Two-component low-viscosity ultralow-temperature adhesive as well as preparation method and use method thereof

Abstract

The invention relates to the technical field of new materials, and mainly relates to a double-component low-viscosity ultralow-temperature adhesive as well as a preparation method and a use method thereof. The double-component low-viscosity ultralow-temperature adhesive comprises a component A and a component B. The component A comprises the following components in percentage by mass: 20-40% of bisphenol A epoxy resin, 4-8% of aromatic epoxy resin, 6-10% of polyurethane modified epoxy resin, 1-2% of a rubber toughening agent, 5-20% of a diluent and the balance of an additive. And the component B comprises the following components in percentage by mass: 10-40% of a polyether amine curing agent, 10-40% of a fatty amine curing agent, 10-40% of an aromatic amine curing agent and 10-40% of a phenolic aldehyde amine curing agent. The adhesive provided by the invention has relatively strong compressive strength and excellent toughness, can keep good toughness in a low-temperature environment, is not easy to cause brittle rupture, can bear relatively large mechanical load, and is suitable for various industrial applications.

Description

Technical Field

[0001] The present application relates to the field of new material technology, and mainly to a two-component low-viscosity ultra-low-temperature adhesive and a preparation method and a use method thereof. Background Art

[0002] With the rapid development of science and technology, adhesives, as an important material, are widely used in many fields such as electronics, aerospace, and automobiles. Among them, ultra-low temperature adhesives have attracted much attention due to their excellent low-temperature resistance, especially in special environments such as aerospace and deep-sea exploration.

[0003] However, many epoxy resin adhesives in the domestic prior art tend to significantly reduce their bonding properties or even lose their adhesion ability when they are subjected to extreme low temperatures. This is mainly attributed to the molecular structure and cross-linking characteristics of traditional epoxy resins, which change their physical properties significantly in low temperature environments, resulting in the cured adhesives showing high brittleness at low temperatures, thus affecting their durability and long-term performance. Existing ultra-low temperature adhesives often need to be prepared under special production conditions, with complex processes and high investment costs, which to a certain extent limits their large-scale application. For example, some adhesives require the addition of a large amount of diluents or modifiers to achieve low viscosity and enhance flexibility, but these additives often have a negative impact on the performance of the adhesive, such as reducing its mechanical strength and heat resistance. The use of high levels of organic solvents or diluents may lead to environmental pollution and health risks, increasing safety hazards. In addition, the storage and operating conditions of imported low-temperature adhesives are also relatively harsh, requiring strict control of temperature and humidity, which causes many inconveniences in practical applications. For example, under extreme environmental conditions, the storage and use of adhesives are restricted, which may lead to their performance degradation or failure. Therefore, it is necessary to develop an ultra-low temperature epoxy resin adhesive with low viscosity and excellent low temperature performance to meet the demand for high-performance adhesives in specific fields, and to promote the development of related industries, reduce production costs, improve material utilization efficiency, and provide possibilities for wider applications. Therefore, the existing technology still needs to be improved and developed. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the purpose of the present application is to provide a two-component low-viscosity ultra-low temperature adhesive and a preparation method and a use method thereof, aiming to solve the problem that the bonding performance of existing epoxy resin adhesives tends to decrease significantly or even lose their adhesion ability when experiencing extremely low temperatures.

[0005] The technical solution of this application is as follows: In a first aspect, the present application provides a two-component low-viscosity ultra-low temperature epoxy resin adhesive, the raw materials of which include component A and component B, wherein the component A, calculated by mass percentage, includes the following components: Bisphenol A epoxy resin 20-40%, aromatic epoxy resin 4-8%, polyurethane modified epoxy resin 6-10%, rubber toughening agent 1-2%, diluent 5-20%, and the balance is additives; The B component, calculated by mass percentage, includes the following components: Polyetheramine curing agent 10-40%, fatty amine curing agent 10-40%, aromatic amine curing agent 10-40%, phenolic amine curing agent 10-40%; The bisphenol A type epoxy resin comprises a first bisphenol A type epoxy resin and a second bisphenol A type epoxy resin; The viscosity of the first bisphenol A epoxy resin is 10-16 Pa·s, and the epoxy value is 0.48-0.54; the viscosity of the second bisphenol A epoxy resin is 6-8 Pa·s, and the epoxy value is 0.55-0.56; The mass ratio of the first bisphenol A epoxy resin to the second bisphenol A epoxy resin is 1:(0.2-0.4).

[0006] The two-component, low-viscosity, ultra-low-temperature epoxy resin adhesive provided in the present application has strong compressive strength and excellent toughness, can withstand large mechanical loads, is suitable for various industrial applications, can maintain good toughness in low-temperature environments, is not prone to brittle cracking, and is suitable for applications requiring high toughness. It also has a low expansion coefficient and can effectively resist thermal stress caused by temperature changes, providing stability for the joint surface.

[0007] Further, the aromatic epoxy resin includes a first aromatic epoxy resin and a second aromatic epoxy resin; The viscosity of the first aromatic epoxy resin is 3-6 Pa·s, and the epoxy value is 0.80-0.90; the viscosity of the second aromatic epoxy resin is 0.55-0.85 Pa·s, and the epoxy value is 0.95-1.05; The mass ratio of the first aromatic epoxy resin to the second aromatic epoxy resin is 1:(0.5-0.7).

[0008] Further, the polyurethane-modified epoxy resin includes a first polyurethane-modified epoxy resin and a second polyurethane-modified epoxy resin; The viscosity of the first polyurethane modified epoxy resin is 10-30 Pa·s, and the epoxy value is 0.45-0.53; the viscosity of the second polyurethane modified epoxy resin is 40-80 Pa·s, and the epoxy value is 0.50-0.56; The mass ratio of the first polyurethane-modified epoxy resin to the second polyurethane-modified epoxy resin is 1:(0.3-0.5).

[0009] Furthermore, the rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the mass ratio of the core-shell particles, polysulfide rubber and nitrile rubber is 1:(0.05-0.1):(0.2-0.4).

[0010] Further, the diluent is an epoxy-based reactive diluent, including a first reactive diluent and a second reactive diluent; The density of the first reactive diluent is 1.1 g / cm 3 , the epoxy value is 0.77; the viscosity of the second reactive diluent is 4-10 mPa·s, and the epoxy value is 0.32-0.34; The mass ratio of the first active diluent to the second active diluent is 1:(0.7-0.8).

[0011] Furthermore, the polyetheramine curing agent is one or more of D400, D2000 and T5000; The fatty amine curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The aromatic amine curing agent is one or more of DDM, DDS, DEDDM and MOCA; The phenolic amine curing agent is one or more of PAA-300, PAA-400 and PAA-500.

[0012] Furthermore, the The additives include leveling agent, silane coupling agent, defoamer, silicon dioxide and nano-alumina, and the mass percentage of the additives in the A component is as follows: Leveling agent 0.1-0.5%, silane coupling agent 0.1-0.5%, defoaming agent 0.1-0.5%, silicon dioxide 20-30%, nano alumina 10-30%.

[0013] Furthermore, the leveling agent is one or more of an organic silicon leveling agent, an acrylic leveling agent, and a fluorocarbon leveling agent; The silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane; The defoamer is one or more of an organosilicon defoamer, a polyether defoamer and a vinyl alcohol defoamer; The silicon dioxide is epoxy silicon dioxide; The nano-alumina is nano-alumina surface-modified by KH570.

[0014] In a second aspect, the present application provides a method for preparing a two-component low-viscosity ultra-low temperature epoxy resin adhesive, which comprises the following steps: Mix bisphenol A epoxy resin, aromatic epoxy resin, polyurethane modified epoxy resin, rubber toughening agent and diluent in proportion, and stir evenly under room temperature and vacuum conditions to obtain component A; The polyetheramine curing agent, the aliphatic amine curing agent, the aromatic amine curing agent and the phenolic amine curing agent are mixed in proportion, and stirred evenly under vacuum conditions at room temperature to obtain component B.

[0015] In a third aspect, a method for using the two-component low-viscosity ultra-low temperature epoxy resin adhesive as described in the first aspect, comprising the following steps: Dam the pouring area with foam or rubber; Add the B component to the A component, stir at 300-400 rpm for 5-10 min, and pump to the casting area for casting; The mass ratio of component A to component B is 20:1; The pouring environment temperature is 13-30℃ and the environment humidity is less than 80%RH.

[0016] Beneficial effects: By controlling the viscosity of bisphenol A epoxy resin, the adhesive system can achieve direct bonding without solvent, with high bonding strength and small curing shrinkage, and the low-viscosity adhesive can better penetrate and infiltrate the material surface, especially in complex structures or small gaps, which can ensure better bonding strength. The prepared two-component low-viscosity ultra-low temperature adhesive has a wide applicable temperature range, can work effectively in extreme environments from -196°C to +40°C, and adapt to various harsh conditions; has strong compressive strength, can withstand large mechanical loads, and is suitable for various industrial applications; has excellent toughness, can maintain good toughness in low-temperature environments, is not prone to brittle cracking, and is suitable for applications requiring high toughness; has a low expansion coefficient, can effectively resist thermal stress caused by temperature changes, and provide stability for the joint surface; has a fast curing rate, can complete curing in a short time, greatly improves production efficiency, and adapts to rapid assembly needs; the low viscosity property makes the adhesive have good fluidity, can be efficiently transported to the construction site by a pump, has good processability, is convenient for construction, reduces material waste, and improves economic benefits. DETAILED DESCRIPTION

[0017] The present application provides a two-component low-viscosity ultra-low temperature adhesive and a preparation method and a use method thereof. To make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0018] The present application provides a two-component low-viscosity ultra-low temperature epoxy resin adhesive, the raw materials of which include component A and component B, wherein component A, calculated by mass percentage, includes the following components: Bisphenol A epoxy resin 20-40%, aromatic epoxy resin 4-8%, polyurethane modified epoxy resin 6-10%, rubber toughening agent 1-2%, diluent 5-20%, and the balance is additives; Component B is calculated by mass percentage and includes the following components: Polyetheramine curing agent 10-40%, fatty amine curing agent 10-40%, aromatic amine curing agent 10-40%, phenolic amine curing agent 10-40%.

[0019] The two-component, low-viscosity, ultra-low-temperature epoxy resin adhesive provided in the present application has strong compressive strength and excellent toughness, can withstand large mechanical loads, is suitable for various industrial applications, can maintain good toughness in low-temperature environments, is not prone to brittle cracking, and is suitable for applications requiring high toughness. It also has a low expansion coefficient and can effectively resist thermal stress caused by temperature changes, providing stability for the joint surface.

[0020] Furthermore, the bisphenol A epoxy resin includes a first aromatic epoxy resin and a second aromatic epoxy resin. Specifically, the viscosity of the first bisphenol A epoxy resin is 10-16 Pa·s, and the epoxy value is 0.48-0.54; the viscosity of the second bisphenol A epoxy resin is 6-8 Pa·s, and the epoxy value is 0.55-0.56; the mass ratio of the first bisphenol A epoxy resin to the second bisphenol A epoxy resin is 1:(0.2-0.4), preferably 1:0.35.

[0021] The first bisphenol A epoxy resin can be specifically selected as E51 epoxy resin which is a colorless viscous liquid and has no softening point; the second bisphenol A epoxy resin can be specifically selected as E55 epoxy resin which is a colorless viscous liquid and has no softening point.

[0022] In the present application, the selected bisphenol A epoxy resin is a low molecular weight epoxy resin, which can be added to the adhesive system of the present application without the need for solvent, can be directly bonded, and the adhesive has the advantages of high bonding strength, small curing shrinkage, high temperature resistance, corrosion resistance, water resistance and high electrical insulation. Moreover, the inventors have also found through long-term research that when the mass ratio of the E51 epoxy resin and the E55 epoxy resin in the adhesive system of the present application is controlled in the ratio range of 1: (0.2-0.4), especially 1: 0.35, the obtained adhesive has strong adhesion, compression resistance, fluidity and curing speed. The inventors speculate that both E51 epoxy resin and E55 epoxy resin are bisphenol A epoxy resins, and can form a dense cross-linked structure after reacting with a curing agent, so that the adhesive has strong compression resistance, wherein the molecular weight of the E51 epoxy resin is relatively high, and there is a small amount of hydroxyl in the structure, which is conducive to improving the bonding strength of the adhesive and accelerating its curing rate. Compared with E51 epoxy resin, E55 epoxy resin has a lower viscosity. When applied to the substrate, it can penetrate into the substrate better. After compounding, the adhesive has stronger adhesion.

[0023] Furthermore, the aromatic epoxy resin includes a first aromatic epoxy resin and a second aromatic epoxy resin. Specifically, the viscosity of the first aromatic epoxy resin is 3-6 Pa·s, and the epoxy value is 0.80-0.90; the viscosity of the second aromatic epoxy resin is 0.55-0.85 Pa·s, and the epoxy value is 0.95-1.05. The mass ratio of the first aromatic epoxy resin to the second aromatic epoxy resin is 1:(0.5-0.7), preferably 1:0.68.

[0024] The first aromatic epoxy resin can be specifically selected as epoxy resin SW-70 which is a colorless viscous liquid and has no softening point; the second aromatic epoxy resin can be specifically selected as epoxy resin SW-0510 which is a light yellow viscous liquid and has no softening point.

[0025] In the present application, the selected epoxy resin SW-70 and epoxy resin SW-0510 are multifunctional epoxy resins with multiple cross-linking reaction groups. The cured product after reacting with the curing agent can form a firm three-dimensional network structure, which makes the adhesive have excellent compressive resistance. Both of them have a rigid structure of benzene rings, which further enhances its compressive resistance. After long-term research, the inventors also found that when the mass ratio of epoxy resin SW-70 and epoxy resin SW-0510 in the adhesive system of the present application is controlled in the ratio range of 1: (0.5-0.7), especially 1: 0.68, the obtained adhesive has excellent compressive resistance and bonding performance. The inventors speculate that the epoxy resin SW-70 has more cross-linking reaction groups than the epoxy resin SW-0510, which can enhance the compressive resistance of the adhesive in a low temperature environment. The epoxy resin SW-0510 used is a low-viscosity epoxy resin, which can reduce the overall viscosity of the adhesive and is more conducive to substrate bonding. After being compounded in a suitable proportion, the overall bonding performance is improved.

[0026] Further, the polyurethane modified epoxy resin includes a first polyurethane modified epoxy resin and a second polyurethane modified epoxy resin. Specifically, the viscosity value of the first polyurethane modified epoxy resin is 10-30 Pa·s, and the epoxy value is 0.45-0.53; the viscosity value of the second polyurethane modified epoxy resin is 40-80 Pa·s, and the epoxy value is 0.50-0.56. The mass ratio of the first polyurethane modified epoxy resin to the second polyurethane modified epoxy resin is 1:(0.3-0.5).

[0027] The first polyurethane-modified epoxy resin can be specifically selected as the polyurethane-modified epoxy resin EU-2000 which is a light yellow to colorless transparent viscous liquid with no softening point; the second polyurethane-modified epoxy resin can be specifically selected as the polyurethane-modified epoxy resin EU-3000 which is a light yellow viscous liquid with no softening point.

[0028] In the present application, the toughness and bonding ability can be further improved by selecting a composition of polyurethane modified epoxy resin EU-2000 and polyurethane modified epoxy resin EU-3000, ensuring that the adhesive can maintain excellent performance in a low temperature environment. The inventors speculate that the polyurethane molecules contain carbamate groups (-NH-COO-) and the molecular chains are flexible, have good vibration resistance and fatigue resistance, and have high elasticity, especially excellent performance at low temperatures.

[0029] Furthermore, the rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the mass ratio of the core-shell particles, polysulfide rubber and nitrile rubber is 1: (0.05-0.1): (0.2-0.4). Among them, the core-shell particles are specifically an epoxy toughening agent LSE-103-30 from Dalian Liansheng, a white viscous liquid with a viscosity of 140-180 Pa·s and an epoxy value of 0.38, composed of bisphenol A epoxy resin and polybutadiene rubber. Polysulfide rubber is a light yellow viscous liquid with a density of 1.125g / cm 3 . Nitrile rubber is a polymer of butadiene and acrylonitrile with a molecular weight of 2000-30000.

[0030] In the adhesive system of this scheme, the toughness of the adhesive can be improved by adding core-shell particles, so that it has excellent crack resistance in low temperature environment. This application can improve the toughness of the adhesive and reduce brittle failure by adding core-shell particles, polysulfide rubber and nitrile rubber, especially in low temperature environment, which helps to improve the toughness and crack resistance of the material.

[0031] Further, the diluent is an epoxy-based reactive diluent, including a first reactive diluent and a second reactive diluent; specifically, the density of the first reactive diluent is 1.1 g / cm 3 The viscosity of the second active diluent is 4-10 mPa·s, and the epoxy value is 0.32-0.34. The mass ratio of the first active diluent to the second active diluent is 1:(0.7-0.8).

[0032] The first active diluent may be a colorless liquid active diluent XY-622, and the second active diluent may be a colorless liquid active diluent XY-748.

[0033] In the present application, the selected composition of active diluent XY-622 and active diluent XY-748 has a cross-linking reaction group, which participates in the curing process, thereby improving the compressive strength, and can also improve the fluidity of the adhesive, enhance flexibility, and improve adhesion and compressive resistance. The inventor speculates that this is because the active long-chain diluent is selected, which can reduce the viscosity of the resin, thereby improving its fluidity, making it easier for the resin to be evenly coated on the surface of the substrate, and both are long-chain structures with a certain degree of flexibility, which can increase the toughness and impact resistance of the final coating, thereby reducing the risk of cracks caused by temperature changes or mechanical stress.

[0034] Furthermore, the additives include a leveling agent, a silane coupling agent, a defoaming agent, silicon dioxide and nano-alumina, and the mass percentage of the A component is as follows: Leveling agent 0.1-0.5%, silane coupling agent 0.1-0.5%, defoaming agent 0.1-0.5%, silicon dioxide 20-30%, nano alumina 10-30%.

[0035] Furthermore, the leveling agent is one or more of an organic silicon leveling agent, an acrylic leveling agent, and a fluorocarbon leveling agent.

[0036] In this application, the added leveling agent is mainly used to improve the fluidity and surface smoothness of the epoxy resin, reduce the surface tension of the epoxy resin, make the resin more evenly distributed during the curing process, and avoid the generation of bubbles and defects.

[0037] Furthermore, the silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane.

[0038] In this application, the added silane coupling agent can enhance the interfacial bonding force in the epoxy resin, improve the bonding performance between the resin and the filler or substrate, and improve the mechanical strength, water resistance, heat resistance and chemical resistance of the resin by forming chemical bonds and physical adsorption. In addition, the silane coupling agent can also improve the weather resistance of the resin and extend its service life.

[0039] Furthermore, the defoaming agent is one or more of a silicone defoaming agent, a polyether defoaming agent and a vinyl alcohol defoaming agent.

[0040] In this application, the defoamer added to the epoxy resin is used to reduce or eliminate the generation of foam, ensuring the quality of the epoxy resin adhesive during the process. Specifically, the foam that is not eliminated may cause bubble defects, affecting the physical properties and appearance of the material. The defoamer can reduce the surface tension of the liquid, making the foam easier to break, thereby effectively improving the fluidity and density of the epoxy resin and ensuring the final strength of the epoxy resin adhesive.

[0041] Furthermore, the silicon dioxide is epoxy silicon dioxide with a particle size of 10-20 nm. The preparation method of epoxy silicon dioxide comprises the following steps: Dissolve the silane coupling agent in the solvent, then slowly stir and add the silica. Stir continuously during the addition process to ensure that the solution is evenly mixed. After the addition is completed, ultrasonically treat for 30-40 minutes, then add it to the E51 epoxy resin, stir and mix evenly, and raise the temperature to 100-130°C until the solvent is removed to obtain epoxy silica.

[0042] The mass ratio of silicon dioxide, silane coupling agent and epoxy resin is 3:0.01:97, and the mass ratio of the total mass of silicon dioxide, silane coupling agent and epoxy resin to the solvent is 1:1.5. The silane coupling agent is one or more than two of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane; and the solvent is acetone.

[0043] In the present application, the silica selected is specifically epoxy silica. The inventors have found that by introducing highly active epoxy functional groups that can react with curing agents into silica, it can be combined with epoxy resin by chemical bonds in epoxy resin adhesives, thereby obtaining an interpenetrating network structure with good interface bonding strength. The synergistic effect of the two can improve the impact strength, elongation at break and heat resistance of the epoxy resin adhesive at the same time.

[0044] Furthermore, the nano-alumina is nano-alumina surface-modified by KH570, and the particle size is 20-50 nm. The preparation method of nano-alumina surface-modified by KH570 comprises the following steps: Add nano-alumina to an anhydrous ethanol / water mixed solution (the volume ratio of anhydrous ethanol to water is 3:1), and fully disperse it under a high-speed shear of 4000-5000 r / min; then, adjust the shear rate to 1000-2000 r / min, the reaction temperature to about 70°C, add a silane coupling agent KH570, and adjust the pH to about 4 with oxalic acid; after reacting for 90 minutes, filter the suspension, and dry and grind the obtained filter cake to obtain KH570 surface-modified nano-alumina powder; The mass ratio of nano-alumina to anhydrous ethanol / water mixed solution is 1:1; the added amount of silane coupling agent KH570 is 20% of the added mass of nano-alumina.

[0045] In the present application, the selected nano-alumina is nano-alumina modified with KH570. The inventors found that adding nano-alumina can improve the compressive properties and toughness of epoxy resin adhesives, but nano-alumina has a small particle size and a large specific surface area, and is easy to agglomerate in epoxy resin, thereby affecting the performance of epoxy resin adhesives. Therefore, the present application grafts KH570 onto nano-alumina to improve the hydrophobicity of nano-alumina, reduce the agglomeration of nano-alumina, and improve its dispersibility in epoxy resin. After the modified nano-alumina is uniformly dispersed in the adhesive system, its compressive properties under low temperature conditions can be improved.

[0046] Furthermore, the polyetheramine curing agent is one or more of D400, D2000 and T5000.

[0047] In this application, the selected polyetheramine curing agent has good flexibility and chemical resistance, and can improve the toughness and impact resistance of epoxy resin. The polyetheramine curing agent reacts with the epoxy groups in the epoxy resin to form a cross-linked network, thereby enhancing the mechanical properties and thermal stability of the resin. In addition, the polyetheramine also has a low viscosity, which facilitates good fluidity in the application and helps to improve the smoothness and adhesion of the adhesive coating.

[0048] Furthermore, the fatty amine curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0049] In this application, the selected aliphatic amine curing agent is commonly used in epoxy resins, mainly because of its good reactivity and moderate curing speed. This type of curing agent usually exhibits high low temperature curing ability and can provide good mechanical properties and heat resistance. Moreover, the chain structure of the aliphatic amine enables it to increase the toughness and impact resistance of the epoxy resin.

[0050] Furthermore, the aromatic amine curing agent is one or more of DDM, DDS, DEDDM and MOCA.

[0051] In the present application, the selected aromatic amine curing agent has a high curing temperature and excellent thermal stability, and is suitable for the application of high-performance epoxy resins. Such curing agents can generally provide good mechanical properties and chemical resistance at higher temperatures.

[0052] Furthermore, the phenalkamine curing agent is one or more of PAA-300, PAA-400 and PAA-500.

[0053] In this application, the selected phenalkamine curing agent is widely used in epoxy resin due to its excellent thermal stability and mechanical properties. This type of curing agent can still maintain good performance in high temperature environments and is suitable for applications requiring severe heat resistance. By reacting with epoxy resin to form a cross-linked structure, phenalkamine can significantly improve the compression and bending resistance of the resin, while providing excellent electrical insulation properties.

[0054] The present application also provides a method for preparing a two-component low-viscosity ultra-low-temperature epoxy resin adhesive, which comprises the following steps: Mix bisphenol A epoxy resin, aromatic epoxy resin, polyurethane modified epoxy resin, rubber toughening agent and diluent in proportion, and stir evenly under room temperature and vacuum conditions to obtain component A; The polyetheramine curing agent, the aliphatic amine curing agent, the aromatic amine curing agent and the phenolic amine curing agent are mixed in proportion, and stirred evenly under vacuum conditions at room temperature to obtain component B.

[0055] The two-component low-viscosity ultra-low-temperature epoxy resin adhesive as described above can also be obtained by preparing component A and component B separately through this preparation method.

[0056] Furthermore, when component A also includes components of silicon dioxide, nano-alumina, a leveling agent, a silane coupling agent and a defoaming agent, the preparation method of a two-component low-viscosity ultra-low-temperature epoxy resin adhesive comprises the following steps: Mix bisphenol A epoxy resin, aromatic epoxy resin, polyurethane modified epoxy resin, rubber toughening agent, diluent, silicon dioxide, nano-alumina, leveling agent, silane coupling agent and defoaming agent in proportion, and stir evenly under room temperature and vacuum conditions to obtain component A; The polyetheramine curing agent, the aliphatic amine curing agent, the aromatic amine curing agent and the phenolic amine curing agent are mixed in proportion, and stirred evenly under vacuum conditions at room temperature to obtain component B.

[0057] The present application also provides a method for using the two-component low-viscosity ultra-low temperature epoxy resin adhesive as described above, which comprises the following steps: Dam the pouring area with foam or rubber; Add component B into component A, stir at 300-400 rpm for 5-10 min, and pump to the pouring area for pouring.

[0058] Furthermore, the mass ratio of component A to component B is 20:1; the casting environment temperature is 13-30° C., and the environment humidity is less than 80% RH.

[0059] Among them, stirring can be carried out through a stirrer; after pouring, an inspection should be carried out to check whether there is any glue leakage. If there is any glue leakage, it should be blocked with a cloth strip and filled with pouring.

[0060] The two-component low-viscosity ultra-low-temperature epoxy resin adhesive prepared in the present application has a construction time of 1-2 hours and good processing performance.

[0061] The invention is further described below by means of specific examples.

[0062] The sources of some raw materials in the examples and comparative examples of the present application are as follows: E51 epoxy resin: Guangzhou Hongsheng Chemical Company; E55 epoxy resin: Hubei Langbowan Biopharmaceutical Co., Ltd.; Aromatic epoxy resin SW-70, epoxy resin SW-0510: Jining Hongming Chemical Reagent Co., Ltd.; Polyurethane modified epoxy resin EU-2000, polyurethane modified epoxy resin EU-3000: Hunan Saierwei New Material Technology Co., Ltd.; Core-shell particles (LSE-103-30): Dalian Liansheng Trading Co., Ltd.; Polysulfide rubber: Shanghai MacLean Biochemical Technology Co., Ltd.; Nitrile rubber: Dalian Liansheng Trading Co., Ltd.; Active diluent XY-622: Jining Baiyi Chemical Co., Ltd.; Active diluent XY-748: Shanghai Fanxiao Chemical Technology Co., Ltd.; Epoxy silica: homemade; KH570 surface modified nano-alumina: homemade; D400, D2000, T5000: Dalian Liansheng Trading Co., Ltd.; Diethylenetriamine, triethylenetetramine, tetraethylenepentamine: Shanghai MacLean Biochemical Technology Co., Ltd.; DDM, DDS, DEDDM and MOCA: Heze Yonghui Composite Materials Co., Ltd.

[0063] The particle size of epoxy silicon dioxide is 20 nm, and the preparation method comprises the following steps: The silane coupling agent is dissolved in acetone, and then the silicon dioxide is slowly added with stirring. The addition process needs to be continuously stirred to ensure that the solution is evenly mixed. After the addition is completed, ultrasonic treatment is performed for 40 minutes, and then added to the E51 epoxy resin, and the mixture is stirred and mixed evenly. The temperature is raised to 100°C until the acetone is removed to obtain epoxy silicon dioxide. Among them, the mass ratio of silicon dioxide, silane coupling agent and epoxy resin is 3:0.01:97, and the mass ratio of the total mass of silicon dioxide, silane coupling agent and epoxy resin to acetone is 1:1.5; the silane coupling agent is epoxy silane.

[0064] The nano-alumina is nano-alumina surface-modified by KH570, with a particle size of 40 nm. The preparation method comprises the following steps: Nano-alumina was added to an anhydrous ethanol / water mixed solution (the volume ratio of anhydrous ethanol to water was 3:1), and fully dispersed under high-speed shearing at 5000 r / min; then, the shear rate was adjusted to 2000 r / min, the reaction temperature was 70°C, and silane coupling agent KH570 was added, and the pH was adjusted to 4 with oxalic acid; after reacting for 90 minutes, the suspension was filtered, and the obtained filter cake was dried and ground to obtain KH570 surface-modified nano-alumina powder. Among them, the mass ratio of nano-alumina to anhydrous ethanol / water mixed solution was 1:1; the amount of silane coupling agent KH570 added was 20% of the mass of nano-alumina added.

[0065] The preparation method of the two-component low-viscosity ultra-low temperature epoxy resin adhesive of the embodiment of the present application comprises the following steps: Mix bisphenol A epoxy resin, aromatic epoxy resin, polyurethane modified epoxy resin, rubber toughening agent, diluent, silicon dioxide, nano-alumina, leveling agent, silane coupling agent and defoaming agent in proportion, and stir evenly under room temperature and vacuum conditions to obtain component A; The polyetheramine curing agent, the aliphatic amine curing agent, the aromatic amine curing agent and the phenolic amine curing agent are mixed in proportion, and stirred evenly under vacuum conditions at room temperature to obtain component B; The method for using the two-component low-viscosity ultra-low temperature epoxy resin adhesive of the embodiment of the present application comprises the following steps: Dam the pouring area with foam or rubber; Add component B into component A, stir at 350 rpm for 5-10 min, and pump to the pouring area for pouring.

[0066] The mass ratio of component A to component B is 20:1; the casting environment temperature is 25°C, and the environment humidity is less than 80%RH.

[0067] Among them, the construction time is 1-2h.

[0068] Example 1 The two-component low-viscosity ultra-low-temperature epoxy resin adhesive of Example 1 is calculated by mass percentage. Component A in the two-component low-viscosity ultra-low-temperature epoxy resin adhesive includes: 40% bisphenol A epoxy resin, 5% aromatic epoxy resin, 10% polyurethane modified epoxy resin, 2% rubber toughening agent, 10% diluent, 22.7% epoxy silicon dioxide, 10% surface-modified nano-alumina, 0.1% leveling agent, 0.1% silane coupling agent, and 0.1% defoaming agent. Component B includes the following components: 15% polyetheramine curing agent, 35% fatty amine curing agent, 40% aromatic amine curing agent, and 10% phenolic amine curing agent.

[0069] Among them, the bisphenol A type epoxy resin is a composition of E51 epoxy resin and E55 epoxy resin, and the corresponding mass ratio is 1:0.35; the aromatic epoxy resin SW-70 and the epoxy resin SW-0510 are a composition, and the corresponding mass ratio is 1:0.68; the polyurethane modified epoxy resin is a composition of polyurethane modified epoxy resin EU-2000 and polyurethane modified epoxy resin EU-3000, and the corresponding mass ratio is 1:0.45; the rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the corresponding mass ratio is 1:0.05:0.32; the diluent is a composition of XY-622 and XY-748, and the corresponding mass ratio is 1:0.77; the leveling agent is acrylic acid. The leveling agent is selected; the silane coupling agent is methacryloxysilane; the defoaming agent is a polysiloxane defoaming agent; the silicon dioxide is epoxy silicon dioxide; the nano alumina is KH570 surface-modified nano alumina; the polyetheramine curing agent is a combination of D400 and D2000, and the corresponding mass ratio is 1:0.5; the fatty amine curing agent is a combination of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the corresponding mass ratio is 1:0.2:0.1; the aromatic amine curing agent is a combination of DDM, DDS and DEDDM, and the corresponding mass ratio is 1:0.1:0.3; the phenolic amine curing agent is a combination of PAA-300 and PAA-400, and the corresponding mass ratio is 1:0.4.

[0070] Example 2 The two-component low-viscosity ultra-low-temperature epoxy resin adhesive of Example 2 is calculated by mass percentage. Component A in the two-component low-viscosity ultra-low-temperature epoxy resin adhesive includes: 35% bisphenol A epoxy resin, 5% aromatic epoxy resin, 10% polyurethane modified epoxy resin, 2% rubber toughening agent, 15% diluent, 22.7% epoxy silicon dioxide, 10% surface-modified nano-alumina, 0.1% leveling agent, 0.1% silane coupling agent, and 0.1% defoaming agent. Component B includes the following components: 15% polyetheramine curing agent, 35% fatty amine curing agent, 40% aromatic amine curing agent, and 10% phenolic amine curing agent.

[0071] Among them, the bisphenol A type epoxy resin is a composition of E51 epoxy resin and E55 epoxy resin, and the corresponding mass ratio is 1:0.35; the aromatic epoxy resin SW-70 and the epoxy resin SW-0510 are a composition, and the corresponding mass ratio is 1:0.68; the polyurethane modified epoxy resin is a composition of polyurethane modified epoxy resin EU-2000 and polyurethane modified epoxy resin EU-3000, and the corresponding mass ratio is 1:0.45; the rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the corresponding mass ratio is 1:0.05:0.32; the diluent is a composition of XY-622 and XY-748, and the corresponding mass ratio is 1:0.77; the leveling agent is acrylic acid. The leveling agent is selected; the silane coupling agent is methacryloxysilane; the defoaming agent is a polysiloxane defoaming agent; the silicon dioxide is epoxy silicon dioxide; the nano alumina is KH570 surface-modified nano alumina; the polyetheramine curing agent is a combination of D400 and D2000, and the corresponding mass ratio is 1:0.5; the fatty amine curing agent is a combination of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the corresponding mass ratio is 1:0.2:0.1; the aromatic amine curing agent is a combination of DDM, DDS and DEDDM, and the corresponding mass ratio is 1:0.1:0.3; the phenolic amine curing agent is a combination of PAA-300 and PAA-400, and the corresponding mass ratio is 1:0.4.

[0072] Example 3 The two-component low-viscosity ultra-low-temperature epoxy resin adhesive of Example 3 is calculated by mass percentage. Component A in the two-component low-viscosity ultra-low-temperature epoxy resin adhesive includes: 40% bisphenol A epoxy resin, 5% aromatic epoxy resin, 10% polyurethane modified epoxy resin, 2% rubber toughening agent, 10% diluent, 22.7% epoxy silicon dioxide, 10% surface-modified nano-alumina, 0.1% leveling agent, 0.1% silane coupling agent, and 0.1% defoaming agent. Component B includes the following components: 15% polyetheramine curing agent, 55% fatty amine curing agent, 20% aromatic amine curing agent, and 10% phenolic amine curing agent.

[0073] Among them, the bisphenol A epoxy resin is a combination of E51 epoxy resin and E55 epoxy resin, and the corresponding mass ratio is 1:0.35; the aromatic epoxy resin SW-70 and the epoxy resin SW-0510 are a combination of 1:0.68; the polyurethane modified epoxy resin is a combination of polyurethane modified epoxy resin EU-2000 and polyurethane modified epoxy resin EU-3000, and the corresponding mass ratio is 1:0.45; the rubber toughening agent is a combination of core-shell particles, polysulfide rubber and nitrile rubber, and the corresponding mass ratio is 1:0.05:0.32; the diluent is a combination of XY-622 and XY-748, and the corresponding mass ratio is 1:0. 77; acrylic leveling agent is selected as leveling agent; methacryloxysilane is selected as silane coupling agent; polysiloxane defoaming agent is selected as defoaming agent; epoxy silica is selected as silica; nano alumina is KH570 surface-modified nano alumina; T5000 is selected as polyetheramine curing agent; the fatty amine curing agent is selected from the combination of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the corresponding mass ratio is 1:0.2:0.1; the aromatic amine curing agent is selected from the combination of DDM, DEDDM and MOCA, and the corresponding mass ratio is 1:0.1:0.2; the phenolic amine curing agent is selected from the combination of PAA-300 and PAA-500, and the corresponding mass ratio is 1:0.5.

[0074] Example 4 The two-component low-viscosity ultra-low-temperature epoxy resin adhesive of Example 4 is calculated by mass percentage. Component A in the two-component low-viscosity ultra-low-temperature epoxy resin adhesive includes: 40% bisphenol A epoxy resin, 5% aromatic epoxy resin, 10% polyurethane modified epoxy resin, 2% rubber toughening agent, 10% diluent, 22.7% epoxy silicon dioxide, 10% surface-modified nano-alumina, 0.1% leveling agent, 0.1% silane coupling agent, and 0.1% defoaming agent. Component B includes the following components: 15% polyetheramine curing agent, 35% fatty amine curing agent, 40% aromatic amine curing agent, and 10% phenolic amine curing agent.

[0075] Among them, the bisphenol A type epoxy resin is E51 epoxy resin; the aromatic epoxy resin is SW-70; the polyurethane modified epoxy resin is polyurethane modified epoxy resin EU-3000, and the rubber toughening agent is core-shell particles; the diluent is a composition of XY-622 and XY-748, and the corresponding mass ratio is 1:0.77; the leveling agent is an acrylic leveling agent; the silane coupling agent is methacryloxy silane; the defoaming agent is a polysiloxane defoaming agent; the silica is epoxy silica; the nano alumina is KH570 surface-modified nano alumina; the polyether amine curing agent is D400; the fatty amine curing agent is tetraethylene pentamine; the aromatic amine curing agent is DDM; and the phenolic amine curing agent is PAA-300.

[0076] Example 5 The two-component low-viscosity ultra-low-temperature epoxy resin adhesive of Example 5 is calculated by mass percentage. Component A in the two-component low-viscosity ultra-low-temperature epoxy resin adhesive includes: 40% bisphenol A epoxy resin, 5% aromatic epoxy resin, 10% polyurethane modified epoxy resin, 2% rubber toughening agent, 10% diluent, 22.7% epoxy silicon dioxide, 10% surface-modified nano-alumina, 0.1% leveling agent, 0.1% silane coupling agent, and 0.1% defoaming agent. Component B includes the following components: 25% polyetheramine curing agent, 25% fatty amine curing agent, 40% aromatic amine curing agent, and 10% phenolic amine curing agent.

[0077] Among them, the bisphenol A type epoxy resin is a composition of E51 epoxy resin and E55 epoxy resin, and the corresponding mass ratio is 1:0.35; the aromatic epoxy resin SW-70 and the epoxy resin SW-0510 are a composition, and the corresponding mass ratio is 1:0.68; the polyurethane modified epoxy resin is a composition of polyurethane modified epoxy resin EU-2000 and polyurethane modified epoxy resin EU-3000, and the corresponding mass ratio is 1:0.45; the rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the corresponding mass ratio is 1:0.05:0.32; the diluent is a composition of XY-622 and XY-748, and the corresponding mass ratio is 1:0.77; the leveling agent is acrylic acid. The leveling agent is selected; the silane coupling agent is methacryloxysilane; the defoaming agent is a polysiloxane defoaming agent; the silicon dioxide is epoxy silicon dioxide; the nano alumina is KH570 surface-modified nano alumina; the polyetheramine curing agent is a combination of D400 and D2000, and the corresponding mass ratio is 1:0.6; the fatty amine curing agent is a combination of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the corresponding mass ratio is 1:0.1:0.2; the aromatic amine curing agent is a combination of DDM, DDS and DEDDM, and the corresponding mass ratio is 1:0.3:0.3; the phenolic amine curing agent is a combination of PAA-300 and PAA-400, and the corresponding mass ratio is 1:0.4.

[0078] Performance Evaluation 1. Compression test: According to the standard test method ASTM D-695, the compression strength, compression modulus and compression toughness of the adhesive were tested. The finished product samples of the adhesives of Examples 1-5 were prepared for testing, respectively, and the sample sizes were 12.7mm×12.7mm×25.4mm and 12.7mm×12.7mm×50.8mm. The compression strength of the adhesive was tested at 20°C, -50°C, -110°C and -196°C, and its compression modulus and compression toughness were calculated, and 5 parallel experiments were performed.

[0079] 2. Bonding shear test of steel and birch: The adhesive was tested for bonding shear test on steel and birch according to standard test method ASTM D-1002. The size of steel and birch was 1.6×25.4×100 mm, the bonding overlap thickness was 12.5 mm, and the adhesive of test examples 1-5 was tested for bonding shear test on steel and birch at 40°C, 20°C and -45°C, and 5 parallel experiments were performed.

[0080] 3. Viscosity test: The viscosity of the adhesive was tested according to the standard test method ASTM D-2196. The viscosity of the adhesives of Examples 1 to 5 before and after mixing at room temperature was tested using a viscometer, and five parallel experiments were performed.

[0081] 4. Hardness test: The hardness of the adhesive was tested according to the standard test method ASTM D-2583. The hardness of the adhesives of Examples 1 to 5 after being completely cured at room temperature was tested using a Barcol hardness tester, and five parallel experiments were performed.

[0082] 5. Tensile test: The tensile strength of the adhesive was tested according to the standard test method ASTM D-638. Dumbbell Type 1 specimens were prepared to test the elongation at break of the finished adhesives of Examples 1 to 5, and five parallel experiments were performed.

[0083] 6. Thermal expansion coefficient test: The thermal expansion coefficient of the adhesive was tested according to the standard test method ASTM D-696. The adhesives of Examples 1-5 were prepared into cuboids with a size of 12.5×6.3×(50-125) mm, and the thermal expansion coefficient of the adhesive was tested at a temperature of -30°C to 30°C, and 5 parallel experiments were performed.

[0084] 7. Thermal conductivity test: The thermal conductivity of the adhesive was tested according to the standard test method ASTM D-5470. The adhesives of Examples 1-5 were prepared into cylinders with a size of 20×6 mm, and the thermal conductivity of the adhesives was tested at room temperature. Five parallel experiments were performed.

[0085] 8. Punch shear test: The punch shear strength of the adhesive was tested according to the standard test method ASTM D-732. The adhesives of Examples 1-5 were prepared into discs with a diameter of 50 mm, a thickness of 1.27-12.7 mm, and a sample with a hole of 11 mm in the middle. The punch shear strength was tested and 5 parallel experiments were performed.

[0086] 9. Creep test: The adhesive was subjected to a creep test. The adhesives of Examples 1-5 were prepared into a cube with a size of 30×30×30 mm, and were continuously compressed with 2MPa for 120 hours. The compression displacement was tested and five parallel experiments were performed. Internal standard for creep test: The test will continuously compress three samples with a size of 30*30*30mm for 120 hours at 300psi (=2MPa). The thickness of each sample was measured; the force applied to the object = stress * the force area of ​​the object (F=ơ*A=2*30*30=1800N), loading (a). The height of the object before compression, loading (b). The height of the object after compression for 120 hours, and the height difference before and after compression for 120 hours was detected. It is generally required that (ab) / a<0.053 under 120 hours of compression creep.

[0087] 10. Curing shrinkage test: The curing shrinkage of the adhesive was tested according to the standard test method ASTM D-2566. The adhesive raw materials of Examples 1-5 were poured into a mold, the length and area before and after curing were measured, and the shrinkage after curing was calculated. Five parallel experiments were performed.

[0088] 11. Curing time test: The curing time of the adhesive was tested. During the curing process of the adhesive in Examples 1-5, the Barcol hardness was tested every 12 hours using a Barcol hardness tester. The final curing time was determined when the Barcol hardness reached 38 or above. Five parallel experiments were performed.

[0089] 12. Application period test: The applicable period of the adhesive was tested. The applicable period refers to the time after the resin and curing agent are mixed that the mixed adhesive can be used for construction. The adhesive raw materials of Examples 1-5 were dipped into a wooden board, and the adhesive was dripped vertically to observe the fluidity of the liquid. The flow and dripping of the liquid were observed and recorded every 5 minutes. The final time when the liquid stopped flowing and dripping was recorded as the applicable period. Five parallel experiments were performed.

[0090] The test results of performance evaluation are shown in Table 1 and Table 2: Table 1 Test items Test Standards Example 1 Example 2 Example 3 Compression strength ASTM D-695 99 MPa(20℃)211 MPa(-50℃)258 MPa(-110℃)175MPa(-196℃) 60 MPa(20℃)130 MPa(-50℃)150MPa(-110℃)105 MPa(-196℃) 68 MPa(20℃)151 MPa(-50℃)187MPa(-110℃)125 MPa(-196℃) Compression modulus ASTM D-695 4546 MPa (20℃) 6614 MPa (-50℃) 7735 MPa (-110℃) 14217 MPa (-196℃) 2034 MPa(20℃)3941 MPa(-50℃)4132 MPa(-110℃)7329 MPa(-196℃) 2315 MPa(20℃)4131 MPa(-50℃)4761 MPa(-110℃)8537 MPa(-196℃) Compression toughness ASTM D-695 546 MPa(20℃)584 MPa(-50℃)560 MPa(-110℃)258MPa(-196℃) 452 MPa(20℃)502 MPa(-50℃)482MPa(-110℃)234 MPa(-196℃) 462 MPa(20℃)517 MPa(-50℃)491MPa(-110℃)239 MPa(-196℃) Bonding of steel ASTM D-1002 13-18 MPa(40℃)14-16MPa(20℃)9-16 MPa(-45℃) 17-22 MPa(40℃)15-19 MPa(20℃)15-20 MPa(-45℃) 16-18 MPa(40℃)15-17 MPa(20℃)16-19 MPa(-45℃) Birch Bonding ASTM D-1002 4-5 MPa (40℃) 4-5 MPa (20℃) 4-5 MPa (-45℃) The bonding surface remains bonded and breaks from the wood board 4-5 MPa (40℃) 4-5 MPa (20℃) 4-5 MPa (-45℃) The bonding surface remains bonded and breaks from the wood board 4-5 MPa (40℃) 4-5 MPa (20℃) 4-5 MPa (-45℃) The bonding surface remains bonded and breaks from the wood board Viscosity ASTM D-2196 Component A - 25120 cps Component B - water-like after mixing - 7088 cps Component A - 2041 cps Component B - water-like after mixing - 6210 cps Component A - 2153 cps Component B - water-like after mixing - 6539 cps hardness ASTM D-2583 42-47 Pasteur 40-45 Pap 38-40 Pap Stretch ASTM D-638 4-5% 7-8% 5-6% Coefficient of thermal expansion ASTM D-696 <![CDATA[35.17x10 -6 mm / mm / ℃]]> <![CDATA[34.13x10 -6 mm / mm / ℃]]> <![CDATA[35.93x10 -6 mm / mm / ℃]]> Punch shear strength ASTM D-732 45 MPa(-110℃) 38 MPa(-110℃) 40 MPa(-110℃) Thermal conductivity ASTM D-5470 0.463 Wm °K 0.483 Wm °K 0.451 Wm °K Creep test - 0.034 mm 0.061 mm 0.054 mm Curing shrinkage ASTM D-2566 0.10% 0.15% 0.13% Curing time - After 48h curing, Barcol hardness 40-42 (25℃) After 48h curing, Barcol hardness 37-39 (25℃) After 48h curing, the Barcol hardness is 38-40 (25℃) Applicable period - 90-150 min 90-150 min 90-150 min Table 2 Test items Test Standards Example 4 Example 5 Compression strength ASTM D-695 95 MPa(20℃)150 MPa(-50℃)168 MPa(-110℃)121MPa(-196℃) 80 MPa(20℃)145 MPa(-50℃)158 MPa(-110℃)105 MPa(-196℃) Compression modulus ASTM D-695 4329 MPa (20℃) 5731 MPa (-50℃) 6121MPa (-110℃) 8621 MPa (-196℃) 4374 MPa (20℃) 5914 MPa (-50℃) 6821 MPa (-110℃) 9143 MPa (-196℃) Compression toughness ASTM D-695 537 MPa(20℃)561 MPa(-50℃)554 MPa(-110℃)241 MPa(-196℃) 407 MPa(20℃)451 MPa(-50℃)441 MPa(-110℃)214 MPa(-196℃) Bonding of steel ASTM D-1002 13-17 MPa(40℃)14-15 MPa(20℃)8-10MPa(-45℃) 13-15 MPa(40℃)10-13 MPa(20℃)5-8 MPa(-45℃) Birch Bonding ASTM D-1002 4-5 MPa (40℃) 4-5 MPa (20℃) 4-5 MPa (-45℃) The bonding surface remains bonded and breaks from the wood board 4-5 MPa (40℃) 4-5 MPa (20℃) 4-5 MPa (-45℃) The bonding surface remains bonded and breaks from the wood board Viscosity ASTM D-2196 Component A - 2421 cps Component B - Water-like mixture - 6926 cps Component A - 2121 cps Component B - Water-like mixture - 6831 cps hardness ASTM D-2583 42-45 Pap 40-43 Pap Stretch ASTM D-638 4-5% 4-5% Coefficient of thermal expansion ASTM D-696 <![CDATA[36.62x10 -6 mm / mm / ℃]]> <![CDATA[35.11x10 -6 mm / mm / ℃]]> Punch shear strength ASTM D-732 36 MPa(-110℃) 40 MPa(-110℃) Thermal conductivity ASTM D-5470 0.463 Wm °K 0.421 Wm °K Creep test - 0.031 mm 0.035 mm Curing shrinkage ASTM D-2566 0.10% 0.10% Curing time - After 48h curing, Barcol hardness 40-42 (25℃) After 48h curing, Barcol hardness 31-33 (25℃) Applicable period - 90-150 min 90-150 min The epoxy resin adhesive prepared in the embodiment of the present application has good comprehensive performance, high compressive strength, and can still maintain good toughness at low temperatures, can avoid brittle fracture, has a wide range of applicable temperatures, can effectively work in extreme environments from -196°C to +40°C, and can adapt to various harsh conditions. Moreover, low-viscosity adhesives can better penetrate and infiltrate the surface of materials, especially in complex structures or small gaps, which can ensure better bonding strength, and low-viscosity adhesives have good fluidity, can be delivered to the construction site by pump transmission, and have good processability.

[0091] It should be understood that the application of the present application is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made according to the above description, and all these improvements and changes should fall within the scope of protection of the present application.

Claims

1. A two-component low-viscosity ultra-low temperature epoxy resin adhesive, the raw materials include component A and component B, characterized in that: The component A is calculated by weight percentage and includes the following components: Bisphenol A epoxy resin 20-40%, aromatic epoxy resin 4-8%, polyurethane modified epoxy resin 6-10%, rubber toughening agent 1-2%, diluent 5-20%, and the balance is additives; The B component, calculated by mass percentage, includes the following components: Polyetheramine curing agent 10-40%, fatty amine curing agent 10-40%, aromatic amine curing agent 10-40%, phenolic amine curing agent 10-40%; The bisphenol A type epoxy resin comprises a first bisphenol A type epoxy resin and a second bisphenol A type epoxy resin; The viscosity of the first bisphenol A epoxy resin is 10-16 Pa·s, and the epoxy value is 0.48-0.54; the viscosity of the second bisphenol A epoxy resin is 6-8 Pa·s, and the epoxy value is 0.55-0.56; The mass ratio of the first bisphenol A epoxy resin to the second bisphenol A epoxy resin is 1:(0.2-0.4).

2. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The aromatic epoxy resin includes a first aromatic epoxy resin and a second aromatic epoxy resin; The viscosity of the first aromatic epoxy resin is 3-6 Pa·s, and the epoxy value is 0.80-0.90; the viscosity of the second aromatic epoxy resin is 0.55-0.85 Pa·s, and the epoxy value is 0.95-1.05; The mass ratio of the first aromatic epoxy resin to the second aromatic epoxy resin is 1:(0.5-0.7).

3. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The polyurethane-modified epoxy resin comprises a first polyurethane-modified epoxy resin and a second polyurethane-modified epoxy resin; The viscosity of the first polyurethane modified epoxy resin is 10-30 Pa·s, and the epoxy value is 0.45-0.53; the viscosity of the second polyurethane modified epoxy resin is 40-80 Pa·s, and the epoxy value is 0.50-0.56; The mass ratio of the first polyurethane-modified epoxy resin to the second polyurethane-modified epoxy resin is 1:(0.3-0.5).

4. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The rubber toughening agent is a composition of core-shell particles, polysulfide rubber and nitrile rubber, and the mass ratio of the core-shell particles, polysulfide rubber and nitrile rubber is 1:(0.05-0.1):(0.2-0.4).

5. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The diluent is an epoxy-based reactive diluent, including a first reactive diluent and a second reactive diluent; The density of the first reactive diluent is 1.1 g / cm 3 , the epoxy value is 0.77; the viscosity of the second reactive diluent is 4-10 mPa·s, and the epoxy value is 0.32-0.34; The mass ratio of the first active diluent to the second active diluent is 1:(0.7-0.8).

6. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The polyetheramine curing agent is one or more of D400, D2000 and T5000; The fatty amine curing agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; The aromatic amine curing agent is one or more of DDM, DDS, DEDDM and MOCA; The phenolic amine curing agent is one or more of PAA-300, PAA-400 and PAA-500.

7. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 1, characterized in that: The additives include a leveling agent, a silane coupling agent, a defoaming agent, silicon dioxide and nano-alumina, and the mass percentage of the additives in the component A is as follows: Leveling agent 0.1-0.5%, silane coupling agent 0.1-0.5%, defoaming agent 0.1-0.5%, silicon dioxide 20-30%, nano alumina 10-30%.

8. The two-component low-viscosity ultra-low temperature epoxy resin adhesive according to claim 7, characterized in that: The leveling agent is one or more of an organic silicon leveling agent, an acrylic leveling agent, and a fluorocarbon leveling agent; The silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane; The defoamer is one or more of an organosilicon defoamer, a polyether defoamer and a vinyl alcohol defoamer; The silicon dioxide is epoxy silicon dioxide; The nano-alumina is nano-alumina surface-modified by KH570.

9. A method for preparing a two-component low-viscosity ultra-low temperature epoxy resin adhesive, characterized in that: The following steps are involved: Mix bisphenol A epoxy resin, aromatic epoxy resin, polyurethane modified epoxy resin, rubber toughening agent and diluent in proportion, and stir evenly under room temperature and vacuum conditions to obtain component A; The polyetheramine curing agent, the aliphatic amine curing agent, the aromatic amine curing agent and the phenolic amine curing agent are mixed in proportion, and stirred evenly under vacuum conditions at room temperature to obtain component B.

10. A method for using the two-component low-viscosity ultra-low temperature epoxy resin adhesive according to any one of claims 1 to 8, characterized in that: The following steps are involved: Dam the pouring area with foam or rubber; Add the B component to the A component, stir at 300-400 rpm for 5-10 min, and pump to the casting area for casting; The mass ratio of component A to component B is 20:1; The pouring environment temperature is 13-30℃ and the environment humidity is less than 80%RH.