CN114605948A - Medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof - Google Patents
Medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114605948A CN114605948A CN202210271950.2A CN202210271950A CN114605948A CN 114605948 A CN114605948 A CN 114605948A CN 202210271950 A CN202210271950 A CN 202210271950A CN 114605948 A CN114605948 A CN 114605948A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- medium
- curing
- low temperature
- parts
- 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.)
- Granted
Links
- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 37
- 238000013035 low temperature curing Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001723 curing Methods 0.000 claims abstract description 48
- 239000000853 adhesive Substances 0.000 claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims description 58
- 229920000647 polyepoxide Polymers 0.000 claims description 58
- 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 26
- 150000004982 aromatic amines Chemical class 0.000 claims description 23
- 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
- 239000011259 mixed solution Substances 0.000 claims description 21
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 239000000203 mixture Substances 0.000 claims description 16
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000006184 cosolvent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000945 filler Substances 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
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 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
- 239000000463 material Substances 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
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 adjusted by the filler. The epoxy adhesive can realize curing at medium and low temperature (not more than 110 ℃), and the pull-shear strength is not lower than 6.5MPa at 250 ℃. The epoxy adhesive provided by the invention is simple in preparation method, mild in curing condition and 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 and high temperature resistant high strength refer to that the curing temperature is not higher than 110 ℃ and the pull-down shear strength at 250 ℃ is 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, is matched with a curing agent for use, is an adhesive with excellent performance, and is widely used in the fields of aerospace, electronic packaging and the like.
The heat-resistant temperature of the common epoxy adhesive is generally below 150 ℃, part of epoxy adhesive with excellent performance can be used at 170-200 ℃, and the maximum tensile-shear strength at 250 ℃ is only about 1-3 MPa.
In addition, high temperature adhesives generally have the manufacturability problems of long gel time, high curing temperature (generally over 120 ℃), long curing time and the like, and the application of the adhesives in aircraft bonding is severely limited. With the increasingly severe service thermal environment of the aircraft, the high temperature resistance requirement of the epoxy adhesive is gradually improved, and the manufacturability of the epoxy adhesive is considered, so that the current commercialized 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, which adopts a mixture of p-aminophenol epoxy resin, glycidyl amine type epoxy resin and glycidyl ether, and adds an aromatic amine curing agent, so that the adhesive achieves the effects of medium-low temperature curing and high temperature bonding strength.
In a first aspect, the 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 p-aminophenol epoxy resin, 20-40 parts of glycidyl amine type epoxy resin, 3-10 parts of glycidyl ether, 25-35 parts of aromatic amine curing agent and 3-10 parts of inorganic filler.
Preferably, the p-aminophenol epoxy resin is triglycidyl p-aminophenol epoxy resin.
Preferably, the glycidyl amine type epoxy resin is a mixture of diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, and 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.
Through the technical scheme, the compatibility between the aminophenol epoxy resin and the 1, 3-diglycidyl hydantoin epoxy resin is effectively improved by the aminodiphenylmethane tetraglycidyl amine, and the thermal stability of the adhesive is further improved by the aminodiphenylmethane tetraglycidyl amine, the 1, 3-diglycidyl hydantoin epoxy resin and a heterocyclic ring in a cured product structure.
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 diaminodiphenylmethane, wherein the total mass of the m-phenylenediamine and the diaminodiphenylmethane is 100%, the mass percentage of the m-phenylenediamine is 70-95%, and the mass percentage of the diaminodiphenylmethane is 5-30%.
Through the technical scheme, the curing temperature of the adhesive is favorably reduced, and the thermal stability of the adhesive is improved. Under the selection of the aromatic amine curing agent, the adhesive realizes medium and low temperature (not more than 110 ℃) curing, and the thermal stability is improved.
Preferably, the inorganic filler is fumed silica, and the specific surface area is 175-225 m2/g。
The specific surface area of the silica is limited, 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 application provides a preparation method of a medium-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) stirring p-aminophenol epoxy resin, glycidyl amine type epoxy resin and glycidyl ether uniformly at room temperature to obtain epoxy resin mixed solution;
(2) preheating an aromatic amine curing agent to obtain a liquid cosolvent; rapidly stirring the epoxy resin mixed solution and the liquid cosolvent, 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 conditions of the adhesive are as follows: the room temperature is 8-24 h, 80 ℃/2-4 h, 100 ℃/6-8 h and 110 ℃/2-4 h.
In summary, the present application at least includes the following beneficial technical effects:
(1) the invention endows the adhesive with good thermal stability through the cooperation of the chemical structures of the p-aminophenol epoxy resin and the glycidylamine epoxy resin, so that the adhesive has higher tensile shear strength under the high-temperature condition, the addition of the glycidyl ether improves the curing activity of the adhesive, the curing at medium and low temperature (not more than 110 ℃) can be realized, the excellent high-temperature bonding performance is realized, and the tensile shear strength is not lower than 6.5MPa at 250 ℃.
(2) The epoxy adhesive provided by the invention has the advantages of simple preparation method, mild curing conditions, 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 should not be construed as limiting the scope of the invention:
ratio of fumed silica in examplesThe area is 200 +/-25 m2/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 p-aminophenol epoxy resin, 32 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenylmethane tetraglycidyl amine, 10 parts of trimethylolpropane triglycidyl ether, 28.5 parts of m-phenylenediamine, 1.5 parts of diaminodiphenylmethane and 10 parts of fumed silica.
A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive comprises the following specific steps:
(1) weighing the raw materials according to the mass part ratio.
(2) Uniformly stirring diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl p-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) heating the mixture of the m-phenylenediamine and the diaminodiphenylmethane in an oven at 85 ℃ 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, quickly stirring to uniformly mix the aromatic amine curing agent and the epoxy resin mixed solution, 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: the room temperature is 12h, 80 ℃/2h, 100 ℃/6h and 110 ℃/2 h.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 18.77MPa, the 210 ℃ tensile shear strength is 14.35MPa, the 250 ℃ tensile shear strength is 13.53MPa, and the 270 ℃ tensile shear strength is 7 MPa.
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 p-aminophenol epoxy resin, 17 parts of 1, 3-diglycidyl hydantoin, 3 parts of diaminodiphenylmethane tetraglycidyl amine, 3 parts of trimethylolpropane triglycidyl ether, 24.5 parts of m-phenylenediamine, 10.5 parts of diaminodiphenylmethane and 3 parts of fumed silica.
A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive comprises the following specific steps:
(1) weighing the raw materials according to the mass part ratio.
(2) Uniformly stirring diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl p-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) heating the mixture of the m-phenylenediamine and the diaminodiphenylmethane in a drying oven at the temperature of 90 ℃ 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, quickly stirring to uniformly mix the aromatic amine curing agent and the epoxy resin mixed solution, 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: the temperature is 24h, 80 ℃/4h, 100 ℃/8h and 110 ℃/4 h.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 14.97MPa, the 210 ℃ tensile shear strength is 13.73MPa, the 250 ℃ tensile shear strength is 12.2MPa, and the 270 ℃ tensile shear strength is 6.5 MPa.
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 p-aminophenol epoxy resin, 12 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenylmethane tetraglycidyl amine, 17.5 parts of m-phenylenediamine, 17.5 parts of diaminodiphenylmethane and 3 parts of fumed silica.
A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive comprises the following specific steps:
(1) weighing the raw materials according to the mass part ratio.
(2) Uniformly stirring diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl p-aminophenol epoxy resin and trimethylolpropane triglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) heating the mixture of the m-phenylenediamine and the diaminodiphenylmethane in an oven at the temperature of 80 ℃ 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, quickly stirring to uniformly mix the aromatic amine curing agent and the epoxy resin mixed solution, 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: the room temperature is 8h, 80 ℃/3h, 100 ℃/7h and 110 ℃/3 h.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 13MPa, the 210 ℃ tensile shear strength is 12MPa, the 250 ℃ tensile shear strength is 10MPa, and the 270 ℃ tensile shear strength is 5.5 MPa.
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 p-aminophenol epoxy resin, 34 parts of 1, 3-diglycidyl hydantoin, 6 parts of diaminodiphenylmethane tetraglycidyl amine, 10 parts of 1, 4-butanediol diglycidyl ether, 12.5 parts of m-phenylenediamine, 12.5 parts of diaminodiphenylmethane and 6 parts of fumed silica.
A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive comprises the following specific steps:
(1) weighing the raw materials according to the mass part ratio.
(2) Uniformly stirring diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, adding triglycidyl-p-aminophenol epoxy resin and 1, 4-butanediol diglycidyl ether, and uniformly mixing to obtain an epoxy resin mixed solution.
(3) And (3) heating the mixture of the m-phenylenediamine and the diaminodiphenylmethane in a drying oven at the temperature of 90 ℃ 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, quickly stirring to uniformly mix the aromatic amine curing agent and the epoxy resin mixed solution, 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: the room temperature is 10h, 80 ℃/4h, 100 ℃/6h and 110 ℃/3 h.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 15MPa, the 210 ℃ tensile shear strength is 13.5MPa, the 250 ℃ tensile shear strength is 9.5MPa, and the 270 ℃ tensile shear strength is 4.5 MPa.
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 p-aminophenol epoxy resin, 32 parts of 1, 3-diglycidyl hydantoin, 8 parts of diaminodiphenylmethane tetraglycidyl amine, 5 parts of 1, 4-butanediol diglycidyl ether, 5 parts of trimethylolpropane triglycidyl ether, 14 parts of m-phenylenediamine, 14 parts of diaminodiphenylmethane and 5 parts of fumed silica.
A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive comprises the following specific steps:
(1) weighing the raw materials according to the mass part ratio.
(2) After uniformly stirring diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin, triglycidyl-p-aminophenol epoxy resin, 1, 4-butanediol diglycidyl ether and trimethylolpropane triglycidyl ether are added and uniformly mixed to obtain epoxy resin mixed solution.
(3) And (3) heating the mixture of the m-phenylenediamine and the diaminodiphenylmethane in a drying oven at the temperature of 90 ℃ for 20min to obtain the preheated aromatic amine curing agent.
(4) Adding the preheated aromatic amine curing agent into the epoxy resin mixed solution, quickly stirring the mixture to uniformly mix the 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: the temperature is 20h, 80 ℃/2h, 100 ℃/6h and 110 ℃/4h at room temperature.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 13MPa, the 210 ℃ tensile shear strength is 11.8MPa, the 250 ℃ tensile shear strength is 9.2MPa, and the 270 ℃ tensile shear strength is 5 MPa.
Comparative example 1
The difference from example 1 is that: 1, 3-diglycidyl hydantoin and diaminodiphenylmethane tetraglycidyl amine were replaced with equal mass of triglycidyl-p-aminophenol epoxy resin.
The adhesive preparation method differs from example 1 in that, in step (2): and uniformly mixing triglycidyl p-aminophenol epoxy resin and trimethylolpropane triglycidyl ether to obtain an epoxy resin mixed solution.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 12.10MPa, the 210 ℃ tensile shear strength is 7.68MPa, the 250 ℃ tensile shear strength is 5.84MPa, and the 270 ℃ tensile shear strength is 3.41 MPa.
Comparative example 2
The difference from example 1 is that: triglycidyl p-aminophenol epoxy resin was replaced with 48 parts of 1, 3-diglycidyl hydantoin and 12 parts of diaminodiphenylmethane tetraglycidyl amine.
The preparation method of the adhesive is different from the preparation method of the example 1 in that in the step (2): uniformly mixing 1, 3-diglycidyl hydantoin, diaminodiphenylmethane tetraglycidyl amine and trimethylolpropane triglycidyl ether to obtain an epoxy resin mixed solution.
The tensile-shear strength test of the cured adhesive is carried out according to the Q/Dq139-94 test method, and the result is as follows: the room temperature tensile shear strength is 14.67MPa, the 210 ℃ tensile shear strength is 7.16MPa, the 250 ℃ tensile shear strength is 5.14MPa, and the 270 ℃ tensile shear strength is 3.81 MPa.
According to examples 1 to 5, it is understood that within the content ranges of the respective components defined in the present invention, the adhesive realizes curing at not higher than 110 ℃ and the pull-down shear strength at 250 ℃ is not lower than 6.5 MPa.
As can be seen from example 1 and comparative examples 1 to 2, the adhesive of example 1 has higher thermal stability than the adhesives of comparative examples 1 to 2, indicating that the adhesive has more thermal stability and higher high-temperature adhesive strength by the synergistic effect of the p-aminophenol epoxy resin and the glycidylamine type epoxy resin.
Parts of the specification not described in detail are common general knowledge of a person skilled in the art.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A middle and low temperature curing high temperature resistant high strength epoxy adhesive is characterized in that: the composite material comprises the following raw materials in parts by mass:
60-80 parts of p-aminophenol epoxy resin, 20-40 parts of glycidyl amine type epoxy resin, 3-10 parts of glycidyl ether, 25-35 parts of aromatic amine curing agent and 3-10 parts of inorganic filler.
2. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 1, characterized in that: the p-aminophenol epoxy resin is triglycidyl p-aminophenol epoxy resin.
3. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 1, characterized in that: the glycidyl amine type epoxy resin is a mixture of diaminodiphenylmethane tetraglycidyl amine and 1, 3-diglycidyl hydantoin.
4. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 3, characterized in that: the total mass of the diaminodiphenylmethane tetraglycidyl amine and the 1, 3-diglycidyl hydantoin is 100%, the mass percentage of the diaminodiphenylmethane tetraglycidyl amine is 15-40%, and the mass percentage of the 1, 3-diglycidyl hydantoin is 60-85%.
5. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 1, characterized in that: the glycidyl ether is at least one of trimethylolpropane triglycidyl ether and 1, 4-butanediol diglycidyl ether.
6. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 1, characterized in that: the aromatic amine curing agent is a mixture of m-phenylenediamine and diaminodiphenylmethane, wherein the total mass of the m-phenylenediamine and the diaminodiphenylmethane is 100%, the mass percentage of the m-phenylenediamine is 70-95%, and the mass percentage of the diaminodiphenylmethane is 5-30%.
7. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 1, characterized in that: the inorganic filler is fumed silica, and the specific surface area of the inorganic filler is 175-225 m2/g。
8. A preparation method of a medium-low temperature curing high temperature resistant high strength epoxy adhesive is characterized in that: the method comprises the following steps:
(1) stirring p-aminophenol epoxy resin, glycidyl amine type epoxy resin and glycidyl ether uniformly at room temperature to obtain epoxy resin mixed solution;
(2) preheating an aromatic amine curing agent to obtain a liquid cosolvent; rapidly stirring the epoxy resin mixed solution and the liquid cosolvent, and adding an inorganic filler after uniformly mixing to obtain an adhesive;
(3) and (3) curing the adhesive obtained in the step (2).
9. The preparation method of the medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 8, 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.
10. The medium-low temperature curing high temperature resistant high strength epoxy adhesive according to claim 8, characterized in that: in the step (3), the curing conditions of the adhesive are as follows: the room temperature is 8-24 h, 80 ℃/2-4 h, 100 ℃/6-8 h and 110 ℃/2-4 h.
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 true CN114605948A (en) | 2022-06-10 |
| CN114605948B 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) |
Cited By (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 |
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114605948B (en) | 2024-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102417804B (en) | Adhesive, its preparation method and application method | |
| CN102453458B (en) | Nano rubber modified room temperature cured high temperature resistant structure adhesive | |
| EP1123348A2 (en) | Impact-resistant epoxide resin compositions | |
| EP2578630B1 (en) | Epoxy resin composition and its preparing method | |
| US4002599A (en) | Epoxy resin compositions from glycidyl derivatives of aminophenols cured with tetracarboxylic dianhydrides | |
| JPS6310683A (en) | Adhesive composition | |
| 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 | |
| CN107815070A (en) | A kind of room temperature-curing low-viscosity high strength epoxy resin castable and preparation method | |
| CN111019580B (en) | Epoxy resin adhesive and preparation method and application thereof | |
| CN104694063A (en) | High-performance double-bond-containing epoxy resin/liquid rubber adhesive | |
| CN114605948A (en) | Medium-low temperature curing high-temperature-resistant high-strength epoxy adhesive and preparation method thereof | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| US3948849A (en) | Adhesive compositions | |
| 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 | |
| CN110885653B (en) | Low-temperature fast-curing epoxy insulating adhesive and preparation method and application thereof | |
| CN114058307A (en) | Preparation method of ultralow-temperature epoxy resin adhesive | |
| KR20160099609A (en) | Epoxy composition containing core-shell rubber | |
| CN109021847A (en) | A kind of and epoxy base carbon fiber composite material co-curing elasticity adhesive film material and preparation method thereof | |
| CN115651579B (en) | Epoxy adhesive capable of being rapidly cured and preparation method thereof | |
| CN102108264B (en) | Single-component epoxy structure adhesive tape and preparation method thereof | |
| CN114752314B (en) | High-durability high-temperature cured epoxy structural adhesive film and preparation method thereof | |
| CN101851395A (en) | Epoxy resin and production method thereof | |
| CN104448240A (en) | Blending method of epoxy resin moderate temperature curing for carbon fiber prepreg |
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 |