Two-component hybrid adhesive and preparation method thereof

Abstract

The invention relates to the technical field of adhesives, in particular to a two-component hybrid adhesive and a preparation method thereof, and the two-component hybrid adhesive comprises a component A and a component B, the component A is prepared from the following raw materials in parts by weight: 50 to 70 parts of silane modified polymer, 10 to 30 parts of reinforcing filler, 2 to 6 parts of silane coupling agent and 3 to 7 parts of curing agent; the component B is prepared from the following raw materials in parts by weight: 40 to 60 parts of modified epoxy resin, 10 to 30 parts of reinforcing filler, 0.5 to 3 parts of catalyst and 0.5 to 2 parts of curing accelerator; the silane modified polymer is selected from a silane modified polyether polymer or a silane modified polyurethane polymer; according to the invention, the combination of the silane modified polymer and the modified epoxy resin is optimized, and the compatibility of the silane modified polymer and the modified epoxy resin is improved, so that the tensile modulus of the two-component hybrid adhesive is improved, and the problems that the compatibility between components of the existing two-component hybrid battery adhesive is poor, so that the prepared material is relatively soft, and the service life of the material is prolonged are solved. The tensile modulus is relatively low, and the use requirement and the safety requirement of the battery glue cannot be met.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and in particular to a two-component hybrid adhesive and a preparation method thereof. Background Art

[0002] Battery structural adhesive is a key adhesive used within battery packs. Its primary function is to securely bond battery cells and protect them from external impact. It also increases the structural stability of the battery pack, preventing deformation during movement. With the rapid development of new energy vehicles, the industry is placing higher demands on the safety of battery structural adhesives. The tensile modulus, defined as the ratio of stress to strain during a material's elastic strain, reflects a material's ability to resist deformation under stress. A higher tensile modulus indicates a smaller deformation under the same stress and a greater stiffness.

[0003] Silane-modified polymers have excellent substrate adhesion and low-temperature elasticity and have been widely used in the development of hybrid battery adhesives. Hybrid adhesives based on silane-modified polymers and epoxy resins have appeared on the market. The two complement each other's advantages, giving the hybrid adhesives high toughness, as well as high strength and elongation over a wide temperature range. However, the components of existing two-component hybrid battery adhesives have poor compatibility, resulting in a softer material and a lower tensile modulus. When the product is applied to a battery pack, the stiffness of the entire battery pack is reduced, and the battery pack is easily deformed under external forces, which cannot meet the use and safety requirements of the battery adhesive. Summary of the Invention

[0004] In response to the problems raised in the background technology, the first purpose of the present invention is to propose a two-component hybrid adhesive, which optimizes the combination of silane-modified polymer and modified epoxy resin, thereby improving the compatibility between the silane-modified polymer and the modified epoxy resin, thereby improving the tensile modulus of the two-component hybrid adhesive, and solving the problem that the compatibility between the components of the existing two-component hybrid battery adhesive is poor, resulting in the prepared material being soft and having a low tensile modulus, which cannot meet the use and safety requirements of the battery adhesive.

[0005] The second purpose of the present invention is to propose a preparation method for the above-mentioned two-component hybrid adhesive. The prepared two-component hybrid adhesive has high bonding performance, high tensile modulus and high strength, which solves the problem that the components of the existing two-component hybrid battery glue are poorly compatible, resulting in the prepared material being soft and having a low tensile modulus, which cannot meet the use requirements and safety requirements of the battery glue.

[0006] To achieve the above-mentioned object, the present invention proposes a two-component hybrid adhesive comprising component A and component B; The component A comprises the following raw materials in parts by weight: 50-70 parts of silane-modified polymer, 10-30 parts of reinforcing filler, 2-6 parts of silane coupling agent and 3-7 parts of curing agent; The B component includes the following raw materials in parts by weight: 40-60 parts of modified epoxy resin, 10-30 parts of reinforcing filler, 0.5-3 parts of catalyst and 0.5-2 parts of curing accelerator; The silane-modified polymer is selected from a silane-modified polyether polymer or a silane-modified polyurethane polymer; When the silane-modified polymer is selected from silane-modified polyether polymer, the modified epoxy resin is selected from at least one of polyether-modified epoxy resin, polyurethane-modified epoxy resin and organosilicon-modified epoxy resin; When the silane-modified polymer is selected from silane-modified polyurethane polymer, the modified epoxy resin is selected from at least one of polyurethane-modified epoxy resin and polyether-modified epoxy resin.

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

[0008] Optionally, the silane-modified polyether polymer is a silane-alkoxy-terminated polyether polymer; and the silane-modified polyurethane polymer is a silane-alkoxy-terminated polyurethane polymer.

[0009] Optionally, the reinforcing filler of component A and the reinforcing filler of component B are respectively selected from one or more of light calcium carbonate, heavy calcium carbonate, nano calcium carbonate and fumed silica.

[0010] Optionally, the silane coupling agent is selected from one or more of vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

[0011] Optionally, the curing agent is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine and 4,4'-diaminodicyclohexylmethane.

[0012] Optionally, the catalyst is selected from one or more of dibutyltin dilaurate, dioctyltin dilaurate and chelated tin.

[0013] Optionally, the curing accelerator is water.

[0014] The present invention also provides a method for preparing a two-component hybrid adhesive, which is used to prepare any of the two-component hybrid adhesives described above, comprising the following steps: Step S1, dehydrating the silane-modified polymer and the reinforcing filler, then cooling to room temperature, adding a curing agent and a silane coupling agent, and mixing uniformly to obtain component A; Step S2, adding the modified epoxy resin, reinforcing filler, catalyst and curing accelerator into a reaction kettle, and mixing under vacuum conditions to obtain component B; Step S3: mixing the component A and the component B in proportion to obtain the two-component hybrid adhesive.

[0015] Optionally, the dehydration treatment in step S1 is performed under vacuum at 90° C.-110° C. for 2 hours; The mixing time in step S2 is 1 h to 2 h.

[0016] Compared with the prior art, the embodiments of the present invention have the following beneficial effects: 1. The silane-modified polymer of the present invention is selected from a silane-modified polyether polymer or a silane-modified polyurethane polymer. For the corresponding silane-modified polymer, the present invention adopts a modified epoxy resin formed by introducing a polymer having the same or similar polarity as the silane-modified polymer into the epoxy resin. When a silane-modified polyether polymer is used, at least one of a polyether-modified epoxy resin, a polyurethane-modified epoxy resin and a silicone-modified epoxy resin is used; when a silane-modified polyurethane polymer is used, at least one of a polyurethane-modified epoxy resin and a polyether-modified epoxy resin is used. The present invention optimizes the combination of silane-modified polymer and modified epoxy resin. By using a modified epoxy resin containing a polymer with the same or similar polarity as the silane-modified polymer, the compatibility between the silane-modified polymer and the modified epoxy resin is improved by utilizing the principle of like dissolves like, thereby improving the tensile modulus of the two-component hybrid adhesive. Moreover, the tensile modulus of the modified epoxy resin is relatively high, while the tensile modulus of the silane-modified polymer is relatively low. Therefore, by introducing a modified epoxy resin with a higher tensile modulus into the silane-modified polymer with a lower tensile modulus, the tensile modulus of the two-component hybrid adhesive can ultimately be improved. Therefore, the present invention has the characteristics of high tensile modulus and can meet the use requirements and safety requirements of battery adhesives.

[0017] 2. The present invention utilizes appropriate weight proportions of a reinforcing filler, a silane-modified polymer, and a modified epoxy resin to ultimately produce a two-component hybrid adhesive with a high tensile modulus. The present invention utilizes an appropriate weight proportion of a reinforcing filler to enhance the interactions between the silane-modified polymer and the reinforcing filler, as well as between the modified epoxy resin and the reinforcing filler, thereby improving the strength of the two-component hybrid adhesive. However, if the reinforcing filler is present in a large weight proportion, the high viscosity of the reinforcing filler will affect the mixing uniformity of component A and component B when they are mixed, resulting in a decrease in the mechanical properties of the two-component hybrid adhesive. Furthermore, a large weight proportion of the reinforcing filler will hinder the self-crosslinking of the silane-modified polymer and the crosslinking reaction between the modified epoxy resin and the curing agent, slowing the curing speed of the two-component hybrid adhesive and affecting the bonding strength and mechanical properties of the two-component hybrid adhesive. The present invention also utilizes a silane coupling agent to increase the crosslinking density of the silane-modified polymer and the modified epoxy resin, further improving the tensile modulus of the two-component hybrid adhesive. DETAILED DESCRIPTION

[0018] The present invention provides a two-component hybrid adhesive.

[0019] In an embodiment of the present invention, the two-component hybrid adhesive includes component A and component B; Component A includes the following raw materials in parts by weight: 50-70 parts of silane-modified polymer, 10-30 parts of reinforcing filler, 2-6 parts of silane coupling agent and 3-7 parts of curing agent; Component B includes the following raw materials in parts by weight: 40-60 parts of modified epoxy resin, 10-30 parts of reinforcing filler, 0.5-3 parts of catalyst and 0.5-2 parts of curing accelerator; The silane-modified polymer is selected from a silane-modified polyether polymer or a silane-modified polyurethane polymer; When the silane-modified polymer is selected from silane-modified polyether polymers, the modified epoxy resin is selected from at least one of polyether-modified epoxy resins, polyurethane-modified epoxy resins, and silicone-modified epoxy resins; When the silane-modified polymer is selected from silane-modified polyurethane polymer, the modified epoxy resin is selected from at least one of polyurethane-modified epoxy resin and polyether-modified epoxy resin.

[0020] The silane-modified polymer of the present invention is selected from a silane-modified polyether polymer or a silane-modified polyurethane polymer. For the corresponding silane-modified polymer, the present invention adopts a modified epoxy resin formed by introducing a polymer having the same or similar polarity as the silane-modified polymer into the epoxy resin. When a silane-modified polyether polymer is used, at least one of a polyether-modified epoxy resin, a polyurethane-modified epoxy resin and a silicone-modified epoxy resin is used; when a silane-modified polyurethane polymer is used, at least one of a polyurethane-modified epoxy resin and a polyether-modified epoxy resin is used. The present invention optimizes the combination of silane-modified polymer and modified epoxy resin. By using a modified epoxy resin containing a polymer with the same or similar polarity as the silane-modified polymer, the compatibility between the silane-modified polymer and the modified epoxy resin is improved by utilizing the principle of like dissolves like, thereby improving the tensile modulus of the two-component hybrid adhesive. Moreover, the tensile modulus of the modified epoxy resin is relatively high, while the tensile modulus of the silane-modified polymer is relatively low. Therefore, by introducing a modified epoxy resin with a higher tensile modulus into the silane-modified polymer with a lower tensile modulus, the tensile modulus of the two-component hybrid adhesive can ultimately be improved. Therefore, the present invention has the characteristics of high tensile modulus and can meet the use requirements and safety requirements of battery adhesives.

[0021] The present invention utilizes a reinforcing filler, a silane-modified polymer, and a modified epoxy resin in appropriate weight proportions to ultimately produce a two-component hybrid adhesive with a high tensile modulus. The present invention utilizes an appropriate weight proportion of the reinforcing filler to enhance the interaction between the silane-modified polymer and the reinforcing filler, as well as between the modified epoxy resin and the reinforcing filler, thereby improving the strength of the two-component hybrid adhesive. However, if the reinforcing filler is present in a large weight proportion, the high viscosity of component A and component B affects the mixing uniformity of the two components when they are mixed, resulting in a decrease in the mechanical properties of the two-component hybrid adhesive. Furthermore, a large weight proportion of the reinforcing filler can hinder the self-crosslinking of the silane-modified polymer and the crosslinking reaction between the modified epoxy resin and the curing agent, slowing the curing speed of the two-component hybrid adhesive and affecting the bonding strength and mechanical properties of the two-component hybrid adhesive. The present invention also utilizes a silane coupling agent to increase the crosslinking density of the silane-modified polymer and the modified epoxy resin, further improving the tensile modulus of the two-component hybrid adhesive.

[0022] It should be noted that, in terms of molecular polarity, the polarity of polyurethane polymer is similar to that of polyether polymer, and the polarity of polyether polymer is similar to that of silicone polymer, while the polarity of polyurethane polymer is greater than that of silicone polymer, and the polarity of the two are not similar.

[0023] It should be noted that if the present invention uses common epoxy resin, the tensile modulus of the two-component hybrid adhesive finally prepared can be lower, and this is because the compatibility of common epoxy resin and silane-modified polymer is poor.Usually common epoxy resin has higher polarity, contains a large amount of polar groups on its molecular chain, such as epoxy group, hydroxyl group etc., and these groups make the interaction force between common epoxy resin molecules stronger, so the polarity of common epoxy resin is higher.But in the molecular structure of silane-modified polymer, overall polarity is lower than common epoxy resin, and the polarity difference between common epoxy resin and silane-modified polymer can cause the intermolecular force between the two to be less than a little, i.e. the compatibility of common epoxy resin and silane-modified polymer is poor, it is difficult to form good interaction and uniform mixed system, so the tensile modulus of the two-component hybrid adhesive finally prepared is lower.

[0024] To further explain, ordinary epoxy resin refers to epoxy resin that has not been modified.

[0025] It should be noted that if a plasticizer is used in the components of the present invention, the tensile modulus of the two-component hybrid adhesive will be reduced. This is because the small molecules of the plasticizer will penetrate between the polymer chains of the silane-modified polymer and the modified epoxy resin, increasing the spacing between the polymer chains and weakening the intermolecular forces between the silane-modified polymer and the modified epoxy resin. Therefore, no plasticizer is used in the components of the present invention.

[0026] The present invention solves the problem that the components of the existing two-component hybrid battery glue have poor compatibility with each other, resulting in the prepared material being soft and having a low tensile modulus. When the product is applied to a battery pack, the rigidity of the entire battery pack is reduced, and the battery pack is easily deformed under the action of external force, thereby failing to meet the use and safety requirements of the battery glue.

[0027] In one embodiment of the present invention, the volume ratio of component A to component B is (1-2):1.

[0028] In the present invention, the volume ratio of component A to component B is (1-2):1. By using components A and B in an appropriate volume ratio, it is possible to ensure that the two-component hybrid adhesive obtained after mixing components A and B can be completely cured, so that the two-component hybrid adhesive has an appropriate viscosity and curing rate, and also has high bonding performance and tensile modulus.

[0029] In one embodiment of the present invention, the silane-modified polyether polymer is a silane-alkoxy terminated polyether polymer; and the silane-modified polyurethane polymer is a silane-alkoxy terminated polyurethane polymer.

[0030] The silane-modified polyether polymer is a silane-alkoxy-terminated polyether polymer, i.e., a silane-modified polyether polymer with a polyether backbone; the silane-modified polyurethane polymer is a silane-alkoxy-terminated polyurethane polymer, i.e., a silane-modified polyurethane polymer with a polyurethane backbone. The present invention employs a silane-alkoxy-terminated polyether polymer or a silane-alkoxy-terminated polyurethane polymer. When component A and component B are mixed, the silane-alkoxy groups at the ends of the silane-modified polyether polymer or silane-modified polyurethane polymer hydrolyze and condense to form a three-dimensional crosslinked network, achieving rapid curing without the foaming that occurs with polyurethane. Furthermore, the silane-modified polymer can form a two-component hybrid adhesive with epoxy resin, exhibiting high toughness and bonding properties, and high strength and elongation over a wide temperature range.

[0031] In one embodiment of the present invention, the reinforcing filler of component A and the reinforcing filler of component B are respectively selected from one or more of light calcium carbonate, heavy calcium carbonate, nano calcium carbonate and fumed silica.

[0032] In the present invention, the reinforcing filler of component A and the reinforcing filler of component B are respectively selected from one or more of light calcium carbonate, heavy calcium carbonate, nano calcium carbonate and fumed silica. By selecting suitable reinforcing fillers, they form high interfacial bonding strength with the silane-modified polymer and the modified epoxy resin, thereby improving the strength of the two-component hybrid adhesive and improving the mechanical properties of the two-component hybrid adhesive.

[0033] In one embodiment of the present invention, the silane coupling agent is selected from one or more of vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

[0034] Silane coupling agents, due to their unique molecular structure, can simultaneously generate a certain binding force with polar and non-polar substances. The present invention selects one or more of vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and diethylenetriaminopropyltrimethoxysilane as silane coupling agents to increase the crosslinking density of the silane-modified polymer and the modified epoxy resin, thereby further improving the compatibility between the silane-modified polymer and the modified epoxy resin, increasing the tensile modulus of the two-component hybrid adhesive, and also increasing the bonding strength of the two-component hybrid adhesive.

[0035] In one embodiment of the present invention, the curing agent is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine and 4,4'-diaminodicyclohexylmethane.

[0036] When components A and B are mixed, the curing agent undergoes a cross-linking reaction with the modified epoxy resin, and a three-dimensional network structure is gradually formed between components A and B, ultimately enabling the two-component hybrid adhesive to achieve an irreversible transformation from liquid to solid. The curing agent is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, and 4,4'-diaminodicyclohexylmethane. The resulting two-component hybrid adhesive has high strength and high bonding performance.

[0037] In one embodiment of the present invention, the catalyst is selected from one or more of dibutyltin dilaurate, dioctyltin dilaurate and chelated tin.

[0038] The catalyst is selected from one or more of dibutyltin dilaurate, dioctyltin dilaurate and chelated tin. In this way, the curing reaction speed of component A can be accelerated, component A can be fully cured, and the two-component hybrid adhesive can be further ensured to reach a higher degree of curing in a shorter time, so that the two-component hybrid adhesive has higher strength and bonding performance.

[0039] In one embodiment of the present invention, the curing accelerator is water.

[0040] When the curing accelerator is water, it can better promote the full curing of component A, further improve the speed and efficiency of the curing reaction, and shorten the curing time.

[0041] The present invention also provides a method for preparing a two-component hybrid adhesive, which is used to prepare the above-mentioned two-component hybrid adhesive, comprising the following steps: Step S1, dehydrating the silane-modified polymer and the reinforcing filler, then cooling to room temperature, adding a curing agent and a silane coupling agent, and mixing uniformly to obtain component A; Step S2, adding the modified epoxy resin, reinforcing filler, catalyst and curing accelerator into a reaction kettle, and mixing under vacuum conditions to obtain component B; Step S3: Mix component A and component B according to a certain proportion to obtain a two-component hybrid adhesive.

[0042] The present invention uses a modified epoxy resin containing a polymer with the same or similar polarity as the silane-modified polymer, and utilizes the principle of like dissolves like to achieve improved compatibility between the silane-modified polymer and the modified epoxy resin. Therefore, the two-component hybrid adhesive prepared by the present invention has high bonding performance, high tensile modulus, and high strength, which solves the problem that the components of the existing two-component hybrid battery adhesive have poor compatibility, resulting in the prepared material being soft and having a low tensile modulus, which cannot meet the use requirements and safety requirements of the battery adhesive.

[0043] Optionally, in step S3, component A and component B are mixed using a two-component mixing tube.

[0044] It is further explained that the two-component hybrid adhesive prepared by the present invention can be used as a battery structural adhesive in battery packs.

[0045] In one embodiment of the present invention, the dehydration treatment in step S1 is performed under vacuum at 90° C.-110° C. for 2 h. The mixing time in step S2 is 1 h-2 h.

[0046] To further illustrate, in step S1 , the vacuum degree is ≤ 0.1 MPa; in step S2 , the vacuum degree is ≤ 0.1 MPa.

[0047] In a preferred embodiment of the present invention, the dehydration treatment conditions in step S1 are: vacuum degree of 0.1 MPa, and dehydration at 100° C. for 2 h.

[0048] In a preferred embodiment of the present invention, the vacuum degree in step S2 is 0.1 MPa and the mixing time is 1.5 h.

[0049] For ease of understanding of the present invention, the present invention will be described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0050] If no specific techniques or conditions are specified in the examples, the experiments were carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. All reagents or instruments used without specifying the manufacturer are commercially available conventional products.

[0051] The amounts of raw materials used in Examples 1-5 are shown in Table 1 below; Table 1 Amounts of raw materials used in Examples 1-5 (in parts by weight) .

[0052] Example 1 In component A, the silane-modified polymer is selected from silane-modified polyether polymer (the silane-modified polyether polymer is a silane-modified polyether resin); the reinforcing filler is selected from nano-calcium carbonate and fumed silica (including 20 parts of nano-calcium carbonate and 5 parts of fumed silica); the silane coupling agent is selected from 3-aminopropyltrimethoxysilane; and the curing agent is selected from 2,4,6-tris(dimethylaminomethyl)phenol; In component B, the modified epoxy resin is selected from polyether modified epoxy resin; the reinforcing filler is selected from light calcium carbonate and nano calcium carbonate (including 15 parts of light calcium carbonate and 15 parts of nano calcium carbonate); the catalyst is selected from dioctyltin dilaurate; and the curing accelerator is water; The volume ratio of component A to component B is 2:1; Among them, silane-modified polyether resin: purchased from Zhonghua Enterprise Management (Shanghai) Co., Ltd., model SAX400; polyether-modified epoxy resin: purchased from Aidico (China) Investment Co., Ltd., model EP4000.

[0053] Example 2 In component A, the silane-modified polymer is selected from silane-modified polyurethane polymer (the silane-modified polyurethane polymer is a silane-modified polyurethane resin); the reinforcing filler is selected from nano-calcium carbonate; the silane coupling agent is selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and vinyltrimethoxysilane (including 5 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 1 part of vinyltrimethoxysilane); and the curing agent is selected from benzyldimethylamine; In component B, the modified epoxy resin is selected from polyurethane modified epoxy resin; the reinforcing filler is selected from nano calcium carbonate; the catalyst is selected from chelated tin; and the curing accelerator is water; The volume ratio of component A to component B is 1:1; Among them, silane-modified polyurethane resin: purchased from Jiangsu Ruiyang Antai New Material Technology Co., Ltd., model 3011; polyurethane-modified epoxy resin: purchased from Dow Chemical Company, model DER791.

[0054] Example 3 In component A, the silane-modified polymer is selected from silane-modified polyether polymer (the silane-modified polyether polymer is a silane-modified polyether resin); the reinforcing filler is selected from fumed silica and ground calcium carbonate (10 parts of fumed silica and 10 parts of ground calcium carbonate); the silane coupling agent is selected from 3-aminopropyltrimethoxysilane and vinyltrimethoxysilane (5 parts of 3-aminopropyltrimethoxysilane and 1 part of vinyltrimethoxysilane); and the curing agent is selected from 4,4'-diaminodicyclohexylmethane; In component B, the modified epoxy resin is selected from silicone modified epoxy resin; the reinforcing filler is selected from nano calcium carbonate; the catalyst is selected from dibutyltin dilaurate; and the curing accelerator is water; The volume ratio of component A to component B is 1:1; Among them, silane-modified polyether resin: purchased from Zhonghua Enterprise Management (Shanghai) Co., Ltd., model SAX400; silicone-modified epoxy resin: purchased from Shenzhen Jipeng Silicone Fluorine Materials Co., Ltd., model JP-H26.

[0055] Example 4 The difference between Example 4 and Example 1 is that in component B of Example 4, the modified epoxy resin is selected from polyurethane-modified epoxy resin, and the other raw material formulas are the same as those in Example 1; Wherein, polyurethane modified epoxy resin: purchased from Dow Chemical Company, model number is DER791.

[0056] Example 5 The difference between Example 5 and Example 1 is that in component A of Example 5, the silane-modified polymer is selected from a silane-modified polyurethane polymer (the silane-modified polyurethane polymer is a silane-modified polyurethane resin), and the modified epoxy resin is selected from a polyether-modified epoxy resin. The remaining raw material formula is the same as that of Example 1. Among them, silane-modified polyurethane resin: purchased from Jiangsu Ruiyang Antai New Material Technology Co., Ltd., model 3011; polyether-modified epoxy resin: purchased from Aidico (China) Investment Co., Ltd., model EP4000.

[0057] The preparation methods of Examples 1-5 are carried out according to the raw material dosages in Table 1, and include the following steps: Step S1, dehydrating the silane-modified polymer and the reinforcing filler under vacuum (vacuum degree of 0.1 MPa) at 100° C. for 2 h, then cooling to room temperature, adding a curing agent and a silane coupling agent, and mixing uniformly to obtain component A; Step S2: adding the modified epoxy resin, reinforcing filler, catalyst and curing accelerator into a reaction kettle and mixing them under vacuum conditions to obtain component B, the vacuum degree is 0.1 MPa, and the mixing time is 1.5 h; Step S3: Mix component A and component B according to a certain proportion to obtain a two-component hybrid adhesive.

[0058] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that ordinary epoxy resin is used in component B of Comparative Example 1, and the amounts of other raw materials and the preparation method are the same as those of Example 1; Among them, ordinary epoxy resin: purchased from Guodu Chemical (Kunshan) Co., Ltd., model number is YD127.

[0059] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the silane-modified polymer in component A of Comparative Example 2 is selected from a silane-modified polyurethane polymer (the silane-modified polyurethane polymer is a silane-modified polyurethane resin), and the modified epoxy resin in component B is selected from an organosilicon-modified epoxy resin. The remaining raw material amounts and preparation methods are the same as those in Example 1. Among them, silane-modified polyurethane resin: purchased from Jiangsu Ruiyang Antai New Material Technology Co., Ltd., model 3011; silicone-modified epoxy resin: purchased from Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd., model JP-H26.

[0060] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the weight parts of the reinforcing filler in component A of Comparative Example 3 is 40 parts, the weight parts of the reinforcing filler in component B is 40 parts, and the remaining raw material amounts and preparation methods are consistent with those of Example 1.

[0061] Mechanical properties test and result analysis: The two-component hybrid adhesives prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to mechanical property tests. The sample preparation method and mechanical property test steps are as follows. The test results are shown in Table 2. Sample preparation: dumbbell specimens were prepared according to GB / T 528 and cured at 25°C and 50% RH for 7 days.

[0062] Mechanical properties test: According to GB / T 528 standard, the sample was clamped on the fixture and stretched at a rate of 10 mm / min using a tensile testing machine. The tensile strength, elongation at break and tensile modulus of the sample were calculated according to the formula.

[0063] Table 2 Mechanical properties test results .

[0064] Result analysis: As can be seen from the data in Table 2, the two-component hybrid adhesives prepared in Examples 1-5 all outperformed those in Comparative Examples 1-3 in terms of tensile strength and tensile modulus. Examples 1-5 exhibited tensile strengths ranging from 7.6 MPa to 9.5 MPa, elongations at break ranging from 68% to 102%, and tensile moduli ranging from 49 MPa to 71 MPa. The present invention optimizes the silane-modified polymer and the modified epoxy resin, and by using a modified epoxy resin containing a polymer with the same or similar polarity as the silane-modified polymer, utilizes the principle of like dissolves like to achieve the improvement of the compatibility between the silane-modified polymer and the modified epoxy resin, thereby improving the tensile modulus of the two-component hybrid adhesive. The present invention introduces a modified epoxy resin with a higher tensile modulus into the silane-modified polymer with a lower tensile modulus. The prepared two-component hybrid adhesive has the characteristic of high tensile modulus. When the two-component hybrid adhesive is applied to a battery pack, the battery pack has appropriate stiffness. The two-component hybrid adhesive can meet the use requirements and safety requirements of battery adhesives.

[0065] As shown in Comparative Example 1, when component B is an ordinary epoxy resin, since the molecular chain of the ordinary epoxy resin contains a large number of polar groups, these groups make the interaction force between the ordinary epoxy resin molecules stronger, and the ordinary epoxy resin exhibits a higher polarity; however, the polyether segment and the silane part of the silane-modified polyether polymer are non-polar, so the polarity of the silane-modified polyether polymer is lower than that of the ordinary epoxy resin. The polarity difference between the two leads to a weak intermolecular force between the two. At this time, the compatibility between the silane-modified polyether polymer and the ordinary epoxy resin is poor, and it is difficult to form a good interaction. When components A and B are mixed, a uniform mixed system cannot be formed. Therefore, the tensile modulus of Comparative Example 1 is lower than that of Example 1.

[0066] As shown in Comparative Example 2, when component A is a silane-modified polyurethane polymer and component B is a silicone-modified epoxy resin, since the polarity of the silane-modified polyurethane polymer is higher and the silicone-modified epoxy resin exhibits low polarity, there is a difference in polarity between the two, resulting in poor compatibility between the silane-modified polyurethane polymer and the silicone-modified epoxy resin, and the tensile modulus of the hybrid adhesive cannot be improved. Therefore, the tensile modulus of Comparative Example 2 is lower than that of Example 1.

[0067] As shown in Comparative Example 3, when the weight of the reinforcing filler in component A is 40 parts and the weight of the reinforcing filler in component B is 40 parts, both the weight of the reinforcing filler in component A and the weight of the reinforcing filler in component B are relatively large. This not only leads to a higher viscosity and affects the mixing uniformity of the two components, but also hinders the self-crosslinking of the silane-modified polymer and the crosslinking reaction between the modified epoxy resin and the curing agent, resulting in a slower curing speed of the two-component hybrid adhesive. Therefore, the tensile strength and tensile modulus of Comparative Example 3 are lower than those of Example 1.

[0068] The above are only preferred embodiments of the present invention and are not intended to limit the patent scope of the present invention. All equivalent structural transformations made using the present invention specification under the inventive concept of the present invention, or direct / indirect applications in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A two-component hybrid adhesive, characterized in that: It includes component A and component B; The component A comprises the following raw materials in parts by weight: 50-70 parts of silane-modified polymer, 10-30 parts of reinforcing filler, 2-6 parts of silane coupling agent and 3-7 parts of curing agent; The B component includes the following raw materials in parts by weight: 40-60 parts of modified epoxy resin, 10-30 parts of reinforcing filler, 0.5-3 parts of catalyst and 0.5-2 parts of curing accelerator; The silane-modified polymer is selected from a silane-modified polyether polymer or a silane-modified polyurethane polymer; When the silane-modified polymer is selected from silane-modified polyether polymer, the modified epoxy resin is selected from at least one of polyether-modified epoxy resin, polyurethane-modified epoxy resin and organosilicon-modified epoxy resin; When the silane-modified polymer is selected from silane-modified polyurethane polymer, the modified epoxy resin is selected from at least one of polyurethane-modified epoxy resin and polyether-modified epoxy resin.

2. The two-component hybrid adhesive according to claim 1, characterized in that: The volume ratio of the component A to the component B is (1-2):

1.

3. The two-component hybrid adhesive according to claim 2, characterized in that: The silane-modified polyether polymer is a silane-alkoxy-terminated polyether polymer; and the silane-modified polyurethane polymer is a silane-alkoxy-terminated polyurethane polymer.

4. The two-component hybrid adhesive according to claim 2, characterized in that: The reinforcing filler of the component A and the reinforcing filler of the component B are respectively selected from one or more of light calcium carbonate, heavy calcium carbonate, nano calcium carbonate and fumed silica.

5. The two-component hybrid adhesive according to claim 1, characterized in that: The silane coupling agent is selected from one or more of vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

6. The two-component hybrid adhesive according to claim 1, characterized in that: The curing agent is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine and 4,4'-diaminodicyclohexylmethane.

7. The two-component hybrid adhesive according to claim 1, characterized in that: The catalyst is selected from one or more of dibutyltin dilaurate, dioctyltin dilaurate and chelated tin.

8. The two-component hybrid adhesive according to claim 1, characterized in that: The curing accelerator is water.

9. A method for preparing a two-component hybrid adhesive, for preparing the two-component hybrid adhesive according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step S1, dehydrating the silane-modified polymer and the reinforcing filler, then cooling to room temperature, adding a curing agent and a silane coupling agent, and mixing uniformly to obtain component A; Step S2, adding the modified epoxy resin, reinforcing filler, catalyst and curing accelerator into a reaction kettle, and mixing under vacuum conditions to obtain component B; Step S3: mixing the component A and the component B in proportion to obtain the two-component hybrid adhesive.

10. The method for preparing a two-component hybrid adhesive according to claim 9, characterized in that: The dehydration treatment condition in step S1 is to dehydrate at 90°C-110°C for 2h under vacuum; The mixing time in step S2 is 1 h to 2 h.