CN115851202B - Bi-component room temperature curing epoxy resin adhesive and preparation method and application thereof - Google Patents
Bi-component room temperature curing epoxy resin adhesive and preparation method and application thereof Download PDFInfo
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- CN115851202B CN115851202B CN202211632703.7A CN202211632703A CN115851202B CN 115851202 B CN115851202 B CN 115851202B CN 202211632703 A CN202211632703 A CN 202211632703A CN 115851202 B CN115851202 B CN 115851202B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 106
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 106
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 239000000853 adhesive Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- -1 alicyclic amine Chemical class 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229920006332 epoxy adhesive Polymers 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 4
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 claims description 4
- ZCZCZLVSKGCRTD-UHFFFAOYSA-N 2-(tridecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCOCC1CO1 ZCZCZLVSKGCRTD-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
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-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
- 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 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 229920006335 epoxy glue Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging 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
- 239000012745 toughening agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 239000000412 dendrimer Substances 0.000 description 1
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Abstract
The invention provides a bi-component room temperature curing epoxy resin adhesive and a preparation method and application thereof, wherein the bi-component room temperature curing epoxy resin adhesive comprises an A component and a B component, the A component comprises a combination of epoxy resin A, epoxy resin B, an epoxy diluent and a filler a, the epoxy resin B is dendritic epoxy resin, and the B component comprises a combination of alicyclic amine curing agent, dendritic curing agent, curing accelerator and filler B; the component A and the component B with the specific components are matched, so that the prepared bi-component epoxy resin adhesive has excellent bonding performance and temperature resistance, has higher shear strength at high temperature, and has no problem of short storage period at normal temperature.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a bi-component room-temperature curing epoxy resin adhesive, and a preparation method and application thereof.
Background
The epoxy adhesive is a synthetic resin adhesive and generally has two curing modes of room temperature curing and medium-high temperature curing. Wherein, the room temperature cured epoxy glue is generally packaged by adopting A, B bi-component, and A, B components respectively take epoxy resin and curing agent as main agents; the epoxy glue cured at medium and high temperature is generally packaged in a single component. The formula contains a latent curing agent or a curing accelerator, so that the storage time is shorter than that of two components.
Generally, the two-component epoxy glue has the advantage of convenient use compared with the single-component epoxy glue due to loose curing conditions, but has low strength after curing and relatively low glass transition temperature, so that the high-temperature resistance is poor. With the rapid development of the fields of electronics, automobiles, mobile communication, mechanical manufacturing and aerospace in recent years, the improvement of production efficiency brings higher requirements on the temperature resistance of the two-component epoxy adhesive.
CN109705785a discloses a room temperature curing high temperature resistant epoxy adhesive, which comprises a component a and a component B, wherein the component a comprises high temperature resistant epoxy resin, general epoxy resin, toughening agent, thixotropic agent, coupling agent and antioxidant; the component B comprises polyamide, aliphatic amine, a high-temperature-resistant curing agent and a thixotropic agent; wherein the weight ratio of the component A to the component B is 1-5:1; the component A comprises the following components in percentage by weight: 20-40% of high-temperature-resistant epoxy resin, 40-60% of general epoxy resin, 5-15% of toughening agent, 1-3% of thixotropic agent, 0.1-1% of coupling agent and 0.1-1% of antioxidant; the weight percentage of each component in the component B is as follows: 10-30% of polyamide, 10-30% of fatty amine, 30-50% of high temperature resistant curing agent and 1-3% of thixotropic agent; the room-temperature-cured high-temperature-resistant epoxy adhesive is particularly suitable for bonding the center of a loudspeaker, is also suitable for repairing aerospace parts, and has the comprehensive characteristics of convenience in construction, good permeability, high bonding strength, high temperature resistance and the like. However, the large amount of multifunctional epoxy resin contained in the formulation thereof is disadvantageous for long-term storage of the a-component.
CN111019580a discloses an epoxy resin adhesive, and a preparation method and application thereof; in order to improve the curing speed and the temperature resistance of a cured product, the main agent of the component B adopts a method of pre-reacting epoxy resin with an aromatic amine curing agent and aliphatic amine (ether amine, polyamide and the like) to obtain a modified curing agent and then mixing a mercaptan curing agent, and the high-temperature performance of the obtained epoxy adhesive at 150 ℃ after normal-temperature curing is not greatly different from that of the epoxy adhesive at normal-temperature. However, the reaction time of the modified curing agent provided by the invention at high temperature is too long, and the production process is time-consuming and complex.
CN104804691a discloses a room temperature curing high temperature resistant high toughness epoxy adhesive and a preparation method thereof. The scheme adopts the conventional epoxy resin and the core-shell rubber particle modified epoxy resin to be compounded as the component A, and the component B adopts the alicyclic amine and modified aliphatic amine compounded curing agent, so that the obtained cured product of the epoxy resin adhesive has higher Tg; however, the epoxy adhesive provided by the invention has lower shear strength and poorer temperature resistance at a high temperature of 150 ℃.
Therefore, development of a two-component room temperature curing epoxy resin adhesive having excellent temperature resistance and adhesive properties is desired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a bi-component room temperature curing epoxy resin adhesive, a preparation method and application thereof, wherein the bi-component room temperature curing epoxy resin adhesive has excellent bonding performance and temperature resistance, still has higher shear strength at high temperature, and has no problem of short storage period at normal temperature.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a two-part room temperature curing epoxy adhesive comprising an a-part and a B-part;
the component A comprises a combination of epoxy resin A, epoxy resin B, an epoxy diluent and a filler a, wherein the epoxy resin B is dendritic epoxy resin;
the component B comprises a combination of alicyclic amine curing agent, dendritic curing agent, curing accelerator and filler B.
The bi-component room temperature curing epoxy resin adhesive provided by the invention comprises a component A and a component B, wherein the component A is used as a main agent, two epoxy resins of epoxy resin A and epoxy resin B are matched to obtain the bi-component room temperature curing epoxy resin adhesive, and the epoxy resin B is defined as resin-shaped epoxy resin; the component B is a curing agent component, and is obtained by matching two curing agent components, namely an alicyclic curing agent and a dendritic curing agent; the component A and the component B with specific components are matched, so that the obtained bi-component epoxy resin adhesive has excellent bonding performance and temperature resistance, has higher shear strength at high temperature, and has no problem of short storage period at normal temperature.
In the present invention, the dendritic epoxy resin refers to grafting an epoxy monomer or an epoxy resin to a dendritic polymer having different functional groups; in particular, CYE-001 and/or CYE-002 of Wired morning source can be selected.
Preferably, the component A comprises the following components in parts by weight:
wherein the epoxy resin a may be 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, or the like.
The epoxy resin B may be 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 parts by weight, or the like.
The epoxy diluent may be 5.2 parts by weight, 5.4 parts by weight, 5.6 parts by weight, 5.8 parts by weight, or the like.
The filler a may be 50.5 parts by weight, 51 parts by weight, 51.5 parts by weight, 52 parts by weight, 52.5 parts by weight, 53 parts by weight, 53.5 parts by weight, or the like.
Preferably, the epoxy equivalent of the epoxy resin A is 160 to 250g/mol, for example 170g/mol, 180g/mol, 190g/mol, 200g/mol, 210g/mol, 220g/mol, 230g/mol or 240g/mol, etc.
Preferably, the epoxy resin a includes any one or a combination of at least two of bisphenol a diglycidyl ether, bisphenol S epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and phenolic epoxy resin, and more preferably bisphenol a diglycidyl ester.
In the present invention, the epoxy resin a may be selected from E51 and/or E44 bisphenol a type epoxy resins.
Preferably, the epoxy equivalent of the epoxy resin B is 185 to 225g/mol, for example 190g/mol, 195g/mol, 200g/mol, 205g/mol, 210g/mol, 215g/mol or 220g/mol, etc.
Preferably, the epoxy diluent comprises a monofunctional reactive epoxy diluent and/or a difunctional reactive epoxy diluent.
Preferably, the epoxy diluent comprises any one or a combination of at least two of butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1, 6-hexanediol diglycidyl ether, and more preferably any one or a combination of at least two of dodecyl glycidyl ether, tridecyl glycidyl ether or tetradecyl glycidyl ether.
Preferably, the filler a and the filler b each comprise any one or a combination of at least two of aluminum oxide, calcium carbonate, talcum powder or silicon micropowder.
Preferably, the mesh number of the filler a and the filler b is 400 to 800 mesh, for example, 500 mesh, 600 mesh, 700 mesh, or the like, each independently.
Preferably, the a-component further comprises an antifoaming agent and/or a coupling agent.
Preferably, the content of the antifoaming agent in the two-component room temperature curing epoxy resin adhesive is 0.2 to 0.4 part by weight, for example, 0.22 part by weight, 0.24 part by weight, 0.26 part by weight, 0.28 part by weight, 0.3 part by weight, 0.32 part by weight, 0.34 part by weight, 0.36 part by weight, 0.38 part by weight, or the like.
Preferably, the content of the coupling agent in the two-component room temperature curing epoxy resin adhesive is 0.2 to 0.4 part by weight, for example, 0.22 part by weight, 0.24 part by weight, 0.26 part by weight, 0.28 part by weight, 0.3 part by weight, 0.32 part by weight, 0.34 part by weight, 0.36 part by weight, 0.38 part by weight, or the like.
Preferably, the coupling agent comprises a silane coupling agent and/or a titanate coupling agent, further preferably a silane coupling agent, for example KH550 and/or KH570 may be selected.
Preferably, the component B comprises the following components in parts by weight:
wherein the alicyclic amine curing agent may be 10.2 parts by weight, 10.4 parts by weight, 10.6 parts by weight, 10.8 parts by weight, 11 parts by weight, 11.2 parts by weight, 11.4 parts by weight, 11.6 parts by weight, 11.8 parts by weight, or the like.
The dendritic curing agent may be 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, 4.8 parts by weight, or the like.
The curing accelerator may be 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, or the like.
The filler b may be 9.2 parts by weight, 9.4 parts by weight, 9.6 parts by weight, 9.8 parts by weight, 10 parts by weight, 10.2 parts by weight, 10.4 parts by weight, 10.6 parts by weight, 10.8 parts by weight, or the like.
In the invention, the dendritic curing agent contains a plurality of (single molecule contains more than or equal to 3) primary amine groups on the surface and has a sphere-like structure, for example, wired morning source CYD-N1403 (the amine value is 340-450 mgKOH/g, the viscosity is 2-4 kcps@25deg.C), wired morning source CYD-N1635, the amine value is 520-620 mgKOH/g, the viscosity is 0.5-1 kcps@25deg.C, and the CYD-N1403 is preferable.
Preferably, the amine value of the alicyclic amine curing agent is 500 to 600mgKOH/g, for example 520mgKOH/g, 540mgKOH/g, 560mgKOH/g, 580mgKOH/g or the like.
Preferably, the equivalent of active hydrogen in the alicyclic amine curing agent is 40 to 60g/eq, for example 42g/eq, 44g/eq, 46g/eq, 48g/eq, 50g/eq, 52g/eq, 54g/eq, 56g/eq or 58g/eq, etc.
Preferably, the amine value of the dendritic curing agent is 300 to 650mgKOH/g, for example 340mgKOH/g, 380mgKOH/g, 420mgKOH/g, 460mgKOH/g or 500mgKOH/g, etc.
Preferably, the mass ratio of the A component to the B component is (3-5): 1, for example 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1 or 4.8:1, etc.
In a second aspect, the present invention provides a method for preparing a two-part room temperature curing epoxy resin adhesive according to the first aspect, the method comprising the preparation of a-part and the preparation of B-part;
the preparation method of the component A comprises the following steps: mixing epoxy resin A, epoxy resin B, epoxy diluent, optional coupling agent and optional defoamer, and adding filler a for mixing to obtain a component A;
the preparation method of the component B comprises the following steps: mixing the alicyclic amine curing agent, the dendritic curing agent and the curing accelerator, and adding the filler B for mixing to obtain the component B.
Preferably, the preparation method of the component A specifically comprises the following steps: mixing epoxy resin A, epoxy resin B, epoxy diluent, optional coupling agent and optional defoaming agent under the stirring condition of 10-20 rpm for 4-6 min, adding filler a, mixing under the stirring condition of 10-20 rpm for 5-15 min, mixing under the stirring condition of 25-35 rpm for 25-35 min, vacuumizing, and continuously mixing under the stirring condition of 25-35 rpm for 15-25 min to obtain the component A.
The preparation method of the component B specifically comprises the following steps: mixing alicyclic amine curing agent, dendritic curing agent and curing accelerator for 4-6 min under the stirring condition of 10-20 rpm, adding filler B, mixing for 5-15 min under the stirring condition of 10-20 rpm, mixing for 25-35 min under the stirring condition of 25-35 rpm, vacuumizing, and continuously mixing for 15-25 min under the stirring condition of 25-35 rpm to obtain the component B.
In a third aspect, the present invention provides the use of a two-part room temperature curing epoxy adhesive as described in the first aspect in an electronic product.
Compared with the prior art, the invention has the following beneficial effects:
the bi-component room temperature curing epoxy resin adhesive provided by the invention comprises a component A and a component B, wherein the component A comprises a combination of epoxy resin A, epoxy resin B, an epoxy diluent and a filler a, the epoxy resin B is dendritic epoxy resin, and the component B comprises a combination of alicyclic amine curing agent, dendritic curing agent, curing accelerator and filler B; by adopting the component A and the component B containing the specific components for matching, the obtained bi-component epoxy resin adhesive has excellent bonding performance and temperature resistance, still has higher shear strength at a high temperature of 150 ℃, and has no problem of short storage period at normal temperature.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The information on the raw materials involved in the detailed description is shown in table 1:
TABLE 1
Examples 1 to 8 and comparative examples 1 to 5
A two-component room temperature curing epoxy resin adhesive, which comprises a component A and a component B in a mass ratio of 4:1;
the preparation raw materials of the A component and the B component are shown in Table 2, wherein the amount is "parts by weight";
TABLE 2
The preparation method of the two-component room temperature curing epoxy resin adhesive provided in the examples and the comparative examples comprises the preparation of the A component and the preparation of the B component;
the preparation method of the component A comprises the following steps: weighing E51 bisphenol A epoxy resin, dendritic epoxy resin, epoxy diluent, defoaming agent and coupling agent, adding into a planetary disperser, dispersing for 5min at 15rpm, adding talcum powder, dispersing for 10min at 15rpm, dispersing for 30min at 30rpm, finally opening vacuum (the vacuum degree is-0.095 MPa), continuing dispersing for 20min at 30rpm, discharging at normal pressure after vacuum defoaming, and obtaining the component A;
the preparation method of the component B comprises the following steps: weighing alicyclic amine curing agent, dendritic curing agent and curing accelerator, adding into a planetary dispersing machine, dispersing for 5min at 15rpm, adding talcum powder, dispersing for 10min at 15rpm, and dispersing for 30min at 30 rpm; and then opening vacuum, (the vacuum degree is-0.095 MPa), continuously dispersing for 20min at the rotating speed of 30rpm, and discharging at normal pressure after vacuum defoaming to obtain the component B.
Performance test:
(1) 180 ° peel strength: testing a testing method provided by a rigid material by referring to a flexible material of a 180-degree peel strength testing method of a national standard GB/T2790-1995 adhesive; the component A and the component B of the bi-component room temperature curing epoxy resin adhesive are fully mixed and then used, a test piece is prepared by adopting a cold rolled steel bar CRS1403 with the thickness of 0.5mm, and the bonding area is 25 multiplied by 100mm; after curing for 7 days at room temperature, testing by a universal material tester at room temperature, wherein the testing speed is 50mm/min;
(2) Tensile shear strength: referring to the national standard GB/T27124-2008 adhesive tensile shear strength measurement (rigid material to rigid material), a component A and a component B of a bi-component room temperature curing epoxy resin adhesive are fully mixed and then used, a prepared test piece adopts a cold-rolled steel sheet CRS1403 with the thickness of 2mm, and the bonding overlap area is 25 multiplied by 12.5mm; after curing for 7 days at room temperature, testing by a universal material tester at room temperature, wherein the testing speed is 10mm/min, and obtaining the normal-temperature tensile shear strength;
balancing the temperature of the test piece in a constant temperature environment box at 150 ℃ for at least 10min, and then testing in situ to obtain tensile shear strength at 150 ℃;
(3) Retention rate: calculating the ratio of the tensile shear strength at 150 ℃ to the tensile shear strength at normal temperature, which is obtained by the test in the step (2), and obtaining the retention rate.
The two-component room temperature curing epoxy resin adhesives provided in examples 1 to 8 and comparative examples 1 to 5 were tested according to the above test methods, and the test results are shown in table 3:
TABLE 3 Table 3
As can be seen from the data in table 3:
as can be seen from the data of examples 1 to 4: the total amount of the two resins in examples 1-2 is equal and 45 parts, but the relative content of the dendritic epoxy resin in the A component in the resin in example 2 is higher, and under the condition that other conditions are basically the same, the tensile shear strength of the cured product of the adhesive provided in example 2 is relatively higher, can reach 24.8MP, and the corresponding peel strength is also higher; the retention of strength at higher temperature was compared, and example 2 could reach 35% and was higher than 28% of example 1; the same is true for examples 3 and 4, except that the total amount of the two resins in the A-component in examples 3 and 4 is slightly reduced (from 45 parts by weight to 40 parts by weight) as compared with examples 1 to 2, and the corresponding adhesive strength and peel strength are also reduced, and it is seen that the relative amounts of the total amount of epoxy resin and dendritic epoxy resin have an effect on both the strength retention and adhesive strength.
As can be seen from comparing the data of examples 1 and examples 5 to 6, when the B component is identical, adjusting the relative proportion of the resin-like epoxy resin in the a component to the total amount of resin lowers the tensile shear strength and peel strength at normal temperature and at high temperature of the obtained adhesive, but the high temperature strength retention rate of example 6 is slightly higher than that of example 5.
Comparing the data of example 1 with the data of examples 7-8, it can be seen that the relative content of the dendritic curing agent of the B component in the curing agent is adjusted under the condition that the A component is consistent, and the strength and the retention rate of the adhesive obtained in example 7 are not greatly changed; in contrast, the adhesive obtained in example 8 has a low room temperature tensile shear strength (19.6 MPa), so that the peel strength is significantly reduced although the high temperature retention is maintained, which may indicate that the positive effect of the alicyclic amine curing agent on the base strength exceeds that of the dendritic curing agent.
As can be seen from a comparison of the data of example 1 and comparative examples 1 to 2, the absence of the dendritic epoxy resin added to the a component resulted in a significant decrease in both the room temperature tensile shear strength and the high temperature holding rate of the resulting adhesive, but the data of comparative example 2 showed a somewhat improved high temperature strength holding rate over that of comparative example 1.
Further comparing the data of example 2 with comparative example 3, example 4 and comparative example 5, it can also be seen that, in the case where the a component is consistent, the dendritic curing agent is replaced, resulting in a significant decrease in the high temperature tensile shear strength and strength retention rate of the resulting adhesive.
Finally, as can be seen from the data of comparative example 3 and comparative example 4, when the B component is consistent, the addition of no dendritic epoxy resin results in a significant decrease in the tensile shear strength, strength retention and peel strength at both normal and high temperatures of the resulting adhesive.
The applicant states that the present invention is illustrated by the above examples as a two-part room temperature curing epoxy adhesive and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (20)
1. A two-component room temperature curing epoxy resin adhesive, characterized in that the two-component room temperature curing epoxy resin adhesive comprises a component A and a component B;
the component A comprises a combination of epoxy resin A, epoxy resin B, an epoxy diluent and a filler a, wherein the epoxy resin B is dendritic epoxy resin, and the brand of the dendritic epoxy resin is CYE-001 and/or CYE-002;
the component A comprises the following components in parts by weight:
25-35 parts by weight of epoxy resin A
10-15 parts by weight of epoxy resin B
5-6 parts by weight of epoxy diluent
50-54 parts of filler a;
the component B comprises a combination of alicyclic amine curing agent, dendritic curing agent, curing accelerator and filler B, wherein the brand of the dendritic curing agent is CYD-N1403 or CYD-N1635;
the component B comprises the following components in parts by weight:
10-12 parts by weight of alicyclic amine curing agent
3-5 parts by weight of dendritic curing agent
1 to 1.5 parts by weight of a curing accelerator
9-11 parts of filler.
2. The two-component room temperature curing epoxy resin adhesive of claim 1, wherein the epoxy resin a has an epoxy equivalent of 160-250 g/mol.
3. The two-part room temperature curing epoxy resin adhesive of claim 1, wherein the epoxy resin a comprises any one or a combination of at least two of bisphenol a diglycidyl ether, bisphenol S epoxy, aliphatic epoxy, cycloaliphatic epoxy, or phenolic epoxy.
4. A two-part room temperature curing epoxy resin adhesive according to claim 3, wherein the epoxy resin a is bisphenol a diglycidyl ester.
5. The two-part room temperature curing epoxy resin adhesive of claim 1, wherein the epoxy diluent comprises a monofunctional reactive epoxy diluent and/or a difunctional reactive epoxy diluent.
6. The two-part room temperature curing epoxy resin adhesive of claim 5, wherein the epoxy diluent comprises any one or a combination of at least two of butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, or 1, 6-hexanediol diglycidyl ether.
7. The two-part room temperature curing epoxy resin adhesive of claim 6, wherein the epoxy diluent is any one or a combination of at least two of dodecyl glycidyl ether, tridecyl glycidyl ether, or tetradecyl glycidyl ether.
8. The two-part room temperature curing epoxy resin adhesive of claim 1, wherein filler a and filler b each comprise any one or a combination of at least two of aluminum oxide, calcium carbonate, talc or silicon micropowder.
9. The two-part room temperature curing epoxy resin adhesive according to claim 1, wherein the mesh numbers of filler a and filler b are each independently 400 to 800 mesh.
10. The two-part room temperature curing epoxy adhesive of claim 1, wherein the a-part further comprises an antifoaming agent and/or a coupling agent.
11. The two-component room temperature curing epoxy resin adhesive according to claim 10, wherein the content of the defoaming agent in the two-component room temperature curing epoxy resin adhesive is 0.2-0.4 parts by weight.
12. The two-component room temperature curing epoxy resin adhesive according to claim 10, wherein the content of the coupling agent in the two-component room temperature curing epoxy resin adhesive is 0.2-0.4 parts by weight.
13. The two-part room temperature curing epoxy adhesive of claim 10, wherein the coupling agent comprises a silane coupling agent and/or a titanate coupling agent.
14. The two-part room temperature curing epoxy adhesive of claim 13, wherein the coupling agent is a silane coupling agent.
15. The two-component room temperature curing epoxy resin adhesive according to claim 1, wherein the amine value of the alicyclic amine curing agent is 500-600 mgKOH/g.
16. The two-component room temperature curing epoxy resin adhesive according to claim 1, wherein the equivalent of active hydrogen in the alicyclic amine curing agent is 40-60 g/eq.
17. The two-component room temperature curing epoxy resin adhesive according to claim 1, wherein the mass ratio of the component A to the component B is (3-5): 1.
18. A method of preparing the two-part room temperature curing epoxy resin adhesive of any one of claims 1-17, wherein the method of preparing comprises preparing a part a and preparing a part B;
the preparation method of the component A comprises the following steps: mixing epoxy resin A, epoxy resin B, epoxy diluent, optional coupling agent and optional defoamer, and adding filler a for mixing to obtain a component A;
the preparation method of the component B comprises the following steps: mixing the alicyclic amine curing agent, the dendritic curing agent and the curing accelerator, and adding the filler B for mixing to obtain the component B.
19. The preparation method of the component A according to claim 18, wherein the preparation method specifically comprises the following steps: firstly mixing epoxy resin A, epoxy resin B, epoxy diluent, optional coupling agent and optional defoaming agent for 4-6 min under the stirring condition of 10-20 rpm, adding filler a, mixing for 5-15 min under the stirring condition of 10-20 rpm, mixing for 25-35 min under the stirring condition of 25-35 rpm, vacuumizing, and continuously mixing for 15-25 min under the stirring condition of 25-35 rpm to obtain the component A;
the preparation method of the component B specifically comprises the following steps: mixing the alicyclic amine curing agent, the dendritic curing agent and the curing accelerator for 4-6 min under the stirring condition of the rotating speed of 10-20 rpm, adding the filler B, mixing for 5-15 min under the stirring condition of the rotating speed of 10-20 rpm, mixing for 25-35 min under the stirring condition of the rotating speed of 25-35 rpm, vacuumizing, and continuously mixing for 15-25 min under the stirring condition of the rotating speed of 25-35 rpm to obtain the component B.
20. Use of the two-component room temperature curing epoxy resin adhesive according to any one of claims 1-17 in electronic products.
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