CN114989757B - Low-temperature rapid-curing moisture-heat-resistant epoxy adhesive and preparation method and application thereof - Google Patents
Low-temperature rapid-curing moisture-heat-resistant epoxy adhesive and preparation method and application thereof Download PDFInfo
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- CN114989757B CN114989757B CN202210746391.6A CN202210746391A CN114989757B CN 114989757 B CN114989757 B CN 114989757B CN 202210746391 A CN202210746391 A CN 202210746391A CN 114989757 B CN114989757 B CN 114989757B
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- 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
Abstract
The invention discloses a low-temperature quick-curing moisture-heat-resistant epoxy adhesive and a preparation method and application thereof, wherein the adhesive comprises the following raw materials: epoxy resin, blocked isocyanate, polythiol curing agent, curing accelerator, filler, pigment and auxiliary agent; the polythiol curing agent is prepared by reacting phenyl dithiol compounds with diisocyanate silane compounds, and the curing accelerator is prepared by compounding tertiary amine curing accelerators and imidazole curing accelerators. The invention prepares the polythiol curing agent through the reaction of the phenyl dithiol compound and the diisocyanate silane compound, and the epoxy resin adhesive containing the polythiol curing agent, the curing accelerator and the blocked isocyanate has good moisture and heat resistance. The epoxy adhesive prepared by the invention can be rapidly cured at 50-60 ℃ for 20-40min, and is suitable for bonding and sealing components sensitive to heat, such as speakers, mobile phone plate-changing glass and the like.
Description
Technical Field
The invention belongs to the technical field of epoxy adhesives, and particularly relates to a low-temperature rapid-curing moisture-heat-resistant epoxy adhesive, and a preparation method and application thereof.
Background
The epoxy adhesive has the characteristics of good adhesion, chemical stability, low shrinkage, excellent thermal performance, mechanical performance and the like, so that the epoxy adhesive is widely applied to the fields of semiconductor devices, integrated circuits, electronic packaging and the like. As disclosed in patent CN201410594264.4, an epoxy resin adhesive and a preparation method thereof are disclosed, wherein the epoxy resin adhesive is prepared by uniformly mixing a component a and a component B according to a weight ratio of 1:0.8-1, and the component a comprises the following raw material components in parts by weight: 376 to 470 parts of polyether polyol; 80-100 parts of toluene diisocyanate; 4560-5700 parts of epoxy resin; 250-313 parts of epoxy diluent; the component B comprises the following raw material components in parts by weight: 20-40 parts of aliphatic polyamine; 40-50 parts of hydroxyl compound; 8-15 parts of mercaptan compounds; 5-10 parts of a composite accelerator; 55-70 parts of compound curing agent; wherein the polyether polyol is selected from at least one of polyether 3050, polyether 3010 and polyether 2070; the epoxy resin is at least one selected from E51 type epoxy resin and E44 type epoxy resin; the mercaptan compound is pentaerythritol mercaptopropionate. Patent CN201380062183.3 discloses a resin curing agent and a one-component epoxy resin composition, and the present invention provides a resin curing agent composed of a compound having 1 or more hydroxyl groups and 2 or more thiol groups in the molecule and having a molecular weight of 100 to 2000. The present invention further provides a one-component epoxy resin composition comprising, as component (1), a compound having 1 or more hydroxyl groups and 2 or more thiol groups in the molecule and having a molecular weight of 100 to 2000, an epoxy resin having 2 or more epoxy groups per 1 molecule on average as component (2), and a latent curing accelerator as component (3). The epoxy adhesive system cured by mercaptan in the prior art has the advantages of quick curing, high bonding strength and low shrinkage rate, but the curing condition of the mixed system is generally more than or equal to 60 ℃/30 minutes, the epoxy resin is a strong polar material and has good affinity with water, complex physical and chemical reactions can occur when water is absorbed and permeated by the adhesive and meets high temperature conditions, such as precipitation of filler, rupture and degradation of chemical bonds and the like, micro cracks finally occur, bonding interface failure is caused, and the shear strength attenuation of the moisture and heat resistant aging (60 ℃/90%RH or 85 ℃/85%RH) for 72 hours is generally up to 50% or even more than 70%, so that the reliability of bonded or packaged products is seriously reduced. At present, in applications such as sealing and bonding of a loudspeaker and cover plate glass, low-temperature rapid curing (less than or equal to 80 ℃/30 minutes, even less than or equal to 55 ℃/30 minutes) and humidity and heat aging resistance for 168hrs strength are generally required to be maintained to be more than 50%, and a certain gap exists between the application effect of the prior art and the application requirement of a client, so that the improvement of the low-temperature rapid curing and humidity and heat aging resistance performance of the epoxy-based adhesive has important significance for further expanding the application of the epoxy adhesive in the fields of electronic components and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-temperature quick-curing moisture-heat-resistant epoxy adhesive, a preparation method and application thereof, wherein a high-molecular polythiol curing agent with a terminal group of mercaptan is prepared by the reaction of a phenyl dithiol compound and a diisocyanate-based silane compound, and the polythiol curing agent, a tertiary amine and imidazole compound curing accelerator and blocked isocyanate are mutually matched, so that the epoxy adhesive provided by the invention is quickly cured at low temperature, has good moisture-heat resistance after curing, and basically has no reduction in shear strength after high-temperature high-humidity aging.
In order to achieve the above purpose, the following specific technical scheme is adopted:
the low-temperature quick-curing wet-heat-resistant epoxy adhesive is characterized by comprising the following raw materials: epoxy resin, blocked isocyanate, polythiol curing agent, curing accelerator, filler and pigment; the polythiol curing agent is prepared by reacting phenyl dithiol compounds with diisocyanate silane compounds, and the curing accelerator is prepared by compounding tertiary amine curing accelerators and imidazole curing accelerators.
Further, the adhesive comprises the following raw materials in parts by weight: 30-50 parts of epoxy resin, 3.0-4.5 parts of blocked isocyanate, 17-35 parts of polythiol curing agent, 5-10 parts of curing accelerator, 10-25 parts of filler and 0.5-1 part of pigment; the molar ratio of the phenyl dithiol compound to the diisocyanate silane compound is 1.12-1.20:1, and the weight ratio of the tertiary amine curing accelerator to the imidazole curing accelerator is 1-3:10.
The polythiol curing agent prepared from the phenyl dithiol compound and the diisocyanate silane compound can improve the hydrophobic property of the epoxy adhesive and improve the high-temperature resistance and the damp-heat resistance.
The phenyl dithiol compound is selected from one or more than two of 1, 4-dimethyl benzene mercaptan, 1, 3-dimethyl benzene mercaptan, 1, 2-dimethyl benzene mercaptan-4, 5-dimethyl, 1, 2-dimethyl benzene mercaptan-3, 6-dimethyl and 1, 4-dimethyl benzene mercaptan-2, 5-dimethyl; the diisocyanate silane compound is selected from one or a combination of two or more of diisocyanate dimethylsilane, diisocyanate dibutylsilane, 1, 3-tetraethyl-1, 3-bis (isocyanatomethyl) disiloxane and 1, 3-tetramethyl-1, 3-bis (isocyanatomethyl) disiloxane.
The blocking agent of the blocked isocyanate is a phenol compound, and is selected from one or a combination of two or more of phenol, cardanol, resorcinol and m-cresol; preferably, the blocking agent of the blocked isocyanate is cardanol; the blocked isocyanate comprises one or a combination of two or more of aromatic isocyanate, aliphatic isocyanate and alicyclic isocyanate, preferably aromatic isocyanate, and more preferably blocked isocyanate is TDI.
The tertiary amine curing accelerator is selected from one or a combination of two or more of triethylamine, triethanolamine and benzyl dimethylamine.
The imidazole curing accelerator is an imidazole adduct, and is selected from one or a combination of two or more of flavor essence fine chemical PN-23, flavor essence fine chemical PN-23J, flavor essence fine chemical PN-31J and flavor essence fine chemical PN-40.
The inventor finds that the addition of the blocked isocyanate, tertiary amine and imidazole compound curing accelerator in the epoxy adhesive can reduce the curing temperature of the polythiol curing agent, shorten the curing time and improve the moisture and heat resistance of the adhesive, and supposedly, the blocked isocyanate can be quickly and low-temperature deblocked in the presence of the tertiary amine curing accelerator to release the phenol compound, and the phenol compound cooperates with the imidazole curing accelerator to further reduce the curing temperature and the curing time of the polythiol curing system. Among the plurality of blocking agent blocked isocyanate, the cardanol blocked isocyanate has long carbon chains, so that on one hand, the moisture and heat resistance of the epoxy adhesive can be improved, and on the other hand, the deblocking temperature can be reduced, and the low-temperature rapid curing can be achieved.
The number average molecular weight of the polythiol curing agent is 1000-1500.
The polythiol curing agent is prepared by a method comprising the following steps:
adding a diisocyanate silane compound and a catalyst into a reaction kettle filled with an organic solvent, heating and keeping the temperature, adding a phenyl dithiol compound, stirring until the mixture is uniform, reacting, and removing low pressure in vacuum after the reaction is finished to obtain the polythiol curing agent.
The organic solvent is selected from one or more of carbon tetrachloride, dimethylbenzene, dichloromethane, tetrahydrofuran, benzene, toluene, ethyl acetate, butyl acetate, dioxane, chloroform, DMSO and DMF; the catalyst is one or the combination of more than two of triethylamine, N, N, N ', N' -tetramethyl-1, 4-butanediamine and triethylenediamine; the dosage of the catalyst is 0.1-0.3wt% of the weight of the phenyl dithiol compound and the diisocyanate silane compound, the temperature is raised to 20-50 ℃, the reaction time is 1-5h, and the vacuum stripping condition is that the temperature is 120-160 ℃, the vacuum degree is 0.09-0.10MPa, and the time is 1-3h.
The epoxy resin is bisphenol type epoxy resin, comprising one or two of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the epoxy equivalent of the epoxy resin is 150-200g/mol.
The particle size of the filler is 3-10 μm, and the filler is not particularly limited, and is commonly used in the art, and at least one of reinforcing filler and toughening filler can be selected from one or a combination of two or more of fumed silica, calcium carbonate, talcum powder and diatomite.
The epoxy adhesive further comprises 1-5 parts of an auxiliary agent, wherein the auxiliary agent is not particularly limited, and can comprise one or a combination of two or more of a coupling agent, a defoaming agent and a stabilizer.
The coupling agent is epoxy silane coupling agent, and is specifically selected from at least one of 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl (dimethoxy) methylsilane, (3-glycidoxypropyl) dimethylethoxy silane, 5, 6-epoxyhexyl triethoxy silane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxy silane and the combination of two or more.
The defoamer is not particularly limited, and is commonly used in the art, and is selected from one or more of BYK 066N, BYK 1790, BYK A535, BYK-067, BYK-051 and BYK-077.
The stabilizer comprises one or a combination of two or more of barbituric acid, oxalic acid and tartaric acid.
A preparation method of a low-temperature fast-curing wet-heat-resistant epoxy adhesive comprises the following steps:
1) Adding blocked isocyanate into epoxy resin, heating and keeping constant temperature, stirring until the blocked isocyanate is uniformly mixed, and cooling to room temperature for standby;
2) Adding a polythiol curing agent, pigment and an auxiliary agent into the mixture obtained in the step 1), vacuumizing, stirring until the components are uniformly mixed, and releasing pressure for later use;
3) And (3) adding filler and curing accelerator into the mixture obtained in the step (2), vacuumizing, stirring until the mixture is uniformly mixed, decompressing and filling to obtain the epoxy adhesive.
The temperature is raised to 70-100 ℃ in the step 1), the vacuumizing vacuum degree is-0.1- (-0.25) MPa in the step 2), and the vacuumizing vacuum degree is-0.1- (-0.25) MPa in the step 3).
The invention also provides application of the low-temperature rapid-curing moisture-heat-resistant epoxy adhesive, wherein the epoxy adhesive is coated on the adhered surface, the thickness of an adhesive layer is 0.1-0.5mm, and curing is carried out under the conditions of 50-60 ℃ and 20-40 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the polythiol curing agent through the reaction of the phenyl dithiol compound and the diisocyanate silane compound, and the epoxy resin adhesive containing the polythiol curing agent, the curing accelerator and the blocked isocyanate has good moisture and heat resistance.
2. The epoxy adhesive prepared by the invention can be rapidly cured at 50-60 ℃ for 20-40min, and is suitable for bonding and sealing components sensitive to heat, such as speakers, mobile phone plate-changing glass and the like.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.
Cardanol blocked isocyanate Trixene BI 7774 is available from Lanxess chemical company,
phenol blocked isocyanate Desmodur AP stable is available from bayer chemistry,
epoxy bisphenol A epoxy resin EPIKOTE TM Resin 828EL, available from Hansen HEXION, USA, epoxy equivalent 185-192g/mol.
Preparation of polythiol curing agents
Preparation example 1
Adding 1mol of dimethyl silane diisocyanate and 0.67g of triethylamine into a reaction kettle filled with an organic solvent consisting of 4.5mol of DMSO and petroleum ether according to the volume ratio of 5:1, heating to 45 ℃ and keeping the temperature, adding 1.12mol of 1, 4-dimethyl benzene mercaptan, stirring until the mixture is uniform, reacting for 3.5h, and removing the gas at 120 ℃ and 0.10MPa for 1.5h after the reaction is finished, thus obtaining the polythiol curing agent. GPC: tetrahydrofuran, column temperature 40 ℃, number average molecular weight 1470.
Preparation example 2
The remainder was the same as in preparation example 1 except that 1, 6-hexamethylene diisocyanate was used in place of diisocyanato dimethylsilane. The number average molecular weight 1360.
Preparation of epoxy adhesive
Example 1
1) 4.5 parts of Trixene BI 7774 are added to 50 parts of bisphenol A epoxy resin EPIKOTE TM In Resin 828EL, heating to 90 ℃ and keeping constant temperature, stirring until the materials are uniformly mixed, and cooling to room temperature for standby;
2) Adding 35 parts of polythiol curing agent prepared in preparation example 1, 0.5 part of carbon black, 0.5 part of 3-glycidoxypropyl trimethoxysilane, 0.3 part of defoamer BYK 066N and 0.4 part of stabilizer barbituric acid into the mixture obtained in step 1), vacuumizing to-0.1 MPa, stirring until uniform mixing is achieved, and releasing pressure for later use;
3) Adding 25 parts of fumed silica and 10 parts of curing accelerator consisting of triethylamine and monosodium glutamate fine chemical PN-23 according to the weight ratio of 3:10 into the mixture obtained in the step 2), vacuumizing to 0.1MPa, stirring until the mixture is uniformly mixed, decompressing and filling to obtain the epoxy adhesive.
Example 2
The remainder was the same as in example 1, except that the polythiol curing agent used was prepared by preparation example 2.
Example 3
The remainder was the same as in example 1 except that the curing accelerator consisted of triethylamine and monosodium glutamate fine chemistry PN-23 in a weight ratio of 1:10.
Example 4
The remainder was the same as in example 1, except that the curing accelerator consisted of triethylamine and monosodium glutamate fine chemistry PN-23 in a weight ratio of 5:10.
Example 5
The remainder was the same as in example 1, except that Trixene BI 7774 was used in an amount of 3 parts.
Example 6
The remainder was the same as in example 1 except that the polythiol curing agent of preparation example 1 was used in an amount of 17 parts.
Example 7
The remainder was the same as in example 1, except that Trixene BI 7774 was replaced with Desmodur AP stable, i.e., phenol was used as the blocking agent for the blocked isocyanate.
Comparative example 1
The remainder is the same as example 1, except that Trixene BI 7774 is not used.
Comparative example 2
The rest was the same as in example 1 except that the curing accelerator was 10 parts of triethylamine.
Application example
The epoxy adhesives prepared in the above examples and comparative examples were dispensed on PC8600 shear slices with a pneumatic dispenser, the thickness of the adhesive layer was controlled to 0.1mm, and cured at 55deg.C for 30min.
The epoxy adhesives prepared in the above application examples and comparative application examples were subjected to the following performance tests:
shear strength: the bonded substrate was tested for shear strength at room temperature by reference to standard ASTM D1002, PC8600 chips.
Humid heat aging: aging is performed in a constant temperature and humidity cabinet at 60 ℃/90% RH/500h, with specific reference to standard GB/T2423.3-2016.
Curing time: isothermal DSC test, N for shielding gas and purge gas 2 And (3) performing constant-temperature curing for different time periods by taking 55 ℃ as a curing temperature to obtain curing time. In the exothermic-time spectrum of DSC, the occurrence of a curing peak indicates that the epoxy system has started to open and undergo a curing crosslinking reaction. In the curing peak, the peak-out temperature is the temperature at which the system starts curing, the peak-junction temperature is the temperature at which the curing reaction is finished, and the time from the peak-out to the peak-end is the time required for curing.
TABLE 1
As can be seen from the above table, the epoxy resin adhesive containing the curing accelerator and blocked isocyanate prepared by compounding the polythiol curing agent, the tertiary amine curing accelerator and the imidazole curing accelerator prepared by the reaction of the phenyl dithiol compound and the diisocyanate silane compound has good wet heat resistance. The test results of examples 1 and 7, comparative examples 1 and 2 illustrate: the tertiary amine curing accelerator is favorable for quick and low-temperature deblocking of blocked isocyanate to release phenol compounds, and cardanol released by deblocking of cardanol blocked isocyanate has the effect of reducing the curing time of a polythiol curing system by cooperating with the imidazole curing accelerator, so that the curing accelerator system formed by phenol and the imidazole curing accelerator has a slightly poorer effect and longer curing time.
The epoxy adhesive prepared by the invention can be rapidly cured at 50-60 ℃ for 20-40min, and is suitable for bonding and sealing components sensitive to heat, such as speakers, mobile phone plate-changing glass and the like.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (12)
1. The low-temperature quick-curing wet-heat-resistant epoxy adhesive is characterized by comprising the following raw materials in parts by weight: 30-50 parts of epoxy resin, 3.0-4.5 parts of blocked isocyanate, 17-35 parts of polythiol curing agent, 5-10 parts of curing accelerator, 10-25 parts of filler and 0.5-1 part of pigment; the polythiol curing agent is prepared by reacting phenyl dithiol compounds with diisocyanate silane compounds, and the curing accelerator is prepared by compounding tertiary amine curing accelerators and imidazole curing accelerators according to the weight ratio of 1-3:10.
2. The low temperature rapid curing moisture and heat resistant epoxy adhesive of claim 1, wherein the phenyl dithiol compound is selected from one or more of 1, 4-xylylene glycol, 1, 3-xylylene glycol, 1, 2-xylylene glycol-4, 5-dimethyl, 1, 2-xylylene glycol-3, 6-dimethyl, 1, 4-xylylene glycol-2, 5-dimethyl; the diisocyanate silane compound is selected from one or a combination of two or more of diisocyanate dimethyl silane, diisocyanate dibutyl silane, 1, 3-tetraethyl-1, 3-bis (isocyanatomethyl) disiloxane and 1, 3-tetramethyl-1, 3-bis (isocyanatomethyl) disiloxane.
3. The low-temperature rapid-curing wet-heat-resistant epoxy adhesive according to claim 1, wherein the blocking agent of the blocked isocyanate is a phenol compound selected from one or a combination of two or more of phenol, cardanol, resorcinol and m-cresol; the blocked isocyanate type comprises one or two or more of aromatic isocyanate, aliphatic isocyanate and alicyclic isocyanate.
4. A low temperature fast cure moisture and heat resistant epoxy adhesive according to claim 3 wherein the blocked isocyanate blocking agent is cardanol and the blocked isocyanate is TDI.
5. The low-temperature rapid-curing wet-heat-resistant epoxy adhesive according to claim 1, wherein the tertiary amine curing accelerator is one or a combination of two or more selected from triethylamine, triethanolamine and benzyl dimethylamine;
the imidazole curing accelerator is an imidazole adduct, and is selected from one or a combination of two or more of flavor essence fine chemical PN-23, flavor essence fine chemical PN-23J, flavor essence fine chemical PN-31J and flavor essence fine chemical PN-40.
6. The low temperature fast cure moisture and heat resistant epoxy adhesive of claim 1 wherein said polythiol curing agent has a number average molecular weight of 1000 to 1500 g/mol.
7. The low temperature fast cure moisture and heat resistant epoxy adhesive of claim 1, wherein the polythiol curing agent is prepared by a method comprising the steps of:
adding a diisocyanate silane compound and a catalyst into a reaction kettle filled with an organic solvent, heating and keeping the temperature, adding a phenyl dithiol compound, stirring until the mixture is uniform, reacting, and removing low pressure in vacuum after the reaction is finished to obtain the polythiol curing agent.
8. The low temperature rapid curing moisture and heat resistant epoxy adhesive of claim 7, wherein the catalyst is one or a combination of two or more of triethylamine, N, N, N ', N' -tetramethyl-1, 4-butanediamine and triethylenediamine; the dosage of the catalyst is 0.1-0.3wt% of the weight of the phenyl dithiol compound and the diisocyanate silane compound, the temperature is raised to 20-50 ℃, and the reaction time is 1-5h.
9. The low temperature rapid curing moisture and heat resistant epoxy adhesive of claim 1, wherein the epoxy resin is bisphenol type epoxy resin, comprising one or two of bisphenol a type epoxy resin and bisphenol F type epoxy resin, and the epoxy resin has an epoxy equivalent of 150-200g/mol.
10. The method for preparing the low-temperature rapid-curing moisture-heat-resistant epoxy adhesive according to any one of claims 1 to 9, comprising the following steps:
adding blocked isocyanate into epoxy resin, heating and keeping constant temperature, stirring until the blocked isocyanate is uniformly mixed, and cooling to room temperature for standby;
adding a polythiol curing agent, pigment and an auxiliary agent into the mixture obtained in the step 1), vacuumizing, stirring until the components are uniformly mixed, and releasing pressure for later use;
and (3) adding filler and curing accelerator into the mixture obtained in the step (2), vacuumizing, stirring until the mixture is uniformly mixed, decompressing and filling to obtain the epoxy adhesive.
11. The method of claim 10, wherein the temperature rise in step 1) is raised to 70-100 ℃, the vacuum degree in step 2) is-0.1 MPa, and the vacuum degree in step 3) is-0.1 MPa.
12. The use of the low temperature fast curing moisture and heat resistant epoxy adhesive of any one of claims 1 to 9, wherein the epoxy adhesive is coated on the surface to be bonded, the thickness of the adhesive layer is 0.1 to 0.5mm, and the curing is carried out under the conditions of 50 to 60 ℃ and 20 to 40 min.
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| KR101991797B1 (en) * | 2016-10-17 | 2019-06-25 | 한국생산기술연구원 | One-pack type epoxy adhesive composition with curing agent of polythiol copolymer and curing catalyst of core-shell |
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