Full-temperature-range MS epoxy hybrid sealant and preparation method thereof

Abstract

The invention provides a full-temperature-range MS epoxy hybrid sealant and a preparation method thereof.The full-temperature-range MS epoxy hybrid sealant comprises a component A and a component B. The component A comprises a silane modified polyether polymer, an antioxidant, a first filler, a silane coupling agent and an epoxy curing agent, the silane modified polyether polymer comprises a 3-isocyanate propyl trimethoxy silane terminated polyether polymer, the first filler comprises hydrophobic fumed silica, the silane coupling agent comprises a secondary amino silane coupling agent, and the epoxy curing agent comprises a phenolic aldehyde amine curing agent; the component B comprises epoxy resin, a second filler, an accelerant and a catalyst, and the second filler comprises silica powder. The aging resistance and the elastic adhesive property of the adhesive can adapt to various severe environments such as long-term damp and heat resistance, high and low temperature impact resistance and water resistance and the requirement for high bonding strength, and the adhesive can be used for bonding and sealing in the manufacturing process of a new energy battery box.

Description

Technical Field

[0001] The present invention belongs to the technical field of sealants, and in particular relates to a full-temperature range MS epoxy hybrid sealant and a preparation method thereof. Background Art

[0002] MS epoxy hybrid sealant with a full temperature range is widely used in sealing building curtain wall joints, bonding body structures in automobile manufacturing, waterproofing electronic equipment, bonding insulation layers of cold chain logistics equipment, protecting precision aerospace components, and treating expansion joints in outdoor projects such as bridges and tunnels due to its excellent high and low temperature resistance (typically covering -40°C to 80°C), strong adhesion, anti-aging and chemical corrosion resistance. It is especially suitable for sealing power battery packs in the new energy field, solving thermal runaway and temperature cycle fatigue, and aging resistance application scenarios. It combines fast curing and environmental protection, making it the preferred material for high-performance sealing in complex working conditions.

[0003] However, analysis and testing have shown that the current full-temperature range MS epoxy hybrid sealant still has some performance defects. For example, after long-term wet-heat aging, high-temperature aging, and water aging tests, the hybrid sealant's body strength gradually decays, the elongation at break decreases significantly, and even some failure phenomena occur at the bonding interface, which will affect the service life and safety performance of the full-temperature range MS epoxy hybrid sealant during application. Summary of the Invention

[0004] In view of this, the present invention provides a full-temperature range MS epoxy hybrid sealant and a preparation method thereof. The aging resistance and elastic bonding properties can adapt to various harsh environments such as long-term resistance to moisture and heat, resistance to high and low temperature impact, and water resistance, as well as the requirements of high bonding strength, and can be used for bonding and sealing in the manufacturing process of new energy battery boxes.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: In the first aspect, the present invention provides a full-temperature range MS epoxy hybrid sealant, comprising component A and component B, component A comprising a silane-modified polyether polymer, an antioxidant, a first filler, a silane coupling agent and an epoxy curing agent, wherein the silane-modified polyether polymer comprises a 3-isocyanatepropyltrimethoxysilane-terminated polyether polymer, the first filler comprises hydrophobic fumed silica, the silane coupling agent comprises a secondary aminosilane coupling agent, and the epoxy curing agent comprises a phenolic amine curing agent; component B comprises an epoxy resin, a second filler, a accelerator and a catalyst, wherein the second filler comprises silicon micropowder.

[0006] Preferably, the component A comprises, by mass: 70-80 parts of silane-modified polyether polymer, 0.5-2 parts of antioxidant, 5-20 parts of first filler, 2-6 parts of silane coupling agent, and 5-15 parts of epoxy curing agent; The component B comprises, by mass, 70-90 parts of epoxy resin, 5-25 parts of second filler, 2-4 parts of accelerator, and 1-3 parts of catalyst.

[0007] Preferably, the volume ratio of the component A to the component B is (1-2):1.

[0008] Preferably, the viscosity of the 3-isocyanatepropyltrimethoxysilane terminated polyether polymer is 5000-20000 mPa·s; and / or, The specific surface area of ​​the hydrophobic fumed silica is 150-200 m 2 / g; and / or, The secondary aminosilane coupling agent includes at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-cyclohexylamino)propyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine and N-(n-butyl)-3-aminopropyltriethoxysilane; and / or, The amine value of the phenalkamine curing agent is 340-380 mg KOH / g; and / or, The particle size of the silicon micropowder is 2000-2500 mesh.

[0009] Preferably, the antioxidant comprises a hindered phenol antioxidant.

[0010] Preferably, the hindered phenol antioxidant includes triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

[0011] Preferably, the epoxy resin comprises bisphenol A type resin; and / or, The accelerator includes deionized water.

[0012] Preferably, the catalyst comprises an organotin catalyst.

[0013] Preferably, the organotin catalyst includes 1,3-dilauroyloxy-1,1,3,3-tetrabutylditinoxy.

[0014] In a second aspect, the present invention further provides a method for preparing the full-temperature range MS epoxy hybrid sealant, comprising the following steps: S1, mixing and dispersing the silane-modified polyether polymer, the antioxidant and the first filler, and then adding the silane coupling agent and the epoxy curing agent and mixing and dispersing them to obtain component A; S2. Mix and disperse the epoxy resin and the second filler, then add the accelerator and the catalyst and mix and disperse them to obtain component B.

[0015] Compared with the prior art, the present invention has the following beneficial effects: (1) In the present invention, in terms of resin, by combining 3-isocyanate propyl trimethoxysilane end-capped polyether polymer with epoxy resin, the advantages of flexible polyether structure and rigid benzene ring structure are combined, which is conducive to obtaining a sealant with good low-temperature toughness and high-temperature strength, and can maintain stable mechanical strength and elastic modulus in low-temperature (-60°C) and high-temperature (120°C) environments; the unique NCO structure in the 3-isocyanate propyl trimethoxysilane modified polyether polymer can effectively catalyze the hydrolysis and cross-linking reaction speed of alkoxy groups; in terms of silane coupling agent, by using secondary amino silane coupling agent, the secondary amino structure containing an active hydrogen can form a chemical bond with the epoxy group, which can improve the cohesive strength of the resin structure; in terms of filler, by filling with hydrophobic fumed silica, the sealant is given higher resistance to Water performance, through the untreated silicon micropowder to provide suitable interface thermal resistance, can effectively transfer and release the heat erosion of the sealant during the heat resistance process; in terms of epoxy curing agent, by using phenolic amine curing agent, the curing reaction speed can be effectively adjusted and controlled; the phenolic skeleton in the system can improve the heat resistance of the cured product, promote the reaction activity of the curing agent, and reduce the curing reaction temperature with the epoxy resin; at the same time, the composite structure of primary amino group, secondary amino group and phenolic hydroxyl group in the system can effectively form an excellent bonding type with the substrate, on the one hand, it can improve the cross-linking degree of epoxy at room temperature, effectively reduce the post-curing problem of the epoxy system, and on the other hand, it can improve the adhesion to a variety of materials; thereby improving the mechanical properties and aging resistance of the full-temperature range MS epoxy hybrid sealant, so that the full-temperature range MS epoxy hybrid sealant has excellent performance.

[0016] (2) The preparation process of the full-temperature range MS epoxy hybrid sealant provided by the present invention is simple and has high production efficiency; the mixing ratio compatibility is high, and the volume ratio of component A to component B can meet (1~2):1, which can meet high mechanical properties; it does not require treatment and has good bonding ability to a variety of metals, composite materials, coatings, etc.; it has high mechanical properties and aging resistance, can effectively resist the deformation of the material caused by temperature shock, and provide a stable bonding and sealing effect; it has the characteristics of high strength and high elongation at break, especially outstanding aging properties such as resistance to moisture and heat, resistance to high and low temperature shock, and resistance to water. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a test chart of the glass transition temperature of the full-temperature range MS epoxy hybrid sealant provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] The present invention will be further described in detail below with reference to specific embodiments so that those skilled in the art can understand the present invention more clearly.

[0019] In the first aspect, the present invention provides a full-temperature range MS epoxy hybrid sealant, comprising component A and component B, component A comprising a silane-modified polyether polymer, an antioxidant, a first filler, a silane coupling agent and an epoxy curing agent, wherein the silane-modified polyether polymer comprises a 3-isocyanatepropyltrimethoxysilane-terminated polyether polymer, the first filler comprises hydrophobic fumed silica, the silane coupling agent comprises a secondary aminosilane coupling agent, and the epoxy curing agent comprises a phenolic amine curing agent; component B comprises an epoxy resin, a second filler, a accelerator and a catalyst, wherein the second filler comprises silicon micropowder.

[0020] In the present invention, in terms of resin, by combining 3-isocyanate propyltrimethoxysilane end-capped polyether polymer with epoxy resin, the advantages of flexible polyether structure and rigid benzene ring structure are combined, which is conducive to obtaining a sealant with good low-temperature toughness and high-temperature strength, and can maintain stable mechanical strength and elastic modulus in low-temperature (-60°C) and high-temperature (120°C) environments; the unique NCO structure in the 3-isocyanate propyltrimethoxysilane modified polyether polymer can effectively catalyze the hydrolysis and cross-linking reaction speed of alkoxy groups; in terms of silane coupling agent, by using a secondary aminosilane coupling agent, the secondary amino structure containing an active hydrogen can form a chemical bond with the epoxy group, which can improve the cohesive strength of the resin structure; in terms of filler, by filling with hydrophobic fumed silica, the sealant is endowed with The sealant is given higher water resistance, and the unsurface-treated silicon micropowder provides suitable interfacial thermal resistance, which can effectively transfer and release the heat erosion of the sealant during the heat-resistant process; in terms of epoxy curing agent, the curing reaction speed can be effectively adjusted and controlled by using phenolic amine curing agent; the phenolic skeleton in the system can improve the heat resistance of the cured product, promote the reaction activity of the curing agent, and reduce the curing reaction temperature with the epoxy resin; at the same time, the composite structure of primary amino group, secondary amino group and phenolic hydroxyl group in the system can effectively form an excellent bonding type with the substrate, on the one hand, it can improve the cross-linking degree of epoxy at room temperature, effectively reduce the post-curing problem of the epoxy system, and on the other hand, it can improve the adhesion to a variety of materials; thereby improving the mechanical properties and aging resistance of MS epoxy hybrid sealant in the full temperature range.

[0021] It should be noted that the structural formula of the 3-isocyanate propyltrimethoxysilane terminated polyether polymer is as follows: The phenolic amine curing agent is specifically formed by the Mannich condensation reaction of phenol, formaldehyde and fatty amine to form a phenolic amine main chain, and the molecule contains active amino groups (-NH-) and phenolic hydroxyl groups (-OH); the silicon micropowder is not surface treated; the A component may also include a first colorant, and the B component may also include a second colorant, and the colors of the first colorant and the second colorant may be different.

[0022] Furthermore, the component A comprises, by mass, 70-80 parts of a silane-modified polyether polymer, 0.5-2 parts of an antioxidant, 5-20 parts of a first filler, 2-6 parts of a silane coupling agent, and 5-15 parts of an epoxy curing agent; The component B comprises, by mass, 70-90 parts of epoxy resin, 5-25 parts of second filler, 2-4 parts of accelerator, and 1-3 parts of catalyst.

[0023] It should be noted that the proportion of the silane-modified polyether polymer in component A can be 70 parts, 72 parts, 75 parts, 78 parts or 80 parts, but not limited thereto; the proportion of the antioxidant in component A can be 0.5 parts, 1 parts, 1.5 parts or 2 parts, but not limited thereto; the proportion of the first filler in component A can be 5 parts, 8 parts, 10 parts, 12 parts or 15 parts, but not limited thereto; the proportion of the silane coupling agent in component A can be 2 parts, 3 parts, 4 parts, 5 parts or 6 parts, but not limited thereto; the proportion of the epoxy curing agent in component A can be 10 parts, 11 parts, 12 parts or 15 parts, but not limited thereto. 12 parts, 14 parts or 15 parts, but not limited to this; the number of epoxy resins in component B can be 70 parts, 75 parts, 80 parts, 85 parts or 90 parts, but not limited to this; the number of second fillers in component B can be 5 parts, 8 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts or 25 parts, but not limited to this; the number of accelerators in component B can be 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, but not limited to this; the number of catalysts in component B can be 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, but not limited to this.

[0024] Furthermore, the volume ratio of the component A to the component B is (1-2): 1. The mixing ratio of the component A and the component B is highly compatible and can both meet high mechanical properties.

[0025] Furthermore, the viscosity of the 3-isocyanate propyltrimethoxysilane-terminated polyether polymer is 5,000 to 20,000 mPa·s. It should be noted that the 3-isocyanate propyltrimethoxysilane-terminated polyether polymer can be selected from at least one of Wacker Chemie E925, Wacker Chemie LM925, and Wacker Chemie E905.

[0026] Furthermore, the specific surface area of ​​the hydrophobic fumed silica is 150-200 m 2 / g.

[0027] Furthermore, the secondary aminosilane coupling agent includes at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-cyclohexylamino)propyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, and N-(n-butyl)-3-aminopropyltriethoxysilane. It should be noted that the secondary aminosilane coupling agent can be selected from at least one of Momentive Y-9669, Dow Corning SZ-6083, Shin-Etsu KBM-573, Noble New Materials SCA-A69M, and Silicon Science New Materials SICO-A118.

[0028] Furthermore, the amine value of the phenalkamine curing agent is 340-380 mg KOH / g. It should be noted that the phenalkamine curing agent can be selected from Ancamine 2636 of Evonik Chemicals.

[0029] Furthermore, the particle size of the silicon micropowder is 2000-2500 mesh.

[0030] Furthermore, the antioxidant includes a hindered phenol antioxidant.

[0031] Furthermore, the hindered phenol antioxidant includes triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

[0032] Furthermore, the epoxy resin includes bisphenol A type resin. It should be noted that the bisphenol A type resin can be selected from at least one of E-44 and E-51.

[0033] The accelerator includes deionized water.

[0034] Furthermore, the catalyst includes an organotin catalyst.

[0035] Furthermore, the organotin catalyst includes 1,3-dilauroyloxy-1,1,3,3-tetrabutylditinoxy.

[0036] In a second aspect, the present invention further provides a method for preparing the full-temperature range MS epoxy hybrid sealant, comprising the following steps: S1, mixing and dispersing the silane-modified polyether polymer, the antioxidant and the first filler, and then adding the silane coupling agent and the epoxy curing agent and mixing and dispersing them to obtain component A; S2. Mix and disperse the epoxy resin and the second filler, then add the accelerator and the catalyst and mix and disperse them to obtain component B.

[0037] For step S1, specifically, the silane-modified polyether polymer, the antioxidant and the first filler are first stirred under vacuum conditions, and then the silane coupling agent and the epoxy curing agent are added and stirred under vacuum conditions to obtain component A; it should be noted that the vacuum degree of the vacuum conditions for the two stirrings can be -0.090 MPa, the frequency of the first stirring can be 40 Hz, the time of the first stirring can be 30 min, the frequency of the second stirring can be 20 Hz, the time of the second stirring can be 20 min, and when component A also includes a first colorant, the first colorant can be added before the first stirring.

[0038] For step S2, specifically, the epoxy resin and the second filler are first stirred under vacuum conditions, and then the accelerator and the catalyst are added and stirred under vacuum conditions to obtain component B; it should be noted that the vacuum degree of the vacuum conditions for the two stirrings can be -0.090 MPa, the frequency of the first stirring can be 40 Hz, the time of the first stirring can be 30 min, the frequency of the second stirring can be 20 Hz, and the time of the second stirring can be 20 min. When component B also includes a second colorant, the second colorant can be added before the first stirring.

[0039] It can be understood that there is no order restriction for step S1 and step S2.

[0040] The raw materials used in the following examples were obtained from the following sources: 3-isocyanatepropyltrimethoxysilane-terminated polyether polymers E925, LM925, and E905 were purchased from Wacker Chemicals (China); the secondary aminosilane coupling agent can be selected from Momentive Y-9669, Dow Corning SZ-6083, Shin-Etsu KBM-573, Noble New Materials SCA-A69M, and Silicon Science New Materials SICO-A118; the epoxy curing agent is Ancamine 2636 from Evonik Chemicals; the epoxy resins E-44 and E-51 are purchased from Changchun Chemical Industry Group Corporation; and the organotin catalyst is purchased from Tokyo Chemical Industry Co., Ltd. All other raw materials are common commercially available and can be purchased through conventional purchasing channels.

[0041] Example 1 A full-temperature range MS epoxy hybrid sealant, the raw material composition of which is as follows: Component A: 700g 3-isocyanate propyltrimethoxysilane end-capped polyether polymer E925 (silane-modified polyether polymer), 2g medium chrome yellow powder (yellow colorant), 10g antioxidant 245 (antioxidant), 150g specific surface area of ​​150m 2 / g hydrophobic fumed silica (first filler), 40g secondary aminosilane coupling agent Y-9669 (silane coupling agent), 100g curing agent Ancamine 2636 (curing agent); Component B: 700g epoxy resin E51 (epoxy resin), 250g 2500 mesh silica powder (secondary filler), 2g phthalocyanine blue powder (blue colorant), 20g deionized water (accelerator), 30g organotin C-12 (catalyst); The preparation method is as follows: Component A: A silane-modified polyether polymer, an antioxidant, a first filler, and a yellow colorant were stirred (stirring frequency: 40 Hz) under vacuum conditions (vacuum degree: -0.090 MPa) for 30 minutes, and then a silane coupling agent and a curing agent were added and stirred (stirring frequency: 20 Hz) under vacuum conditions (vacuum degree: -0.090 MPa) for 20 minutes to obtain component A. Component B: The epoxy resin, the second filler and the blue colorant were stirred (stirring frequency was 40 Hz) under vacuum conditions (vacuum degree was -0.090 MPa) for 30 min, and then the accelerator and the catalyst were added and stirred (stirring frequency was 20 Hz) under vacuum conditions (vacuum degree was -0.090 MPa) for 20 min to obtain component B.

[0042] The structural formula of secondary aminosilane coupling agent Y-9669 is as follows: .

[0043] Example 2 A full-temperature range MS epoxy hybrid sealant, referring to Example 1, differs in that: Component A: 750g 3-isocyanate propyltrimethoxysilane end-capped polyether polymer E925 (silane-modified polyether polymer), 2g medium chrome yellow powder (yellow colorant), 5g antioxidant 245 (antioxidant), 105g specific surface area of ​​170m 2 / g hydrophobic fumed silica (first filler), 30g secondary aminosilane coupling agent SCA-A69M (silane coupling agent), 110g curing agent Ancamine 2636 (curing agent); Component B: 800g epoxy resin E51 (epoxy resin), 150g 2000 mesh silica powder (second filler), 2g phthalocyanine blue powder (blue colorant), 30g deionized water (accelerator), 20g chelated tin U-130 (catalyst).

[0044] Example 3 A full-temperature range MS epoxy hybrid sealant, referring to Example 1, differs in that: Component A: 400g 3-isocyanate propyltrimethoxysilane end-capped polyether polymer E925 (silane-modified polyether polymer), 400g 3-isocyanate propyltrimethoxysilane end-capped polyether polymer E905 (silane-modified polyether polymer), 2g medium chrome yellow powder (yellow colorant), 20g antioxidant 245 (antioxidant), 50g specific surface area of ​​200m 2 / g hydrophobic fumed silica (first filler), 20g secondary aminosilane coupling agent SICO-A118 (silane coupling agent), 120g curing agent Ancamine 2636 (curing agent); Component B: 900g epoxy resin E44 (epoxy resin), 50g 2000 mesh silica powder (second filler), 2g phthalocyanine blue powder (blue colorant), 40g deionized water (accelerator), 10g chelated tin U-220H (catalyst).

[0045] Comparative Example 1 A full-temperature range MS epoxy hybrid sealant is described with reference to Example 1, except that the silane-modified polyether polymer is a 3-isocyanatepropylmethyldimethoxysilane-terminated polyether polymer.

[0046] The structural formula of 3-isocyanatepropylmethyldimethoxysilane terminated polyether polymer is as follows: .

[0047] Comparative Example 2 A full-temperature range MS epoxy hybrid sealant is described with reference to Example 1, except that: in component A, the first filler is hydrophilic fumed silica with a high specific surface area, and in component B, the second filler is nano-calcium carbonate.

[0048] Comparative Example 3 A full-temperature range MS epoxy hybrid sealant is described with reference to Example 1, except that the curing agent is 2,4,6-tris(dimethylaminomethyl)phenol (curing agent DMP-30).

[0049] Comparative Example 4 A full-temperature range MS epoxy hybrid sealant is described with reference to Example 1, except that the silane coupling agent is a primary aminosilane coupling agent Momentive A-1110.

[0050] The structural formula of primary aminosilane coupling agent Momentive A-1110 is as follows: .

[0051] Performance testing and results The components A and B obtained in Example 1 were mixed in a volume ratio of 2:1 to form a film with a thickness of 2 mm ± 0.5 mm. No air bubbles were allowed to form the film. After being placed in a standard environment (atmospheric pressure of 101.325 kPa, temperature of 25 ± 2 ° C, humidity of 50 ± 5% RH) for 7 days, 4 mm ± 0.5 mm cubes were cut out with a special cutter and the glass transition temperature was tested. The results are shown in Table 1. Figure 1 The specific steps of the glass transition temperature test are as follows: accurately measure the length, width and thickness of the cut tensile specimens, determine the measurement temperature range to be -90℃~160℃, the heating rate to be 1K / min, and the test frequency to be 33.333Hz. After the test is completed, mark the glass transition temperature according to the curve.

[0052] Component A and component B obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were extruded and mixed uniformly in a volume ratio of 2:1 using a glue gun to degas. A 2 mm thick glue layer was formed on a polytetrafluoroethylene plate. No bubbles were allowed to remain in the glue. After being placed in a standard environment (atmospheric pressure of 101.325 kPa, temperature of 25±2°C, humidity of 50±5%RH) for 7 days, various properties were tested. The test results are shown in Table 1.

[0053] Tensile strength and elongation at break test method: Refer to the method specified in GB / T 528-2009 "Vulcanized rubber or thermoplastic rubber - Determination of tensile stress-strain properties", select dumbbell I-type sheet, and use a tensile speed of 100 mm / min to test the tensile strength and elongation at break of the cured product.

[0054] Shear strength test method: Referring to the method specified in GB / T 7124-2008 "Determination of tensile shear strength of adhesives", component A and component B obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were extruded and mixed uniformly in a volume ratio of 2:1 using a glue gun to form shear specimens of epoxy coating substrates. The thickness of the adhesive layer was 0.5 mm ± 0.05. After being placed in a standard environment (atmospheric pressure of 101.325 kPa, temperature of 25 ± 2°C, humidity of 50 ± 5% RH) for 7 days, the shear strength was tested at a tensile speed of 5 mm / min.

[0055] Aging test method: After curing for 7 days, place the samples in a double 85 high temperature and high humidity test chamber and a -40℃~100℃ high and low temperature alternating cycle test chamber for 1000 hours, then take them out and place them in a standard environment with constant temperature for 24 hours. Then test the tensile strength, elongation at break and shear strength after double 85 aging for 1000 hours and high and low temperature impact for 1000 hours.

[0056] Different temperature test method: Place the above samples after curing for 7 days in a constant temperature test chamber at -30℃ and 55℃ for 2 hours, and test the tensile strength, elongation at break and shear strength in different temperature environments.

[0057] Table 1 Performance test results of epoxy hybrid sealants in the full temperature range of various examples and comparative examples

[0058] Conclusion: From Figure 1 It can be seen that the full-temperature range MS epoxy hybrid sealant prepared in the embodiment of the present invention has two Tg temperatures, namely -60°C and 120°C, when subjected to glass transition temperature testing. Therefore, it can maintain stable mechanical strength and elastic modulus in low temperature (-60°C) and high temperature (120°C) environments. As can be seen from Table 1, the full-temperature range MS epoxy hybrid sealant prepared in the embodiment of the present invention exhibits high bonding strength and failure mode, excellent tensile strength and elongation at break, and excellent mechanical property retention in low and high temperature environments, and excellent mechanical property retention after aging in double 85 high temperature and high humidity and high and low temperature alternating environments; It can be seen from Example 1 and Comparative Example 1 that when the 3-isocyanatepropyltrimethoxysilane-terminated polyether polymer with a trimethoxy structure in component A is replaced with a 3-isocyanatepropylmethyldimethoxysilane-terminated polyether polymer with a methyldimethoxy structure, the mechanical strength is significantly reduced, which is mainly due to the change in structural strength caused by the reaction speed and cross-linking sites; It can be seen from Example 1 and Comparative Example 2 that when hydrophilic fumed silica is used as the main filler and calcium carbonate is used as the auxiliary filler in the system, the mechanical strength of the product is improved, mainly because the large number of hydroxyl groups on the surface of the hydrophilic fumed silica adds more active hydroxyl groups to the system; however, it can be seen that after the product is aged at double 85 degrees of high temperature and high humidity, the shear strength decreases significantly, mainly because the excessive number of hydrophilic groups causes the hydrophobicity of the system to deteriorate, and the internal adhesive layer is severely eroded, resulting in strength loss and debonding. At the same time, after being subjected to high and low temperature shock, since the thermal conductivity of calcium carbonate is lower than that of silicon powder, the heat concentrates on the adhesive layer and increases the intensity, resulting in a significant attenuation of the elongation at break after high and low temperature alternating aging; As can be seen from Example 1 and Comparative Example 3, when using tertiary amine curing agents, since tertiary amine curing agents do not contain active hydrogen, they rely solely on phenolic hydroxyl groups to increase the reactivity of the curing agent, initiating the self-ring-opening curing of the epoxy resin, resulting in a higher elongation under room temperature curing conditions. However, due to the water-containing nature of the system, the degree of reaction between the epoxy and tertiary amine curing agents is restricted, resulting in certain post-curing problems. Therefore, after double 85 and high and low temperature alternating aging, the elongation is severely attenuated, and the bulk strength increases further after curing. The adhesion failure form to epoxy coating materials is very poor, mainly because the tertiary amine curing agents do not contain primary and secondary amino groups and cannot react with the hydroxyl and epoxy groups in the epoxy coating on the substrate surface to form chemical bonds, resulting in poor adhesion to epoxy coating materials. Phenolic amine curing agents contain multiple active reactive groups such as primary amino groups, swollen amino groups, and phenolic hydroxyl groups, and therefore have the best adhesion to epoxy coating materials. However, due to the small number of phenolic hydroxyl groups and the aqueous environment, when used alone, the high rigidity strength of the epoxy component cannot be effectively released, resulting in mechanical properties of medium strength and high toughness. It can be seen from Example 1 and Comparative Example 4 that when primary aminosilane is used, the strength of the product decreases to a certain extent. This is because the product system is an aqueous solvent environment. The -NH2 of the primary amine may be more easily solvated because there are two H groups that can form hydrogen bonds, while the secondary amine has only one H group and may have a lower degree of solvation. Because of less solvation, there are more free amines, so the nucleophilicity of the secondary amine may be stronger in the actual reaction; at the same time, the primary amino group is more likely to compete with water (NH2 + H2O → NH3·H2O), resulting in the consumption of some amino groups. The secondary amino group is more hydrophobic and is more likely to migrate to the epoxy resin interface in an aqueous environment, resulting in a higher measured interfacial binding energy; In summary, the full-temperature range MS epoxy hybrid sealant of the present invention adopts 3-isocyanate propyltrimethoxysilane-terminated polyether polymer, epoxy resin, hydrophobic fumed silica and thermal interface filler silicon powder, as well as a combination of secondary amine silane coupling agent and phenolic amine curing agent. It can prepare high-performance full-temperature range MS epoxy hybrid sealant under simple preparation process conditions. It has high mechanical strength at room temperature and critical performance in low and high temperature environments, as well as high performance retention rate after long-term aging under double 85 high temperature and high humidity and high and low temperature alternation. It can meet the bonding requirements of various substrates and maintain 100% cohesive bonding failure mode in various environments. It can be used in the full temperature range.

[0059] The raw materials not specifically described in the present invention are all existing materials that can be directly purchased from the market.

[0060] The above is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A full-temperature range MS epoxy hybrid sealant, characterized in that: include: Component A comprises a silane-modified polyether polymer, an antioxidant, a first filler, a silane coupling agent, and an epoxy curing agent, wherein the silane-modified polyether polymer comprises a 3-isocyanatepropyltrimethoxysilane-terminated polyether polymer, the first filler comprises hydrophobic fumed silica, the silane coupling agent comprises a secondary aminosilane coupling agent, and the epoxy curing agent comprises a phenalkamine curing agent; and Component B includes epoxy resin, a second filler, a accelerator and a catalyst, wherein the second filler includes silicon powder.

2. The full-temperature range MS epoxy hybrid sealant according to claim 1, characterized in that: The component A comprises, by mass, 70-80 parts of a silane-modified polyether polymer, 0.5-2 parts of an antioxidant, 5-20 parts of a first filler, 2-6 parts of a silane coupling agent, and 5-15 parts of an epoxy curing agent; The component B comprises, by mass, 70-90 parts of epoxy resin, 5-25 parts of second filler, 2-4 parts of accelerator, and 1-3 parts of catalyst.

3. The full-temperature range MS epoxy hybrid sealant according to claim 2, characterized in that: The volume ratio of the component A to the component B is (1~2):

1.

4. The full-temperature range MS epoxy hybrid sealant according to claim 1, characterized in that: The viscosity of the 3-isocyanatepropyltrimethoxysilane terminated polyether polymer is 5000-20000 mPa·s; and / or, The specific surface area of ​​the hydrophobic fumed silica is 150-200 m 2 / g; and / or, The secondary aminosilane coupling agent includes at least one of N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-cyclohexylamino)propyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine and N-(n-butyl)-3-aminopropyltriethoxysilane; and / or, The amine value of the phenalkamine curing agent is 340-380 mg KOH / g; and / or, The particle size of the silicon micropowder is 2000-2500 mesh.

5. The full-temperature range MS epoxy hybrid sealant according to claim 1, characterized in that: The antioxidant includes a hindered phenol antioxidant.

6. The full-temperature range MS epoxy hybrid sealant according to claim 5, characterized in that: The hindered phenol antioxidant includes triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

7. The full-temperature range MS epoxy hybrid sealant according to claim 1, characterized in that: The epoxy resin includes bisphenol A type resin; and / or, The accelerator includes deionized water.

8. The full-temperature range MS epoxy hybrid sealant according to claim 1, characterized in that: The catalyst includes an organotin catalyst.

9. The full-temperature range MS epoxy hybrid sealant according to claim 8, characterized in that: The organotin catalyst includes 1,3-dilauroyloxy-1,1,3,3-tetrabutylditinoxy.

10. The method for preparing the full-temperature range MS epoxy hybrid sealant according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1, mixing and dispersing the silane-modified polyether polymer, the antioxidant and the first filler, and then adding the silane coupling agent and the epoxy curing agent and mixing and dispersing them to obtain component A; S2. Mix and disperse the epoxy resin and the second filler, then add the accelerator and the catalyst and mix and disperse them to obtain component B.

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