Two-component silane-modified polyether adhesive, its preparation method and application

Abstract

The application discloses a two-component silane modified polyether adhesive as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The two-component silane modified polyether adhesive provided by the application can realize good mechanical properties and storage stability of the two-component silane modified polyether adhesive by selecting a certain structure of acrylate and a plasticizer to form a mixture, and reasonably matching the A component and the B component, and has good bonding performance to low surface energy materials. Meanwhile, the two-component silane modified polyether adhesive provided by the application has fast curing speed, low odor and excellent storage performance. In addition, the preparation method of the two-component silane modified polyether adhesive is simple in operation and is beneficial to actual production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to a two-component silane-modified polyether adhesive, its preparation method, and its application. Background Technology

[0002] As the market size of the new energy vehicle industry continues to expand, the demand for power batteries is also increasing. Currently, the main forms of power battery cells on the market are prismatic cells, pouch cells, and cylindrical cells. During the assembly of power batteries, adhesives are needed to bond and fix cells to cells, cells to foam, cells to module housings, and cells to condenser plates. Because high-frequency vibrations occur during vehicle operation, and the charging and discharging process of power batteries generates a large amount of heat, the bonding strength and fatigue resistance of the adhesives at high temperatures are particularly critical. Currently, most mainstream prismatic power batteries use an insulating blue film on their surface to improve insulation. This insulating blue film is a relatively difficult polymer material to bond. Currently, mainstream two-component polyurethane structural adhesives have poor adhesion to the insulating blue film.

[0003] Silane-modified polyether resins have been widely used in the construction and industrial fields due to their excellent properties. However, commercially available silane-modified polyether products are mainly used for low-strength elastic bonding and sealing. Their slow curing speed and low strength limit their application in the power battery field. Epoxy adhesives, as a type of high-strength, fast-curing adhesive, have wide applications in the industrial field. However, epoxy adhesives have poor toughness, with their elongation at break generally not exceeding 10%, limiting their application in the battery industry.

[0004] Chinese patent CN115558452A discloses a "two-component adhesive for bonding power batteries and its preparation method," which includes component A and component B. Component A includes the following raw materials in parts by weight: 25-35 parts of silane-modified polyether polymer, 20-30 parts of powder, 25-35 parts of inorganic flame retardant filler, 2-5 parts of epoxy curing agent, 1-3 parts of crosslinking agent, and 2-5 parts of coupling agent. Component B includes the following raw materials in parts by weight: 20-25 parts of organosilicon-modified bisphenol A epoxy resin, 5-10 parts of plasticizer, 55-65 parts of inorganic flame retardant filler, 1-2 parts of thixotropic agent, and 1-2 parts of catalyst. Component B of this adhesive does not contain added water. The curing of the silane-modified polyether polymer in component A mainly relies on the moisture in the filler in component B. If the moisture content of component B is too high, it will reduce the storage stability of component B; if the moisture content of component B is too low, it will result in a very slow curing speed of the silane-modified polyether. Chinese patent CN108048015B discloses a "two-component silane-modified polyether adhesive for bonding wind turbine blade cover plates," which places both epoxy resin and silane-modified polyether in component A. However, the compatibility between the two is generally poor, and phase separation is prone to occur, failing to form an ideal interpenetrating network structure. The final product has low strength and poor adhesion to low surface energy materials. Furthermore, when using epoxy resin, tertiary amine epoxy curing accelerators such as DMP-30 are used to achieve faster curing speeds, resulting in a strong odor and an unfriendly preparation environment. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a two-component silane-modified polyether adhesive with excellent storage stability, high mechanical strength, good adhesion, low odor, and fast curing speed, as well as its preparation method and application.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a two-component silane-modified polyether adhesive, the two-component silane-modified polyether adhesive comprising component A and component B;

[0007] Component A comprises the following components in parts by weight: 50-80 parts of silane-modified polyether, 10-40 parts of a mixture of acrylate and plasticizer, 30-60 parts of epoxy resin, 40-80 parts of flame-retardant filler, 0.5-2 parts of UV additive, 0.5-2 parts of antioxidant, 0.5-2.5 parts of thixotropic agent, 0.5-2 parts of colorant, and 1-5 parts of dehydrating agent;

[0008] Component B comprises the following components in parts by weight: 10-20 parts epoxy curing agent, 2-4 parts organotin catalyst, 1-5 parts tackifier, 10-20 parts flame retardant filler, and 1-5 parts thixotropic agent.

[0009] The structural formula of the acrylate is shown in Formula I;

[0010]

[0011] The ratio of x, y, and z is x:y:z = (10-18):(1-2):(1-4);

[0012] In the mixture of acrylate and plasticizer, the mass ratio of acrylate to plasticizer is acrylate:plasticizer = (2-6):1.

[0013] The two-component silane-modified polyether adhesive provided by this invention exhibits excellent mechanical properties and storage stability, and also demonstrates good adhesion to low surface energy materials such as insulating blue films. Specifically, by adding acrylates with a specific structure and mixing them with plasticizers in a certain mass ratio, this invention significantly improves the compatibility between epoxy resin and silane-modified polyether, thereby increasing the product's strength and elongation. Furthermore, by mixing the epoxy curing agent with an organotin catalyst and other components to form component B, the curing speed of the product can be greatly improved. Simultaneously, this invention avoids the operational complexity and low storage stability issues caused by adding both silane-modified polyether and organotin catalyst to component A and simultaneously heating and dehydrating component A in existing technologies, thus achieving good storage stability for the product.

[0014] For example, the silane-modified polyether resin of the present invention may be at least one of SAX350, SAX400 and SAX750 produced by Kaneka Corporation of Japan.

[0015] Preferably, the silane-modified polyether resin is SAX750 from Kaneka Corporation of Japan.

[0016] In a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, the ratio of x, y, and z in the acrylate is x:y:z = (12-14):(1-2):(1-4).

[0017] This invention has discovered that resins containing a polyolefin backbone and an acrylate structure exhibit better wetting effects on low surface energy materials, effectively enhancing the adhesion of adhesives to substrates. This invention utilizes dialkoxy-based acrylate polymers; the dialkoxy acrylate structure has lower reactivity and better storage stability compared to trialkoxy structures. Furthermore, the acrylates provided by this invention, containing alkoxysilane structures and epoxy groups, promote the compatibility of silane-modified polyether resins and epoxy resins, resulting in improved strength and elongation of the final adhesive, while also exhibiting higher shear strength for low surface energy materials. Moreover, further selecting the x, y, z ratios in the acrylate structure within the aforementioned range further enhances the compatibility between epoxy resins and silane-modified polyether resins, leading to a product with superior overall performance.

[0018] In a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, the mass ratio of the acrylate to the plasticizer in the mixture of acrylate and plasticizer is acrylate:plasticizer = (4-5):1.

[0019] The present invention has found that the mass ratio of acrylate to plasticizer also affects the performance of the product. When the mass ratio of the two is further selected to be (4-5):1, an adhesive with better mechanical properties can be obtained.

[0020] In a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, the acrylate comprises the following raw materials in parts by weight:

[0021] 150-181 parts of methyl methacrylate, 14-29 parts of glycidyl methacrylate, 23-93 parts of γ-methacryloyloxypropylmethyldimethoxysilane, 1-5 parts of initiator, 0.1-1 parts of chain transfer agent, and 45-55 parts of organic solvent.

[0022] The present invention has found that when acrylates are prepared using raw materials within the above-mentioned mass fraction range, acrylates with x, y, z ratios within the range of the present invention can be obtained.

[0023] In a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, the initiator includes at least one of hydrogen peroxide, ditert-alkyl peroxide, acyl peroxide, carboxylic acid peroxide, and dicarbonate peroxide.

[0024] And / or, the chain transfer agent comprises at least one of n-dodecyl mercaptan (NDM), tert-dodecyl mercaptan (TDM), 2-ethylhexyl 3-mercaptopropionate (2-EHMP), 2-methylhexyl 3-mercaptoacetic acid (2-EQMP), and 2,4-diphenyl-4-methyl-1-pentene (TPMS);

[0025] And / or, the organic solvent includes at least one of toluene, xylene, and ethyl acetate.

[0026] Preferably, the initiator includes at least one of tert-butyl hydroperoxide (TBHP) and di-tert-pentyl peroxide (DTAP).

[0027] As a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, the method for preparing the mixture of acrylate and plasticizer includes the following steps:

[0028] (1) Methyl methacrylate, glycidyl methacrylate, γ-methacryloyloxypropylmethyldimethoxysilane, initiator and chain transfer agent were refluxed in an organic solvent to obtain a mixture of acrylate and organic solvent.

[0029] (2) Add plasticizer to the mixture of acrylate and organic solvent, and then remove the organic solvent to obtain a mixture of acrylate and plasticizer.

[0030] In the preparation method of the mixture of acrylate and plasticizer provided by the present invention, in step (1), a mixture of acrylate and organic solvent is prepared. At this time, the organic solvent can be directly removed to obtain acrylate, and then the acrylate and plasticizer are mixed to form a mixture of acrylate and plasticizer. Alternatively, the preparation method in the present invention can be used to mix the plasticizer with the mixture of acrylate and organic solvent and then remove the organic solvent. In this way, the efficiency of the organic solvent removal process is higher and the residual amount of organic solvent is lower in actual operation.

[0031] Preferably, the organic solvent is toluene.

[0032] Preferably, the reflux reaction time is 1.5-2.5 hours.

[0033] Preferably, the removal of organic solvent is achieved by vacuum distillation at 110-120°C to remove toluene.

[0034] As a preferred embodiment of the two-component silane-modified polyether adhesive of the present invention, at least one of the following (a)-(j) is used:

[0035] (a) The plasticizer comprises at least one of diisononyl cyclohexane 1,2-dicarboxylate (DINCH), dioctyl(2-ethylhexyl) 4,5-epoxytetrahydrophthalic acid (EPS), and alkyl sulfonate phenyl ester (Mesamoll);

[0036] (b) The epoxy resin includes at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin;

[0037] (c) The flame-retardant filler includes at least one of aluminum hydroxide and magnesium hydroxide;

[0038] (d) The UV additives include at least one of light stabilizers and UV absorbers;

[0039] (e) The antioxidants include hindered phenolic antioxidants;

[0040] (f) The thixotropic agent comprises a specific surface area ≥150 m² 2 / g of hydrophobic fumed silica;

[0041] (g) The color powder is at least one of pigment carbon black and rutile titanium dioxide;

[0042] (h) The dehydrating agent includes at least one of hexamethyldisilazane and vinyltrimethoxysilane;

[0043] (i) The epoxy curing agent includes polyetheramine curing agents;

[0044] (j) The tackifier comprises at least one of γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and oligomeric aminosilane.

[0045] For example, the light stabilizer may be at least one of the hindered amine light stabilizers TINUVIN 765 and TINUVIN 770 manufactured by BASF.

[0046] Preferably, the ultraviolet absorber includes benzotriazole ultraviolet absorbers.

[0047] For example, the ultraviolet absorber may be at least one of the benzotriazole ultraviolet absorbers TINUVIN571, TINUVIN 326, and TINUVIN 328 manufactured by BASF.

[0048] For example, the antioxidant may be at least one of IRGANOX 1135, IRGANOX 1010, and IRGANOX 245 manufactured by BASF.

[0049] For example, the epoxy curing agent may be at least one of Baxxodur EC130 and Baxxodur EC280 manufactured by BASF.

[0050] For example, the organotin catalyst may be at least one of NEOSTANN U-220H, NEOSTANN S-1, and NEOSTANN U-303 produced by Nitto Chemical Corporation of Japan.

[0051] In a second aspect, the present invention provides a method for preparing the two-component silane-modified polyether adhesive, the method comprising the following steps:

[0052] (1) Preparation of component A: Mix and stir the components other than the dehydrating agent, then add the dehydrating agent until the water content of component A is 2000-3500ppm, then vacuum, discharge the material, and obtain component A;

[0053] (2) Preparation of component B: The epoxy curing agent and organotin catalyst are mixed and stirred, and then the tackifier, thixotropic agent and flame retardant filler are added and dispersed at a temperature below 50°C. Then, the mixture is vacuumed and discharged to obtain component B.

[0054] In the preparation method provided by this invention, during the preparation of component A, the water content of component A is controlled at 2000-3500ppm by adding a dehydrating agent at the end, which can significantly improve the storage stability of component A; in the preparation of component B, by mixing epoxy curing agent and organotin catalyst first, the two pre-react to form a complex, which can effectively improve the curing reaction speed and reduce odor without adding tertiary amine accelerator.

[0055] In a preferred embodiment of the preparation method of the present invention, in step (1), the mixing and stirring time is 60-120 min; the vacuum degree of the vacuum is (-0.09) to (-0.1) MPa, and the time is 25-35 min.

[0056] In a preferred embodiment of the preparation method of the present invention, in step (2), the mixing and stirring time is 100-140 min; the dispersion time is 25-35 min; the vacuum degree of vacuuming is (-0.09) to (-0.1) MPa, and the time is 25-35 min.

[0057] In a third aspect, the present invention provides the application of the two-component silane-modified polyether adhesive in the bonding of insulating blue film materials for power batteries.

[0058] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0059] The two-component silane-modified polyether adhesive provided by this invention achieves excellent mechanical properties and storage stability by first forming a mixture of acrylates and plasticizers with a specific structure, and then rationally combining components A and B. It also exhibits good adhesion to materials with low surface energy. Furthermore, the two-component silane-modified polyether adhesive provided by this invention has a fast curing speed, low odor, and excellent storage performance. Specifically, the obtained two-component silane-modified polyether adhesive has a tensile strength above 10.8 MPa, an elongation above 75%, a tensile shear strength above 5.2 MPa, an odor rating below 3.0, a pot life below 27 minutes, and a viscosity change rate below 28%. Moreover, the preparation method of the two-component silane-modified polyether adhesive provided by this invention is simple to operate and beneficial for practical production. Attached Figure Description

[0060] Figure 1 Infrared results for mixture 1 of acrylate and plasticizer. Detailed Implementation

[0061] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0062] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0063] Silane-modified polyether resin 1: KANEKA MS POLYMER SAX750, Kaneka Trading (Shanghai) Co., Ltd.;

[0064] Silane-modified polyether resin 2: KANEKA MS POLYMER SAX400, Kaneka Trading (Shanghai) Co., Ltd.;

[0065] Silane-modified polyether resin 3: KANEKA MS POLYMER SAX350, Kaneka Trading (Shanghai) Co., Ltd.;

[0066] Plasticizer: Diisononyl 1,2-dicarboxylate, commercially available;

[0067] Epoxy resin: Bisphenol A type epoxy resin, SM828, Jiangsu Sanmu Group Co., Ltd.;

[0068] Flame-retardant filler: aluminum hydroxide, commercially available;

[0069] UV additives: The light stabilizer is TINUVIN 765, BASF; the UV absorber is TINUVIN 571, BASF; the light stabilizer and UV absorber are a mixture formed in a 1:1 mass ratio.

[0070] Antioxidant: IRGANOX 1135, BASF;

[0071] Thixotropic agent: hydrophobic fumed silica with a specific surface area ≥150 m² 2 / g, HDK18, Wacker Chemie;

[0072] Pigment: Rutile titanium dioxide, commercially available;

[0073] Dehydrating agent: Hexamethyldisilazane, commercially available;

[0074] Epoxy curing agent: Baxxodur EC130, BASF;

[0075] Organotin catalyst: NEOSTANN U-220H, Nitto Kasei Corporation, Japan;

[0076] Tackifier: γ-aminopropyltrimethoxysilane, commercially available;

[0077] Initiator: tert-butyl hydrogen peroxide, commercially available;

[0078] Chain transfer agent: n-dodecyl mercaptan, commercially available.

[0079] Example

[0080] This invention provides a mixture of acrylate and plasticizer, wherein the raw materials (parts by mass) of the acrylate and the x, y, z ratios of the prepared acrylate are shown in Table 1.

[0081] Table 1

[0082]

[0083]

[0084] The preparation method of the mixture 1 of acrylate and plasticizer is as follows:

[0085] (1) Weigh out methyl methacrylate, glycidyl methacrylate, γ-methacryloyloxypropylmethyldimethoxysilane, initiator and chain transfer agent in toluene according to the corresponding component parts of acrylate 1 in Table 1, and reflux at 100°C for 2 hours to obtain a mixture of acrylate 1 and toluene.

[0086] (2) Add plasticizer to the mixture of acrylate 1 and toluene, heat to 115°C, remove toluene in a vacuum distillation apparatus to obtain a mixture of acrylate and plasticizer 1; wherein the mass ratio of acrylate 1 to plasticizer is 4:1.

[0087] The only difference between the acrylate and plasticizer mixtures 2-6 and acrylate and plasticizer mixture 1 is that in step (1), the proportion of acrylate raw materials is changed according to the proportion of components in Table 1 to obtain different acrylate and toluene mixtures.

[0088] The infrared spectrum of the prepared acrylate and plasticizer mixture 1 is shown in Figure 1. Figure 1 As shown, from Figure 1 As can be seen, the raw materials in the synthesis of acrylate reacted successfully.

[0089] The only difference between the acrylate and plasticizer mixture 7 and the acrylate and plasticizer mixture 1 is that the amount of plasticizer added in step (2) is changed so that the mass ratio of acrylate 1 to plasticizer is 5:1.

[0090] The only difference between the acrylate and plasticizer mixture 8 and the acrylate and plasticizer mixture 1 is that the amount of plasticizer added in step (2) is changed so that the mass ratio of acrylate 1 to plasticizer is 2:1.

[0091] The only difference between the acrylate and plasticizer mixture 9 and the acrylate and plasticizer mixture 1 is that the amount of plasticizer added in step (2) is changed so that the mass ratio of acrylate 1 to plasticizer is 6:1.

[0092] The only difference between the acrylate and plasticizer mixture 10 and the acrylate and plasticizer mixture 1 is that the amount of plasticizer added in step (2) is changed so that the mass ratio of acrylate 1 to plasticizer is 1:1.

[0093] The only difference between the acrylate and plasticizer mixture 11 and the acrylate and plasticizer mixture 1 is that the amount of plasticizer added in step (2) is changed so that the mass ratio of acrylate 1 to plasticizer is 10:1.

[0094] Examples 1-5

[0095] This invention provides a two-component silane-modified polyether adhesive, the components (parts by mass) of which are shown in Table 2.

[0096] Table 2

[0097]

[0098] The preparation method of the two-component silane-modified polyether adhesive provided in Example 1 includes the following steps:

[0099] (1) Preparation of component A: Add the components other than the dehydrating agent to a planetary mixer and mix at 500 rpm for 80 min. Then add the dehydrating agent until the water content of component A is 2000-3500 ppm. Then, under a vacuum of -0.1 MPa, vacuum for 30 min and discharge to obtain component A.

[0100] (2) Preparation of component B: The epoxy curing agent and organotin catalyst were added to a planetary mixer and mixed at 300 rpm for 120 min. Then, the tackifier, thixotropic agent and flame retardant filler were added at 50°C and stirred at 600 rpm for 30 min. Then, the mixture was vacuumed for 30 min under a vacuum of -0.1 MPa to obtain component B.

[0101] The preparation methods of the two-component silane-modified polyether adhesives provided in Examples 2-5 are consistent with those provided in Example 1.

[0102] Example 6

[0103] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 2 of acrylate and plasticizer.

[0104] Example 7

[0105] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 3 of acrylate and plasticizer.

[0106] Example 8

[0107] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 4 of acrylate and plasticizer.

[0108] Example 9

[0109] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 7 of acrylate and plasticizer.

[0110] Example 10

[0111] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 8 of acrylate and plasticizer.

[0112] Example 11

[0113] This invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 9 of acrylate and plasticizer.

[0114] Comparative Example 1

[0115] The present invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 5 of acrylate and plasticizer.

[0116] Comparative Example 2

[0117] The present invention provides a comparative example of a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 6 of acrylate and plasticizer.

[0118] Comparative Example 3

[0119] The present invention provides a comparative example of a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 10 of acrylate and plasticizer.

[0120] Comparative Example 4

[0121] The present invention provides a comparative example of a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that it uses a mixture 11 of acrylate and plasticizer.

[0122] Comparative Example 5

[0123] This invention provides a comparative example of a two-component silane-modified polyether adhesive, the preparation method of which includes the following steps:

[0124] (1) Preparation of acrylate 1: According to the mass parts of the components of acrylate 1, methyl methacrylate, glycidyl methacrylate, γ-methacryloyloxypropylmethyldimethoxysilane, initiator and chain transfer agent were weighed into toluene and refluxed at 100°C for 2 hours to obtain a mixture of acrylate 1 and toluene. Then, the mixture was heated to 115°C and the toluene was removed in a vacuum distillation apparatus to obtain acrylate 1.

[0125] (2) Preparation of component A: According to the component mass parts of Example 1 in Table 2 (except that the acrylate and plasticizer do not form a mixture first, the rest are the same, that is, the mass parts of acrylate 1 in this comparative example are 20 parts and the mass parts of plasticizer are 5 parts), the components except the dehydrating agent are added to the planetary mixer and mixed. The mixture is stirred at 500 rpm for 80 min. Then the dehydrating agent is added until the water content of component A is 2000-3500 ppm. Then the mixture is vacuumed for 30 min under a vacuum degree of -0.1 MPa to obtain component A.

[0126] (3) Preparation of component B: The epoxy curing agent and organotin catalyst were added to a planetary mixer and mixed at 300 rpm for 120 min. Then, the tackifier, thixotropic agent and flame retardant filler were added at 50°C and stirred at 600 rpm for 30 min. Then, the mixture was evacuated for 30 min under a vacuum of -0.1 MPa to obtain component B.

[0127] Comparative Example 6

[0128] This invention provides a two-component silane-modified polyether adhesive as a comparative example. The only difference between this two-component silane-modified polyether adhesive and Example 1 is the preparation method. The preparation method of this comparative example includes the following steps:

[0129] (1) Preparation of component A: Add the components other than the dehydrating agent to a planetary mixer and mix at 500 rpm for 80 min. Then add the dehydrating agent until the water content of component A is 2000-3500 ppm. Then, under a vacuum of -0.1 MPa, vacuum for 30 min and discharge to obtain component A.

[0130] (2) Preparation of component B: Epoxy curing agent, organotin catalyst, tackifier, thixotropic agent and flame retardant filler were added to a planetary mixer and mixed. The mixture was stirred at 300 rpm for 120 min. Then, the mixture was evacuated for 30 min under a vacuum of -0.1 MPa to obtain component B.

[0131] Comparative Example 7

[0132] The present invention provides a two-component silane-modified polyether adhesive, the only difference between the two-component silane-modified polyether adhesive and Example 1 is that in step (1), a dehydrating agent is added until the water content of component A is 1000-1500 ppm.

[0133] Comparative Example 8

[0134] The present invention provides a two-component silane-modified polyether adhesive. The only difference between the two-component silane-modified polyether adhesive and Example 1 is that no dehydrating agent is added in step (1), and the water content of component A is 4000-4500 ppm.

[0135] Example of effect

[0136] The performance of the two-component silane-modified polyether adhesives prepared in Examples 1-11 and Comparative Examples 1-8 is verified by the following tests (items 1-4) performed on the mixture of components A and B:

[0137] 1. Tensile strength and elongation: Tested according to the methods specified in GB / T 528-2009;

[0138] 2. Tensile shear strength: The test was conducted according to the method specified in GB / T 7124-2008. The test substrate was an aluminum sheet with a blue insulating coating. This value can be used to evaluate the adhesion of the two-component silane-modified polyether adhesive.

[0139] 3. Odor test: The test shall be conducted in accordance with the method specified in VDA270-2016. The sample treatment conditions shall be 80℃ for 2 hours. The evaluation level shall be 1-5, where 0 is odorless and 5 is a strong odor that can be smelled and causes a strong irritation to the human body.

[0140] 4. Pot life: Refer to GB 7123.1-2015 Method 4, tack test. This value can evaluate the curing speed of two-component silane modified polyether adhesive.

[0141] 5. Storage stability: Component A was packaged in a sealant and placed in a 40℃ water bath for 14 days. The viscosity change rate before and after the storage was tested. The viscosity change rate was calculated as (viscosity after storage - viscosity before storage) / viscosity before storage * 100%. The viscosity was tested according to the viscosity specifications in GB / T 2794-2013. A #7 rotor was used, with a rotation speed of 20 r / min. The test temperature was 20℃ for 120 seconds.

[0142] 6. Moisture content test of component A: The moisture content was tested using the Karl Fischer volumetric method;

[0143] The test results are shown in Table 3.

[0144] Table 3

[0145]

[0146] As can be seen from Table 3, when the preparation method provided in this invention is used, the obtained two-component silane-modified polyether adhesive has excellent mechanical strength, adhesive strength, low odor, fast curing speed and good storage stability; specifically, the tensile strength of the obtained product is above 10.8 MPa, the elongation is above 75%, the tensile shear strength is above 5.2 MPa, the odor level is below 3.0, the pot life is below 27 min, and the viscosity change rate in the storage stability test is below 28%.

[0147] As can be seen from Examples 1, 6-8, and Comparative Examples 1-2, the structure of the acrylate affects the overall performance of the product. When the ratio of x, y, z in the acrylate is further selected as x:y:z = (12-14):(1-2):(1-4), the overall performance of the obtained product is better, with tensile strength above 12.9 MPa, elongation above 118%, tensile shear strength above 6.2 MPa, odor rating below 3.0, pot life below 22 min, and viscosity change rate below 22% in storage stability test. However, when the acrylate used is not the substance provided in this invention, the overall performance of the obtained product decreases significantly. Compared with Example 1, the elongation of the product in Comparative Example 1 decreases significantly, and the tensile strength and tensile shear strength of the product in Comparative Example 2 decrease significantly.

[0148] As can be seen from Examples 1, 9-11, and Comparative Examples 3-4, the mass ratio of acrylate and plasticizer in the mixture also affects the overall performance of the product. When the mass ratio is within the range given in this invention, the resulting product exhibits superior overall performance, with tensile strength exceeding 13.7 MPa, elongation exceeding 107%, tensile shear strength exceeding 6.3 MPa, odor rating below 3.0, pot life below 23 minutes, and viscosity change rate below 22% in storage stability tests. Conversely, when the mass ratio of acrylate and plasticizer used is outside the range given in this invention, the overall performance of the resulting product significantly decreases. Compared to Example 1, the tensile strength and tensile shear strength of the product in Comparative Example 3 are lower, while the pot life is also somewhat increased. The product in Comparative Example 4 has an excessively strong odor, and the elongation also shows a significant downward trend.

[0149] As can be seen from Example 1 and Comparative Example 5, when the acrylate and plasticizer are not mixed together first during the preparation process, but are mixed with other components simultaneously, the resulting product has a stronger odor, and compared with Example 1, the tensile strength and elongation of the resulting product also show a certain downward trend.

[0150] As can be seen from Example 1 and Comparative Example 6, when the epoxy curing agent and organotin catalyst are not mixed first during the preparation process, but are mixed simultaneously with other components, the product has a pot life of up to 78 minutes, and the tensile strength and tensile shear strength of the product also show a certain decreasing trend, while the odor shows an increasing trend.

[0151] As can be seen from Examples 1 and Comparative Examples 7-8, the water content in component A also affects the overall performance of the product. When the water content in component A is not within the range given in this invention, specifically, when the water content of component A in Comparative Example 7 is too low, the pot life of the obtained product increases significantly, reaching 40 minutes. When the water content of component A in Comparative Example 8 is too high, the viscosity of the obtained product increases by 55%, both exceeding the requirements.

[0152] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A two-component silane-modified polyether adhesive, characterized in that, The two-component silane-modified polyether adhesive comprises component A and component B; Component A comprises the following components in parts by weight: 50-80 parts of silane-modified polyether, 10-40 parts of a mixture of acrylate and plasticizer, 30-60 parts of epoxy resin, 40-80 parts of flame-retardant filler, 0.5-2 parts of UV additive, 0.5-2 parts of antioxidant, 0.5-2.5 parts of thixotropic agent, 0.5-2 parts of colorant, and 1-5 parts of dehydrating agent; Component B comprises the following components in parts by weight: 10-20 parts epoxy curing agent, 2-4 parts organotin catalyst, 1-5 parts tackifier, 10-20 parts flame retardant filler, and 1-5 parts thixotropic agent. The structural formula of the acrylate is shown in Formula I; Formula I The ratio of x, y, and z is x:y:z = (12-14):(1-2):(1-2); In the mixture of acrylate and plasticizer, the mass ratio of acrylate to plasticizer is acrylate:plasticizer = (2-6):1; The preparation method of the two-component silane-modified polyether adhesive includes the following steps: (1) Preparation of component A: Mix and stir the components other than the dehydrating agent, then add the dehydrating agent until the water content of component A is 2000-3500ppm, then vacuum, discharge the material, and obtain component A; (2) Preparation of component B: The epoxy curing agent and organotin catalyst are mixed and stirred, and then the tackifier, thixotropic agent and flame retardant filler are added and dispersed at a temperature below 50°C. Then, the mixture is vacuumed and discharged to obtain component B.

2. The two-component silane-modified polyether adhesive according to claim 1, characterized in that, In the mixture of acrylate and plasticizer, the mass ratio of acrylate to plasticizer is acrylate:plasticizer = (4-5):

1.

3. The two-component silane-modified polyether adhesive according to claim 1, characterized in that, The acrylate comprises the following raw materials in parts by weight: 150-181 parts of methyl methacrylate, 14-29 parts of glycidyl methacrylate, 23-93 parts of γ-methacryloyloxypropylmethyldimethoxysilane, 1-5 parts of initiator, 0.1-1 parts of chain transfer agent, and 45-55 parts of organic solvent.

4. The two-component silane-modified polyether adhesive according to claim 3, characterized in that, The initiator includes at least one of hydrogen peroxide, ditert-alkyl peroxide, acyl peroxide, carboxylic acid peroxide, and dicarbonate peroxide. And / or, the chain transfer agent comprises at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, 2-ethylhexyl 3-mercaptopropionate, 2-methylhexyl 3-mercaptoacetic acid, and 2,4-diphenyl-4-methyl-1-pentene; And / or, the organic solvent includes at least one of toluene, xylene, and ethyl acetate.

5. The two-component silane-modified polyether adhesive according to claim 3, characterized in that, The method for preparing the mixture of acrylate and plasticizer includes the following steps: (1) Methyl methacrylate, glycidyl methacrylate, γ-methacryloyloxypropylmethyldimethoxysilane, initiator and chain transfer agent were refluxed in an organic solvent to obtain a mixture of acrylate and organic solvent; (2) Add plasticizer to the mixture of acrylate and organic solvent, and then remove the organic solvent to obtain a mixture of acrylate and plasticizer.

6. The two-component silane-modified polyether adhesive according to claim 1, characterized in that, At least one of the following (a)-(j): (a) The plasticizer comprises at least one of diisononyl cyclohexane 1,2-dicarboxylate, dioctyl(2-ethylhexyl) 4,5-epoxytetrahydrophthalic acid, and alkyl sulfonate phenyl ester; (b) The epoxy resin includes at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin; (c) The flame-retardant filler includes at least one of aluminum hydroxide and magnesium hydroxide; (d) The UV additive includes at least one of light stabilizers and UV absorbers; (e) The antioxidants include hindered phenolic antioxidants; (f) The thixotropic agent comprises a specific surface area ≥150 m² 2 / g of hydrophobic fumed silica; (g) The color powder is at least one of pigment carbon black and rutile titanium dioxide; (h) The dehydrating agent includes at least one of hexamethyldisilazane and vinyltrimethoxysilane; (i) The epoxy curing agent includes polyetheramine curing agents; (j) The tackifier includes at least one of γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and oligomeric aminosilane.

7. The method for preparing the two-component silane-modified polyether adhesive according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: (1) Preparation of component A: Mix and stir the components other than the dehydrating agent, then add the dehydrating agent until the water content of component A is 2000-3500ppm, then vacuum, discharge the material, and obtain component A; (2) Preparation of component B: The epoxy curing agent and organotin catalyst are mixed and stirred, and then the tackifier, thixotropic agent and flame retardant filler are added and dispersed at a temperature below 50°C. Then, the mixture is vacuumed and discharged to obtain component B.

8. The application of the two-component silane-modified polyether adhesive as described in any one of claims 1-6 in the bonding of insulating blue film materials for power batteries.

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