CN116656295A - Medium-low temperature cured high-strength high-toughness epoxy adhesive and preparation method thereof - Google Patents
Medium-low temperature cured high-strength high-toughness epoxy adhesive and preparation method thereof Download PDFInfo
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- CN116656295A CN116656295A CN202310743503.7A CN202310743503A CN116656295A CN 116656295 A CN116656295 A CN 116656295A CN 202310743503 A CN202310743503 A CN 202310743503A CN 116656295 A CN116656295 A CN 116656295A
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- epoxy resin
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- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 90
- 229920002635 polyurethane Polymers 0.000 claims abstract description 46
- 239000004814 polyurethane Substances 0.000 claims abstract description 46
- 238000001723 curing Methods 0.000 claims abstract description 42
- 238000013035 low temperature curing Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 238000009736 wetting Methods 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000013530 defoamer Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000012745 toughening agent Substances 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000539 dimer Substances 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- 238000000034 method Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- -1 modified alicyclic amine Chemical class 0.000 claims description 5
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004026 adhesive bonding Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- 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
- C09J11/08—Macromolecular additives
-
- 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
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a medium-low temperature curing high-strength high-toughness epoxy adhesive and a preparation method thereof. The adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.8 to 1.2; the component A comprises the following components in parts by mass: 80-100 parts of flexible epoxy resin containing polyurethane modified epoxy resin, 5-15 parts of reactive diluent, 40-60 parts of flexibilizer, 0.5-1 part of wetting dispersant, 40-60 parts of filler and 4-6 parts of coupling agent; the component B comprises the following components in parts by mass: 50-100 parts of modified flexible amine curing agent, 1-2 parts of wetting dispersant, 1-2 parts of defoamer and 40-80 parts of filler. The epoxy adhesive provided by the invention has the characteristics of high adhesion, good toughness, good low-temperature performance and medium-low temperature curing, and has the advantages of simple preparation method and moderate curing speed, and can meet the requirements of different working conditions.
Description
Technical Field
The invention relates to the field of adhesives, in particular to an epoxy adhesive with high strength and high toughness and a preparation method thereof.
Background
The epoxy adhesive is prepared by taking epoxy resin as a main body. The end of the macromolecule of the resin has epoxy groups, hydroxyl groups and ether bonds are arranged among chains, hydroxyl groups and ether bonds can be continuously generated in the curing process, the structure contains benzene rings and heterocyclic rings, and the structure determines that the epoxy adhesive has excellent performance. The epoxy adhesive has the advantages of high adhesive strength, excellent chemical stability, low curing shrinkage, easy processing and forming and the like. The adhesive has high adhesive force to various polar materials such as metal, glass, wood, plastic, ceramic, composite material, cement and the like, and is widely applied to various fields such as building home decoration, machining, electronic industry, national defense and military industry and the like.
In recent years, higher demands have been made on the low-temperature properties of epoxy adhesives in certain fields. Pure epoxy resins have very high crosslinking density and suffer from the disadvantages of brittle quality, low toughness, poor impact resistance, etc. even at normal temperature. However, in the cooling process after solidification, thermal stress is generated inside the resin matrix due to thermal shrinkage, and when the temperature is reduced from room temperature to lower temperature, internal stress generated by thermal shrinkage in the matrix is more remarkable, and once the thermal stress exceeds the strength of the resin itself, the resin matrix is damaged. Therefore, how to improve toughness is critical to the use of epoxy resins at low temperatures.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a medium-low temperature curing high-strength high-toughness epoxy adhesive and a preparation method thereof, which have the advantages of high toughness, good adhesive property, proper operation time, rapid strength improvement and good low-temperature property, thereby solving the technical problems in the prior art.
The invention aims at realizing the following technical scheme:
a medium and low temperature cured high strength high toughness epoxy adhesive comprising: A. the component A and the component B are matched according to the mass ratio of 1:0.8-1.2; wherein, the liquid crystal display device comprises a liquid crystal display device,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
preferably, in the adhesive, the flexible epoxy resin containing polyurethane modified epoxy resin in the component a is composed of at least one of polyurethane modified epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenolic epoxy resin, alicyclic epoxy resin, polyurethane modified epoxy resin, and dimer acid modified epoxy resin.
Preferably, in the adhesive, the polyurethane modified epoxy resin in the flexible epoxy resin is polyurethane modified epoxy resin prepared in the following manner, and the adhesive comprises the following components:
adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer; and adding the E-44 type epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to 75-85 ℃ for continuous reaction for 2h, and stopping the reaction to obtain the polyurethane modified epoxy resin.
Preferably, in the adhesive, the reactive diluent in the component a is: one or more of 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol triglycidyl ether, resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether;
the toughening agent in the component A is as follows: one or more of a core-shell toughening agent, a Qishi toughening agent and a modified epoxy resin;
the coupling agent in the component A is as follows: one or more of epoxy silane coupling agent, nitrogenous silane coupling agent, mercapto silane coupling agent and titanate coupling agent.
Preferably, in the adhesive, the core-shell toughening agent is a blend formed by uniformly dispersing core-shell rubber in epoxy resin;
the Qishi toughening agent is one or more of QS-BE and QS-EC;
the modified epoxy resin is nitrile rubber modified epoxy resin.
Preferably, in the adhesive, the filler in the component A and the filler in the component B are: one or more of aluminum hydroxide, aluminum oxide, talcum powder, calcium carbonate and silicon micropowder.
Preferably, in the adhesive, the modified flexible amine curing agent in the component B is: one or more of a modified fatty amine curing agent, a modified polyamide curing agent, a modified alicyclic amine curing agent, and a modified polyether amine curing agent;
the defoaming agent in the component B is as follows: one or more of organosilicon defoamer, polyether defoamer and mineral oil defoamer.
Preferably, in the adhesive, in the amine curing agent, the modified fatty amine curing agent is: one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, m-xylylenediamine, 1, 3-cyclohexanedimethylamine;
the modified polyamide curing agent is as follows: one or more of polyether modified polyamide, polyurethane modified polyamide, dimer acid modified polyamide;
the modified alicyclic amine curing agent is as follows: one or more of methylcyclopentylene diamine, 4-diamino dicyclohexyl methane and N-aminoethylpiperazine.
The preparation method of the medium-low temperature curing high-strength high-toughness epoxy adhesive comprises the following steps:
preparing a component A and a component B respectively; wherein, the liquid crystal display device comprises a liquid crystal display device,
preparing a component A: taking raw materials according to the A component formula of the medium-low temperature curing high-strength high-toughness epoxy adhesive, adding flexible epoxy resin containing polyurethane modified epoxy resin and a toughening agent in the A component raw materials into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding an active diluent, a wetting dispersant and a coupling agent, continuously stirring for 15min at the previous rotating speed, finally adding a filler of the A component, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain an A component colloid;
and (3) preparing a component B: according to the formula of the component A of the medium-low temperature curing high-strength high-toughness epoxy adhesive, the raw materials are taken, a modified flexible amine curing agent, a wetting dispersing agent and a defoaming agent in the component B are added into a stirrer, stirring and mixing are carried out for 40min at the rotating speed of 400-600r/min, then the filler of the component B is added, stirring is carried out for 2h, vacuum defoaming is carried out after the mixing is finished, and the component B colloid is obtained after filtration and encapsulation;
the component A and the component B are mixed according to the weight ratio of 1: mixing the components in a mass ratio of 0.8-1.2 to obtain the medium-low temperature curing high-strength high-toughness epoxy adhesive.
Preferably, in the above method, the polyurethane modified epoxy resin in the flexible epoxy resin containing polyurethane modified epoxy resin in the a component is polyurethane modified epoxy resin prepared in the following manner, and includes:
adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to 75-85 ℃ for continuous reaction for 2 hours, and stopping the reaction to obtain polyurethane modified epoxy resin;
the curing conditions of the component A and the component B when being mixed and used are any one of the following:
(1) Solidifying for 3-4 h at 60-70 ℃;
(2) Solidifying for 1-2 h at 80-90 ℃;
(3) Curing for 0.5-1 h at 100-110 ℃.
Compared with the prior art, the medium-low temperature curing high-strength high-toughness epoxy adhesive and the preparation method thereof provided by the invention have the beneficial effects that:
the flexible epoxy resin which is used as the toughening agent and matched with the flexible epoxy resin which contains polyurethane modified epoxy resin, the coupling agent and the modified flexible amine of the curing agent of the component B can synergistically toughen the epoxy resin system, so that the prepared epoxy adhesive has the characteristics of high strength and high toughness, is beneficial to improving the bonding performance of the epoxy adhesive, controlling proper operation time and improving the adhesive force of materials, has good bonding performance and peeling resistance at low temperature, and overcomes the defect that the common epoxy system is easy to crack and has insufficient impact resistance at the low temperature below-20 ℃. The polyurethane modified epoxy resin adopted by the invention has the advantages that the polyurethane molecule contains a urethane group (-NH-COO-) molecular chain, the flexibility is good, the vibration resistance and the fatigue resistance are good, the high elasticity is realized, and the performance is excellent especially at low temperature. The invention has the characteristics of high adhesion, good toughness, good low-temperature performance, proper operation time and rapid strength improvement, and the preparation method is simple, the curing speed is moderate, and the requirements of different working conditions can be met.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below in combination with the specific content of the invention; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "consisting of … …" is meant to exclude any technical feature element not explicitly listed. If such term is used in a claim, the term will cause the claim to be closed, such that it does not include technical features other than those specifically listed, except for conventional impurities associated therewith. If the term is intended to appear in only a clause of a claim, it is intended to limit only the elements explicitly recited in that clause, and the elements recited in other clauses are not excluded from the overall claim.
The term "parts by mass" means a mass ratio relationship between a plurality of components, for example: if the X component is described as X parts by mass and the Y component is described as Y parts by mass, the mass ratio of the X component to the Y component is expressed as x:y;1 part by mass may represent any mass, for example: 1 part by mass may be expressed as 1kg or 3.1415926 kg. The sum of the mass parts of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or 100 parts or equal. The parts, proportions and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as a range of values, the range is to be understood as specifically disclosing all ranges formed from any pair of upper and lower values within the range of values, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, that numerical range should be interpreted to include the ranges of "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", and the like. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.
The low-temperature curing high-strength high-toughness epoxy adhesive and the preparation method thereof provided by the invention are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
In order to clearly show the technical scheme and the technical effects, the low-temperature curing high-strength high-toughness epoxy adhesive and the preparation method thereof provided by the embodiment of the invention are described in detail in the following.
The following describes the embodiments of the present invention in further detail with reference to examples. The following preferred examples are illustrative of the present invention, but are not intended to limit the scope of the invention.
The test method adopted by each embodiment of the invention is as follows:
shear strength: the results were tested according to standard GB/T7124-2008.
Peel strength: the results were tested according to standard GB/T2791-1995.
Operating time: the results were tested according to standard GB/T7123.1-2015.
Example 1:
the embodiment provides a middle-low temperature curing high-strength high-toughness epoxy adhesive, which is prepared from the following raw materials in parts by weight:
polyurethane modified epoxy resin in the preparation of flexible epoxy resin: adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to about 80 ℃ and continuing to react for 2 hours to stop the reaction, thus obtaining polyurethane modified epoxy resin;
preparing a component A: adding 75 parts of bisphenol A epoxy resin, 25 parts of the prepared polyurethane modified epoxy resin and 45 parts of nitrile rubber modified epoxy resin into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 10 parts of 1, 4-butanediol diglycidyl ether, 1 part of wetting and dispersing agent (BYK series) and 5 parts of silane coupling agent, continuously stirring for 15min at the previous rotating speed, finally adding 50 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain a component A colloid;
and (3) preparing a component B: adding 40 parts of dimer acid modified polyurethane, 40 parts of D220 polyether amine, 1 part of wetting dispersant (BYK-940) and 1 part of defoamer (BYK-9920) into a stirrer, stirring and mixing for 40min at a rotating speed of 400-600r/min, adding 60 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after mixing, filtering and packaging to obtain a component B colloid;
the component A and the component B are mixed according to the weight ratio of 1: mixing the materials according to the mass ratio of 0.8-1.2, gluing (aluminum sheet) in the applicable period, and optionally heating and curing the materials under any one of the following conditions: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
Example 2:
the embodiment provides a middle-low temperature curing high-strength high-toughness epoxy adhesive, which is prepared from the following raw materials in parts by weight:
polyurethane modified epoxy resin in the preparation of flexible epoxy resin: adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to about 80 ℃ and continuing to react for 2 hours to stop the reaction, thus obtaining polyurethane modified epoxy resin;
preparing a component A: adding 80 parts of bisphenol A epoxy resin, 20 parts of the prepared polyurethane modified epoxy resin and 50 parts of nitrile rubber modified epoxy resin into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 8 parts of neopentyl glycol diglycidyl ether, 0.5 part of wetting dispersant (BYK series) and 5 parts of silane coupling agent, continuously stirring for 15min at the previous rotating speed, finally adding 50 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain a component A colloid;
and (3) preparing a component B: 50 parts of dimer acid modified polyurethane, 30 parts of D220 polyether amine, 2 parts of wetting dispersant (BYK-940) and 1 part of defoamer (BYK-9920) are added into a stirrer, stirred and mixed for 40min at a rotating speed of 400-600r/min, 70 parts of aluminum hydroxide is added, stirred for 2h, vacuum defoamation is carried out after the mixing is finished, and the component B colloid is obtained after filtration and encapsulation;
the component A and the component B are mixed according to the weight ratio of 1: mixing the materials according to the mass ratio of 0.8-1.2, gluing (aluminum sheet) in the applicable period, and optionally heating and curing the materials under any one of the following conditions: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
Example 3:
the embodiment provides a middle-low temperature curing high-strength high-toughness epoxy adhesive, which is prepared from the following raw materials in parts by weight:
the preparation method of the polyurethane modified epoxy resin comprises the following steps: adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to about 80 ℃ and continuing to react for 2 hours to stop the reaction, thus obtaining polyurethane modified epoxy resin;
the preparation step of the component A comprises the following steps: adding 70 parts of bisphenol A epoxy resin, 30 parts of polyurethane modified epoxy resin and 45 parts of core-shell toughening agent into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 12 parts of 1, 4-butanediol diglycidyl ether, 1 part of wetting dispersant (BYK series) and 4 parts of silane coupling agent, continuously stirring for 15min at the previous rotating speed, finally adding 60 parts of aluminum hydroxide, stirring for 2h, carrying out vacuum defoaming after the mixing is finished, and filtering and packaging to obtain a component A colloid;
the preparation step of the component B comprises the following steps: adding 80 parts of dimer acid modified polyurethane, 1 part of wetting dispersant (BYK-940) and 2 parts of defoamer (BYK-9920) into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 70 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after mixing, filtering and packaging to obtain a component B colloid;
the component A and the component B are mixed according to the weight ratio of 1: mixing the materials according to the mass ratio of 0.8-1.2, gluing (aluminum sheet) in the applicable period, and optionally heating and curing the materials under any one of the following conditions: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
Example 4:
the embodiment provides a middle-low temperature curing high-strength high-toughness epoxy adhesive, which is prepared from the following raw materials in parts by weight:
the preparation method of the polyurethane modified epoxy resin comprises the following steps: adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to about 80 ℃ and continuing to react for 2 hours to stop the reaction, thus obtaining polyurethane modified epoxy resin;
preparing a component A: adding 75 parts of bisphenol A epoxy resin, 25 parts of prepared isocyanate-terminated polyurethane prepolymer polyurethane modified epoxy resin and 50 parts of core-shell toughening agent into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 10 parts of neopentyl glycol diglycidyl ether, 1 part of wetting and dispersing agent (BYK series) and 5 parts of silane coupling agent, continuously stirring for 15min at the previous rotating speed, finally adding 55 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain a component A colloid;
and (3) preparing a component B: adding 80 parts of D220 polyetheramine, 2 parts of wetting dispersant (BYK-940) and 2 parts of defoamer (BYK-9920) into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 80 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after mixing, filtering and packaging to obtain a component B colloid;
the component A and the component B are mixed according to the weight ratio of 1: mixing the materials according to the mass ratio of 0.8-1.2, gluing (aluminum sheet) in the applicable period, and optionally heating and curing the materials under any one of the following conditions: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
Comparative example 1:
the comparative example was not of the prior art, but was designed to confirm the effect of removing certain components on the performance of the product of the invention, and the epoxy adhesive was prepared by the following steps, including (in parts by weight for each amount):
preparing a component A: adding 100 parts of bisphenol A epoxy resin and 45 parts of nitrile rubber modified epoxy resin into a stirrer, stirring and mixing for 40min at the rotation speed of 400-600r/min, adding 10 parts of 1, 4-butanediol diglycidyl ether, 1 part of wetting dispersant (BYK series) and 5 parts of silane coupling agent, continuously stirring for 15min at a high speed, finally adding 50 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain a component A colloid;
and (3) preparing a component B: adding 40 parts of dimer acid modified polyurethane, 40 parts of D220 polyether amine, 1 part of wetting dispersant (BYK-940) and 1 part of defoamer (BYK-9920) into a stirrer, stirring and mixing for 40min at a rotating speed of 400-600r/min, adding 60 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after mixing, filtering and packaging to obtain a component B colloid;
the component A and the component B are mixed according to the proportion of 1: mixing the materials according to the mass ratio of 0.8-1.2, and gluing (aluminum sheet) in the applicable period, wherein the heating and curing conditions are as follows: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
Comparative example 2:
the comparative example was not of the prior art, but was designed to confirm the effect of removing certain components on the performance of the product of the invention, and the epoxy adhesive was prepared by the following steps, including (in parts by weight for each amount):
preparing a component A: adding 40 parts of bisphenol A epoxy resin, 60 parts of polyurethane modified epoxy resin and 45 parts of nitrile rubber modified epoxy resin into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding 10 parts of 1, 4-butanediol diglycidyl ether, 1 part of wetting dispersant (BYK series) and 5 parts of silane coupling agent, continuously stirring for 15min at a high speed, adding 50 parts of aluminum hydroxide, stirring for 2h, carrying out vacuum defoamation after mixing, filtering and packaging to obtain a component A colloid;
and (3) preparing a component B: adding 40 parts of dimer acid modified polyurethane, 40 parts of D220 polyether amine, 1 part of wetting dispersant (BYK-940) and 1 part of defoamer (BYK-9920) into a stirrer, stirring and mixing for 40min at a rotating speed of 400-600r/min, adding 60 parts of aluminum hydroxide, stirring for 2h, performing vacuum defoaming after mixing, filtering and packaging to obtain a component B colloid;
the component A and the component B are mixed according to the weight ratio of 1: mixing the materials according to the mass ratio of 0.8-1.2, and gluing (aluminum sheet) in the applicable period, wherein the heating and curing conditions are as follows: curing for 3-4 h at 60-70 ℃, 1-2 h at 80-90 ℃ and 0.5-1 h at 100-110 ℃. Performance testing can be performed after stable bonding.
The test results of the above examples and comparative examples are shown in table 1 below:
table 1 shows the basic performance comparison
Comparing the experimental results of the examples of the present invention and the comparative examples, it can be found that: when the addition amount of the polyurethane modified epoxy resin is 20 to 30 parts by mass, examples 1, 2, 3 and 4 all have good operation time, initial setting time, shear strength and peel strength, have good strength and toughness, and have good comprehensive properties and good bonding performance at low temperature. When the content of the polyurethane-modified epoxy resin was very low, the comparative example 1 had poor toughness and poor low-temperature adhesive property, although it had higher shear strength. When the polyurethane-modified epoxy resin is more than 50 parts by mass, in comparative example 2, various strengths thereof are poor although there is high toughness. As can be seen from Table 2, the epoxy adhesive has better related performance and lower-temperature bonding performance than the prior art.
TABLE 2 comparison of the basic mechanical Properties of the inventive product with the existing market products
In summary, the epoxy adhesive provided by the embodiment of the invention has the characteristics of high adhesion, good toughness and good low-temperature performance, and the preparation method is simple, the curing speed is moderate, and the requirements of different working conditions can be met.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Claims (10)
1. The medium-low temperature curing high-strength high-toughness epoxy adhesive is characterized by comprising the following components: A. the component A and the component B are matched according to the mass ratio of 1:0.8-1.2; wherein, the liquid crystal display device comprises a liquid crystal display device,
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
2. the medium and low temperature curing high strength and high toughness epoxy adhesive according to claim 1, wherein the flexible epoxy resin containing polyurethane modified epoxy resin in the a component is composed of polyurethane modified epoxy resin and at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac epoxy resin, alicyclic epoxy resin, polyurethane modified epoxy resin, dimer acid modified epoxy resin.
3. The medium and low temperature curing high strength and high toughness epoxy adhesive according to claim 2, wherein the polyurethane modified epoxy resin in the flexible epoxy resin is a polyurethane modified epoxy resin prepared in the following manner, comprising:
adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer; and adding the E-44 type epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to 75-85 ℃ for continuous reaction for 2h, and stopping the reaction to obtain the polyurethane modified epoxy resin.
4. The medium and low temperature curing high strength high toughness epoxy adhesive according to claim 1, wherein the reactive diluents in the a component are: one or more of 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol triglycidyl ether, resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether;
the toughening agent in the component A is as follows: one or more of a core-shell toughening agent, a Qishi toughening agent and a modified epoxy resin;
the coupling agent in the component A is as follows: one or more of epoxy silane coupling agent, nitrogenous silane coupling agent, mercapto silane coupling agent and titanate coupling agent.
5. The medium-low temperature curing high-strength high-toughness epoxy adhesive according to claim 4, wherein the core-shell toughening agent is a blend formed by uniformly dispersing core-shell rubber in epoxy resin;
the Qishi toughening agent is one or more of QS-BE and QS-EC;
the modified epoxy resin is nitrile rubber modified epoxy resin.
6. The medium and low temperature cured high strength high toughness epoxy adhesive according to any of claims 1-5, wherein the fillers in the a and B components are: one or more of aluminum hydroxide, aluminum oxide, talcum powder, calcium carbonate and silicon micropowder.
7. The medium-low temperature cured high strength high toughness epoxy adhesive according to any one of claims 1-5, wherein the modified flexible amine curing agent in the B component is: one or more of a modified fatty amine curing agent, a modified polyamide curing agent, a modified alicyclic amine curing agent, and a modified polyether amine curing agent;
the defoaming agent in the component B is as follows: one or more of organosilicon defoamer, polyether defoamer and mineral oil defoamer.
8. The medium and low temperature cured high strength and high toughness epoxy adhesive according to claim 7, wherein the amine curing agent is: one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, m-xylylenediamine, 1, 3-cyclohexanedimethylamine;
the modified polyamide curing agent is as follows: one or more of polyether modified polyamide, polyurethane modified polyamide, dimer acid modified polyamide;
the modified alicyclic amine curing agent is as follows: one or more of methylcyclopentylene diamine, 4-diamino dicyclohexyl methane and N-aminoethylpiperazine.
9. A method for preparing the medium-low temperature curing high-strength high-toughness epoxy adhesive according to any one of claims 1-8, which is characterized by comprising the following steps:
preparing a component A and a component B respectively; wherein, the liquid crystal display device comprises a liquid crystal display device,
preparing a component A: taking all raw materials according to the A component formula of the medium-low temperature curing high-strength high-toughness epoxy adhesive according to any one of claims 1-8, adding flexible epoxy resin containing polyurethane modified epoxy resin and a toughening agent in the A component raw materials into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding an active diluent, a wetting dispersant and a coupling agent, continuing stirring for 15min at the previous rotating speed, finally adding a filler of the A component, stirring for 2h, performing vacuum defoamation after the mixing is finished, and filtering and packaging to obtain an A component colloid;
and (3) preparing a component B: taking all the raw materials according to the A component formula of the middle-low temperature curing high-strength high-toughness epoxy adhesive according to any one of claims 1-8, adding the modified flexible amine curing agent, the wetting dispersant and the defoamer in the B component raw materials into a stirrer, stirring and mixing for 40min at the rotating speed of 400-600r/min, adding the B component filler, stirring for 2h, performing vacuum defoaming after the mixing is finished, and filtering and packaging to obtain the B component colloid;
the component A and the component B are mixed according to the weight ratio of 1: mixing the components in a mass ratio of 0.8-1.2 to obtain the medium-low temperature curing high-strength high-toughness epoxy adhesive.
10. The method for preparing the medium-low temperature curing high-strength high-toughness epoxy adhesive according to claim 9, wherein the polyurethane modified epoxy resin in the flexible epoxy resin containing polyurethane modified epoxy resin in the component A is prepared by the following steps:
adding hexamethylene diisocyanate and polytetrahydrofuran glycol into a four-neck flask filled with nitrogen, heating to 85 ℃, and reacting for 3 hours to obtain an isocyanate-terminated polyurethane prepolymer; adding the E-44 epoxy resin and the prepared isocyanate-terminated polyurethane prepolymer into a three-necked bottle filled with nitrogen, heating to 75-85 ℃ for continuous reaction for 2 hours, and stopping the reaction to obtain polyurethane modified epoxy resin;
the curing conditions of the component A and the component B when being mixed and used are any one of the following:
(1) Solidifying for 3-4 h at 60-70 ℃;
(2) Solidifying for 1-2 h at 80-90 ℃;
(3) Curing for 0.5-1 h at 100-110 ℃.
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