MPa, the tensile and shear strength at 250 ℃ is 5.14MPa, and the tensile and shear strength at 270 ℃ is 3.81MPa.
According to examples 1 to 5, the adhesive was cured at not higher than 110℃and the tensile shear strength at 250℃was not lower than 6.5MPa in the content ranges of the respective components defined in the present invention.
From example 1 and comparative examples 1-2, the adhesive of example 1 has higher thermal stability than that of comparative examples 1-2, indicating that the adhesive has higher thermal stability and higher high-temperature bonding strength by the synergistic effect of the para-aminophenol epoxy resin and the glycidylamine type epoxy resin.
The parts of the specification not described in detail are common general knowledge to the person skilled in the art.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (9)
1. A medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive is characterized in that: according to the mass portion, the material comprises the following raw materials:
60-80 parts of p-aminophenol epoxy resin, 20-40 parts of glycidol amine type epoxy resin, 3-10 parts of glycidol ether, 25-35 parts of aromatic amine curing agent and 3-10 parts of inorganic filler;
the glycidylamine type epoxy resin is a mixture of diaminodiphenyl methane tetraglycidyl amine and 1, 3-diglycidyl hydantoin.
2. The medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 1, wherein the epoxy adhesive is characterized in that: the para-aminophenol epoxy resin is a triglycidyl para-aminophenol epoxy resin.
3. The medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 1, wherein the epoxy adhesive is characterized in that: the mass percentage of the diaminodiphenylmethane tetraglycidyl amine is 15-40% and the mass percentage of the 1, 3-diglycidyl hydantoin is 60-85% based on 100% of the total mass of the diaminodiphenylmethane tetraglycidyl amine and the 1, 3-diglycidyl hydantoin.
4. The medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 1, wherein the epoxy adhesive is characterized in that: the glycidyl ether is at least one of trimethylolpropane triglycidyl ether and 1, 4-butanediol diglycidyl ether.
5. The medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 1, wherein the epoxy adhesive is characterized in that: the aromatic amine curing agent is a mixture of m-phenylenediamine and diaminodiphenyl methane, and the mass percentage of the m-phenylenediamine is 70-95% and the mass percentage of the diaminodiphenyl methane is 5-30% based on the total mass of the m-phenylenediamine and the diaminodiphenyl methane as 100%.
6. The medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 1, wherein the epoxy adhesive is characterized in that: the inorganic filler is fumed silica, and the specific surface area is 175-225 m 2 /g。
7. A method for preparing the medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive according to any one of claims 1-6, which is characterized in that: the method comprises the following steps:
(1) Uniformly stirring p-aminophenol epoxy resin, glycidol amine type epoxy resin and glycidyl ether at room temperature to obtain an epoxy resin mixed solution;
(2) Preheating an aromatic amine curing agent to obtain a liquid co-solution; rapidly stirring the epoxy resin mixed solution and the liquid co-solvent, and adding an inorganic filler after uniformly mixing to obtain an adhesive;
(3) And (3) curing the adhesive obtained in the step (2).
8. The method for preparing the medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 7, which is characterized in that: in the step (2), the preheating temperature of the curing agent is 80-90 ℃ and the preheating time is 20-40 min.
9. The method for preparing the medium-low temperature curing high-temperature and high-strength epoxy adhesive according to claim 7, which is characterized in that: in the step (3), the curing conditions of the adhesive are as follows: 8-24 hours at room temperature, 2-4 hours at 80 ℃/2-4 hours at 100 ℃/6-8 hours at 110 ℃/2-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210271950.2A CN114605948B (en) | 2022-03-18 | 2022-03-18 | Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210271950.2A CN114605948B (en) | 2022-03-18 | 2022-03-18 | Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114605948A CN114605948A (en) | 2022-06-10 |
| CN114605948B true CN114605948B (en) | 2024-02-09 |
Family
ID=81864593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210271950.2A Active CN114605948B (en) | 2022-03-18 | 2022-03-18 | Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114605948B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537163A (en) * | 2022-11-04 | 2022-12-30 | 四川大学 | Medium-low temperature curing high-temperature-resistant flexible epoxy adhesive and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000087000A (en) * | 1998-09-08 | 2000-03-28 | Murata Mfg Co Ltd | Heat-resistant adhesive |
| CN101096412A (en) * | 2006-06-30 | 2008-01-02 | 中国科学院理化技术研究所 | Curing agent for epoxy resin and low-temperature using epoxy adhesive |
| CN102850978A (en) * | 2011-06-28 | 2013-01-02 | 上海市合成树脂研究所 | Room temperature cured high-temperature resistant epoxy adhesive |
| CN104559064A (en) * | 2015-01-28 | 2015-04-29 | 江苏恒神纤维材料有限公司 | High-toughness high-Tg-value epoxy resin and preparation method |
-
2022
- 2022-03-18 CN CN202210271950.2A patent/CN114605948B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000087000A (en) * | 1998-09-08 | 2000-03-28 | Murata Mfg Co Ltd | Heat-resistant adhesive |
| CN101096412A (en) * | 2006-06-30 | 2008-01-02 | 中国科学院理化技术研究所 | Curing agent for epoxy resin and low-temperature using epoxy adhesive |
| CN102850978A (en) * | 2011-06-28 | 2013-01-02 | 上海市合成树脂研究所 | Room temperature cured high-temperature resistant epoxy adhesive |
| CN104559064A (en) * | 2015-01-28 | 2015-04-29 | 江苏恒神纤维材料有限公司 | High-toughness high-Tg-value epoxy resin and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114605948A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110128982B (en) | Normal-temperature fast-curing structural adhesive and preparation method thereof | |
| CN107779147B (en) | High-strength epoxy honeycomb adhesive and preparation method thereof | |
| CN111040701A (en) | High-temperature-resistant and high-toughness epoxy resin adhesive and preparation method thereof | |
| CN111019580B (en) | Epoxy resin adhesive and preparation method and application thereof | |
| JP2013506030A (en) | Curable epoxy resin composition and composite material produced therefrom | |
| CN105670223B (en) | Epoxy resin composition for wind turbine blade and composite material | |
| CN114605948B (en) | Middle-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof | |
| CN102453458B (en) | Nano rubber modified room temperature cured high temperature resistant structure adhesive | |
| CN111592849B (en) | Semi-cured epoxy adhesive film and preparation method thereof | |
| CN102040935B (en) | Weak-exothermic room temperature curing epoxy adhesive | |
| CN111334232A (en) | Weather-resistant intermediate-temperature curing epoxy resin adhesive and preparation method thereof | |
| US4002599A (en) | Epoxy resin compositions from glycidyl derivatives of aminophenols cured with tetracarboxylic dianhydrides | |
| CN105602202A (en) | Resin composition, prepreg thereof and composite material | |
| CN104449508A (en) | Flexible epoxy structural adhesive and preparation method thereof | |
| CN107556954A (en) | A kind of aramid fiber cellular composite material epoxy structural rubber and preparation method thereof | |
| JP2020041144A (en) | Epoxy composition containing core-shell rubber | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| CN114854347A (en) | Insulating and heat-conducting adhesive, preparation method thereof and heat-conducting adhesive material | |
| CN114410260A (en) | Modified epoxy resin adhesive and preparation method thereof | |
| US3948849A (en) | Adhesive compositions | |
| CN110885653A (en) | Low-temperature fast-curing epoxy insulating adhesive and preparation method and application thereof | |
| JP2018502195A5 (en) | ||
| CN108485187A (en) | Modified epoxy material and preparation method thereof, application and fan blade | |
| CN108611036A (en) | A kind of preparation method of cardanol glycidyl ether modified epoxy adhesive | |
| CN115651579B (en) | Epoxy adhesive capable of being rapidly cured and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |