Hyperbranched water-based polyurea acrylic resin, carbon-coated slurry, carbon-coated aluminum foil and preparation method and application of hyperbranched water-based polyurea acrylic resin

Abstract

The invention discloses hyperbranched water-based polyurea acrylic resin, carbon-coated slurry, carbon-coated aluminum foil and a preparation method and application of the hyperbranched water-based polyurea acrylic resin. The preparation method of the hyperbranched water-based polyurea acrylic resin comprises the following steps: (1) preparing a polyurea prepolymer; (2) reacting the polyurea prepolymer with acrylic resin, and then adding an amine compound to obtain hyperbranched water-based polyurea acrylic resin; the amine compound has three or more amino groups; or the amine compound has two or more amino groups and at least one imino group. The hyperbranched polyurea acrylic resin can be used as an adhesive of a carbon-coated aluminum foil to improve the water resistance of the carbon-coated aluminum foil, improve the thermal stability and enhance the mechanical property.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives; more specifically, it relates to a hyperbranched waterborne polyurea acrylic resin, a carbon-coated slurry, a carbon-coated aluminum foil, and a preparation method and use thereof. Background Art

[0002] Water-based paints are gradually replacing traditional solvent-based paints due to their environmental advantages. Common water-based paints include epoxy and acrylic. Among them, the main component of the adhesive commonly used in the field of carbon-coated aluminum foil is acrylic resin (PSA), which has the advantages of good light resistance, good weather resistance, high hardness, and low cost. However, conventional acrylic resins have the disadvantages of high film-forming temperature, low film hardness, poor anti-rebound, water resistance, and poor adhesion.

[0003] At present, polyurethane-modified acrylic resin is commonly used as an adhesive in the field of carbon-coated aluminum foil, which can effectively achieve the complementary advantages of the two. Waterborne polyurethane (WPU) has the advantages of excellent wear resistance, high bonding strength and good flexibility, and is non-toxic. However, the water-based adhesive based on polyurethane-modified acrylic resin has greatly affected the mechanical properties due to problems such as low double bond content, high viscosity and low solid content. And due to the limitations of its structure and chemical composition, the heat resistance of polyurethane-modified acrylic resin is poor and cannot be used at high temperatures for a long time. And most waterborne polyurethane-modified acrylic resins have more hydrophilic groups in their structure and are not water-resistant, which limits the application of this adhesive in some fields. Summary of the invention

[0004] In view of the above-mentioned existing technical problems, the primary purpose of the present invention is to provide a method for preparing a hyperbranched water-based polyurea acrylic resin. The prepared hyperbranched water-based polyurea acrylic resin can be used as an adhesive to significantly improve the water resistance, heat resistance and mechanical properties of carbon-coated aluminum foil.

[0005] The second object of the present invention is to provide a method for preparing a hyperbranched waterborne polyurea acrylic resin to obtain a hyperbranched waterborne polyurea acrylic resin.

[0006] The third object of the present invention is to provide a use of a hyperbranched waterborne polyurea acrylic resin in an adhesive or in a carbon-coated aluminum foil.

[0007] A fourth object of the present invention is to provide a carbon coating slurry.

[0008] A fifth object of the present invention is to provide a carbon-coated aluminum foil.

[0009] In order to achieve the above object, the present invention is implemented by the following technical solutions:

[0010] The present invention claims a method for preparing a hyperbranched waterborne polyurea acrylic resin, comprising the following steps:

[0011] (1) preparing a polyurea prepolymer;

[0012] (2) reacting a polyurea prepolymer with an acrylic resin, and then adding an amine compound to obtain a hyperbranched waterborne polyurea acrylic resin;

[0013] The amine compound has three or more amino groups; or the amine compound has two or more amino groups and at least one imino group.

[0014] The invention provides a hyperbranched waterborne polyurea acrylic resin. Acrylic resin is added as a capping agent to a prepared polyurea prepolymer to carry out a capping reaction, and then an amine compound with a specific number of amino groups is added to react to obtain the hyperbranched waterborne polyurea acrylic resin.

[0015] The present invention adopts the reaction of polyurea prepolymer and acrylic resin for modification, and the free radical polymerization and reaction of acrylate groups form a cross-linked chemical network. The polyurea contains urea bonds, which are strong polar groups. The intermolecular hydrogen bonds formed can promote the physical cross-linking of the molecular system. Therefore, compared with the polyurethane containing carbamate, it has more excellent performance and has the effect of strengthening and toughening, thereby improving the bonding performance of carbon-coated aluminum foil. The bidentate urea repeating unit group of the polyurea system has stronger hydrolysis resistance than the repeating unit group of the carbamate bond in the polyurethane. On this basis, an amine compound with a specific amino group number is added for reaction, which greatly improves the water resistance, heat resistance and mechanical properties of the hyperbranched polyurea acrylic resin.

[0016] The hyperbranched polyurea acrylic resin synthesized by the present invention has a unique three-dimensional spherical structure and has better mechanical properties than linear polymers. In addition, the unique three-dimensional spherical structure enables it to have abundant active end groups (such as double bonds, ester groups or amino groups) and more suitable viscosity, thereby improving the viscosity of the carbon-coated slurry and further improving the water resistance of the carbon-coated aluminum foil.

[0017] The synthesized hyperbranched waterborne polyurea acrylic resin of the present invention adopts a polyurea system, which has better heat resistance and a high melting point than a polyurethane system and other polymers, and the hyperbranched polyurea acrylic resin makes the structure dense, and the heat resistance of each functional group affects the decomposition temperature of the polymer. Based on the above influence, the carbon-coated aluminum foil has better thermal stability.

[0018] Preferably, the amine compound is selected from one or more of tris(2-aminoethyl)amine, diethylenetriamine, and triethylenetetramine.

[0019] Preferably, the acrylic resin is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

[0020] Preferably, in step (2), the reaction is carried out at room temperature after the acrylic resin is added. Further preferably, the room temperature is 15-30°C.

[0021] Preferably, in step (2), the reaction is carried out at room temperature after the amine compound is added. Further preferably, the room temperature is 15-30°C.

[0022] Preferably, in step (1), polyurea prepolymer is prepared by using polyol, diisocyanate and chain extender.

[0023] The invention adopts diisocyanate and polyol to prepare polyurea prepolymer under simple conditions and without using a catalyst, and then adds a chain extender into the polyurea prepolymer to increase the molecular weight and improve the mechanical properties and process properties of the polymer.

[0024] Preferably, in some specific embodiments, the polyurea prepolymer can be prepared by the following preparation method: keep the polyol and diisocyanate at 40-60°C for 0.5-1h, then heat to 80-100°C, continue to react for 2-5h, add a chain extender and react at 50-70°C for 0.5-2h to obtain the polyurea prepolymer.

[0025] Preferably, the molar ratio of the diisocyanate to the acrylic resin is 1:1.0-2.0.

[0026] Preferably, the molar ratio of the diisocyanate to the amine compound is 1:1.05-1.5.

[0027] Preferably, the mass ratio of the polyol to the diisocyanate is 1.07-2.68:1.

[0028] Preferably, the polyol is selected from one or both of polyether polyol and polyester polyol.

[0029] Further preferably, the polyether polyol is selected from one or more of polypropylene glycol, polybutylene glycol, polytetramethylene ether glycol, glycerol and polymers of alkylene oxide.

[0030] More preferably, the polyester polyol is one or more of polycaprolactone polyol, polycarbonate diol, and adipic acid polyester polyol.

[0031] Preferably, the diisocyanate is selected from one or both of aromatic diisocyanate and aliphatic diisocyanate.

[0032] More preferably, the aromatic diisocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate.

[0033] More preferably, the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and methylcyclohexyl diisocyanate.

[0034] Preferably, the chain extender is selected from one or more of 2,2-dimethylolpropionic acid, ethylenediamine, and diethylenetriamine.

[0035] Furthermore, the present invention seeks to protect the hyperbranched waterborne polyurea acrylic resin prepared by the above preparation method.

[0036] Furthermore, the present invention claims the use of the hyperbranched waterborne polyurea acrylic resin in an adhesive or in a carbon-coated aluminum foil.

[0037] Furthermore, the present invention seeks protection for a carbon-coated slurry comprising a conductive agent, a dispersant, an adhesive and a solvent; the adhesive is the above-mentioned hyperbranched waterborne polyurea acrylic resin.

[0038] Preferably, the mass ratio of the conductive agent, adhesive, dispersant and solvent is (1-10): (10-30): (0-17): (43-89). More preferably, the mass ratio of the conductive agent, adhesive, dispersant and solvent is (3-8): (12-20): (0.1-5): (60-85). More preferably, the mass ratio of the conductive agent, adhesive, dispersant and solvent is (4-6): (13-16): (0.15-0.4): (70-82).

[0039] Preferably, the conductive agent is selected from one or more of carbon black, graphite, carbon nanotubes, and conductive microspheres.

[0040] Preferably, the dispersant is selected from one or more of propanol (such as isopropanol), butanol (such as n-butanol), ethanol, propylene glycol methyl ether, BYK-20990, Tpg621, and polyvinyl pyrrolidone.

[0041] Preferably, the solvent is an aqueous solvent, such as water.

[0042] Preferably, in some specific embodiments, a carbon coating slurry can be prepared by the following preparation method: water, a binder, and a dispersant are uniformly mixed, a conductive agent is added for dispersion, and sand-milling is performed to obtain the carbon coating slurry.

[0043] Further preferably, the sand mill has a rotation speed of 500-1000 rpm / min.

[0044] More preferably, the dispersion time is 0.5-4h.

[0045] Furthermore, the present invention claims protection for a carbon-coated aluminum foil, which is obtained by coating the carbon-coated slurry on the aluminum foil and drying it.

[0046] Preferably, the drying temperature is 30-100°C.

[0047] Preferably, in some specific embodiments, the slurry formed by the adhesive is coated on the aluminum foil using a scraper. More specifically, the thickness of the scraper is 3-15 μm, preferably 4-6 μm.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] The invention provides a hyperbranched waterborne polyurea acrylic resin, which is prepared by reacting a polyurea prepolymer, an acrylic resin and an amine compound with a specific number of amino groups. The hyperbranched polyurea acrylic resin can be used as an adhesive for carbon-coated aluminum foil to improve the water resistance, thermal stability and mechanical properties of the carbon-coated aluminum foil. DETAILED DESCRIPTION

[0050] The present invention is further described below in conjunction with the specification and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0051] Example 1

[0052] S1: Weigh polytetramethylene ether glycol (PTMG1000, 40 g, 0.04 mol) and place it in a three-necked flask, set the temperature to 55° C., and stir for 30 min.

[0053] S2: Add 37.12 g (0.167 mol) of isophorone diisocyanate (IPDI) solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of 2,2-dihydroxymethylpropionic acid (DMPA), and react for 1 h to obtain a polyurea prepolymer solution.

[0054] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 23.2 g (0.2 mol) of hydroxyethyl acrylate under room temperature stirring for 2 h, and 25.88 g (0.177 mol) of tris(2-aminoethyl)amine was added and stirred under room temperature to obtain a hyperbranched waterborne polyurea acrylic resin (its infrared spectrum FTIR is: ν = 3474, 3286, 1730, 1680, 1412, 1285, 1237, 810 cm -1 ).

[0055] Example 2

[0056] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask, set the temperature to 60° C., and stir for 30 min.

[0057] S2: Add 24.51 g (0.14 mol) of toluene diisocyanate (TDI) solution to the PTMG1000 obtained in step S1, keep the temperature at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0058] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 26.0 g (0.2 mol) of hydroxyethyl methacrylate under stirring at room temperature for 1 h, and 21.7 g (0.148 mol) of tris(2-aminoethyl)amine was added, and the mixture was reacted and stirred at room temperature to obtain a hyperbranched waterborne polyurea acrylic resin adhesive (its infrared spectrum FTIR is: ν = 3345, 3174, 1716, 1600, 1375, 1189, 1153, 769 cm -1 ).

[0059] Example 3

[0060] S1: Weigh 45 g (0.0225 mol) of PTMG2000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0061] S2: Add 31.6 g (0.142 mol) of IPDI solution to the PTMG2000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0062] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 22.17 g (0.17 mol) of hydroxypropyl acrylate at room temperature for 1 h under stirring, and 22.01 g (0.15 mol) of tris(2-aminoethyl)amine was added and stirred at room temperature to obtain a hyperbranched waterborne polyurea acrylic resin adhesive (its infrared spectrum FTIR is: ν = 3500, 3389, 1742, 1726, 1680, 1425, 1248, 826 cm -1 ).

[0063] Example 4

[0064] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0065] S2: Add 37.12 g (0.167 mol) of IPDI solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0066] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 22.17 g (0.17 mol) of hydroxypropyl acrylate at room temperature for 1 h under stirring, and 18.26 g (0.177 mol) of diethylenetriamine was added and stirred at room temperature to obtain a hyperbranched waterborne polyurea acrylic resin adhesive (its infrared spectrum FTIR is: ν = 3400, 3362, 1730, 1689, 1625, 1513, 1200, 750 cm -1 ).

[0067] Example 5

[0068] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0069] S2: Add 37.12 g (0.167 mol) of IPDI solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0070] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 22.17 g (0.17 mol) of hydroxypropyl acrylate under stirring at room temperature for 1 h, and 38.79 g (0.177 mol) of triethylenetetramine was added and stirred at room temperature to obtain a hyperbranched waterborne polyurea acrylic resin adhesive (its infrared spectrum FTIR is: ν = 3444, 3258, 1697, 1668, 1421, 1150, 1105, 720 cm -1 ).

[0071] Example 6

[0072] (1) Add 0.35 g of isopropanol, 0.35 g of dispersant (BYK-20990), and 15.12 g of adhesive (hyperbranched waterborne polyurea acrylic resin prepared in Example 1) into a beaker, stir at 600 rpm / min for 30 min, then add 3 g of carbon black (Guangzhu New Materials Co., Ltd., 20WB), 2 g of graphite (Guangdong Kaijin New Energy Materials Co., Ltd., AML400), and 79.18 g of water, maintain stirring at 600 rpm / min for 30 min, then add a pickaxe bead for sand grinding for 3 h to obtain a carbon-coated slurry.

[0073] (2) The carbon-coated slurry was coated on aluminum foil using a 5 μm wire rod and dried at 100° C. for 3 min to obtain carbon-coated aluminum foil.

[0074] Example 7

[0075] (1) Add 0.5 g of isopropanol, 0.3 g of dispersant (Lubrizol Corporation, TPG621), and 14.21 g of adhesive (hyperbranched waterborne polyurea acrylic resin prepared in Example 2) into a beaker, stir at 800 rpm / min for 20 min, then add 2.6 g of carbon black (Guangzhu New Materials Co., Ltd., 20WB), 2.6 g of graphite (Guangdong Kaijin New Energy Materials Co., Ltd., AML400), and 79.79 g of water, maintain stirring at 800 rpm / min for 30 min, then add a pickaxe bead for sand grinding for 4 h to obtain a carbon-coated slurry.

[0076] (2) The carbon-coated slurry was coated on aluminum foil using a 7 μm wire rod and dried at 90° C. for 3 min to obtain carbon-coated aluminum foil.

[0077] Example 8

[0078] (1) Add 0.35 g isopropanol, 0.35 g BYK-20990, and 15.12 g adhesive (hyperbranched waterborne polyurea acrylic resin prepared in Example 3) into a beaker, stir at 600 rpm / min for 30 min, then add 3 g carbon black (Guangzhu New Materials Co., Ltd., 20WB), 2 g graphite (Guangdong Kaijin New Energy Materials Co., Ltd., AML400), and 79.18 g water, maintain stirring at 600 rpm / min for 30 min, then add a pickaxe bead for sand grinding for 3 h to obtain a carbon-coated slurry.

[0079] (2) The carbon-coated slurry was coated on aluminum foil using a 5 μm wire rod and dried at 100° C. for 3 min to obtain carbon-coated aluminum foil.

[0080] Example 9

[0081] (1) Add 0.35 g isopropanol, 0.35 g BYK-20990, and 15.12 g adhesive (hyperbranched waterborne polyurea acrylic resin prepared in Example 4) into a beaker, stir at 600 rpm / min for 30 min, then add 3 g carbon black (Guangzhu New Materials Co., Ltd., 20WB), 2 g graphite (Guangdong Kaijin New Energy Materials Co., Ltd., AML400), and 79.18 g water, maintain stirring at 600 rpm / min for 30 min, then add a pickaxe bead for sand grinding for 3 h to obtain a carbon-coated slurry.

[0082] (2) The carbon-coated slurry was coated on aluminum foil using a 5 μm wire rod and dried at 100° C. for 3 min to obtain carbon-coated aluminum foil.

[0083] Example 10

[0084] (1) Add 0.35 g isopropanol, 0.35 g BYK-20990, and 15.12 g adhesive (hyperbranched waterborne polyurea acrylic resin prepared in Example 5) into a beaker, stir at 600 rpm / min for 30 min, then add 3 g carbon black (Guangzhu New Materials Co., Ltd., 20WB), 2 g graphite (Guangdong Kaijin New Energy Materials Co., Ltd., AML400), and 79.18 g water, maintain stirring at 600 rpm / min for 30 min, then add a pickaxe bead for sand grinding for 3 h to obtain a carbon-coated slurry.

[0085] (2) The carbon-coated slurry was coated on aluminum foil using a 5 μm wire rod and dried at 100° C. for 3 min to obtain carbon-coated aluminum foil.

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 6 is that the adhesive used in Comparative Example 1 is a hyperbranched waterborne polyurea, and its preparation method is as follows:

[0088] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0089] S2: Add 37.12 g (0.167 mol) of IPDI solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0090] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 13.1 g (0.089 mol) of tris(2-aminoethyl)amine under stirring at room temperature to obtain a hyperbranched waterborne polyurea (its infrared spectrum FTIR is: ν = 3450, 3295, 1728, 1706, 1248 cm -1 ).

[0091] Comparative Example 2

[0092] The difference between this comparative example and Example 6 is that the adhesive used in Comparative Example 2 is a water-based polyurea adhesive, and its preparation method is as follows:

[0093] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0094] S2: Add 37.12 g (0.167 mol) of IPDI solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0095] S3: Add 121 g (0.13 mol) of polyether diamine ED-900 to the polyurea prepolymer solution obtained in step S2 at a molar ratio of 1:1.06, and react and stir at room temperature to obtain a water-based polyurea adhesive.

[0096] Comparative Example 3

[0097] The difference between this comparative example and Example 6 is that the adhesive used in Comparative Example 3 is an acrylic resin adhesive (aqueous acrylic resin adhesive, manufactured by Blue Ocean Black Stone New Materials Co., Ltd., brand BC602).

[0098] Comparative Example 4

[0099] The difference between this comparative example and Example 6 is that the adhesive used in Comparative Example 4 is a polyurea acrylic resin adhesive, and its preparation method is as follows:

[0100] S1: Weigh 40 g (0.04 mol) of PTMG1000 and place it in a three-necked flask. Set the temperature to 55° C. and stir for 30 min.

[0101] S2: Add 37.12 g (0.167 mol) of IPDI solution to the PTMG1000 obtained in step S1, keep the mixture at 55°C for 30 min, raise the temperature to 80°C, continue the reaction for 2 h, cool the mixture to 70°C, add 3.62 g (0.027 mol) of DMPA, and react for 1 h to obtain a polyurea prepolymer solution.

[0102] S3: The polyurea prepolymer solution obtained in step S2 was reacted with 23.2 g (0.2 mol) of hydroxyethyl acrylate under stirring at room temperature for 2 h, and 7.98 g (0.177 mol) of ethylamine was added and stirred at room temperature to obtain a polyurea acrylic resin (its infrared spectrum FTIR is: ν = 3432, 3289, 2850, 1709, 1673, 1620, 1297, cm -1 ).

[0103] Test Case

[0104] The carbon-coated aluminum foils obtained in Examples 6-10 and Comparative Examples 1-4 were tested for water wiping resistance, square resistance, NMP wiping resistance, thermal weight loss performance, and peeling performance. The specific test methods are as follows, and the test results are shown in Table 1.

[0105] Test method:

[0106] (1) Water-resistant wiping performance: Cut the carbon-coated aluminum foil into rectangular slices of 15 cm × 3 cm. Dip cotton in water and rub the carbon-coated aluminum foil up and down to observe whether there are leaks at the bottom or spots.

[0107] (2) Square resistance: The carbon-coated aluminum foil film was cut into a 10 cm × 10 cm square and placed on a stage. The square resistance was tested using a ST-2258C multifunctional digital four-probe tester.

[0108] (3) NMP wiping resistance: The carbon-coated aluminum foil was cut into rectangular slices of 15 cm × 3 cm. Cotton was dipped in NMP solution and rubbed up and down on the carbon-coated aluminum foil to observe whether there were any leaks or spots.

[0109] (4) Thermal weight loss performance: A certain mass of carbon-coated aluminum foil was taken and its thermal stability was characterized using a thermogravimetric analyzer. The thermal stability and decomposition temperature of the carbon-coated aluminum foil were tested under nitrogen conditions, and the foil was heated from 25°C to 700°C at a heating rate of 15°C / min.

[0110] (5) Stripping performance: Cut the prepared carbon-coated aluminum foil into rectangular slices of 15 cm × 2.5 cm, place them in the test port of a universal tensile testing machine tester, and measure the stripping strength.

[0111] Table 1

[0112]

[0113]

[0114] From the data of the above examples, it can be seen that the hyperbranched waterborne polyurea acrylate resin prepared by the present invention can significantly improve the water resistance, heat resistance and mechanical properties of the carbon-coated aluminum foil as an adhesive. Specifically, the prepared carbon-coated aluminum foil has excellent water wiping resistance and NMP wiping resistance, and can achieve no bottom leakage after 200 times; it has excellent bonding strength and extremely low resistance, and its stripping strength exceeds 85 N·m -1 , surface resistivity ≤ 2.1 mΩ / square; it has excellent heat resistance, and the thermal weight loss ≥ 295 °C.

[0115] From Example 1 and Comparative Example 1, it can be seen that after the polyurea prepolymer is crosslinked with the acrylate resin and then reacts with the amine compound, when the hyperbranched waterborne polyurea acrylate resin is used as an adhesive, the carbon-coated aluminum foil has more excellent water wiping resistance and NMP wiping resistance, and its mechanical strength, resistance and heat resistance are also more excellent.

[0116] From Example 1 and Comparative Example 2, it can be seen that when the waterborne polyurea adhesive is prepared without crosslinking with the acrylate resin and reacting with the amine compound having two amino groups and used as an adhesive, the carbon-coated aluminum foil has poor water wiping resistance, NMP wiping resistance, mechanical strength, resistance and heat resistance.

[0117] From Example 1 and Comparative Example 3, it can be seen that the hyperbranched waterborne polyurea acrylate resin prepared by the present invention has more excellent water wiping resistance, NMP wiping resistance, mechanical strength, resistance and heat resistance compared with the conventionally used acrylate resin adhesive.

[0118] From Example 1 and Comparative Example 4, it can be seen that when the amine compound has only one amino group, it is difficult to achieve the technical effects of the present invention.

[0119] The foregoing examples are illustrative only and are used to explain some of the features of the method of the present invention. The appended claims are intended to claim the broadest scope possible, and the examples presented herein are supported by the applicant's actual test results. Therefore, the applicant's intention is that the appended claims should not be limited by the selection of examples that illustrate the features of the present invention. Some of the numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be construed as being covered by the appended claims where possible.

Claims

1. A method for preparing a hyperbranched waterborne polyurea acrylic resin, characterized in that: The steps include: (1) preparing a polyurea prepolymer; (2) reacting a polyurea prepolymer with an acrylic resin, and then adding an amine compound to obtain a hyperbranched waterborne polyurea acrylic resin; The amine compound has three or more amino groups; or the amine compound has two or more amino groups and at least one imino group.

2. The preparation method according to claim 1, characterized in that: The amine compound is selected from one or more of tris(2-aminoethyl)amine, diethylenetriamine, and triethylenetetramine.

3. The preparation method according to claim 1, characterized in that: The acrylic resin is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

4. The preparation method according to claim 1, characterized in that: The polyurea prepolymer is prepared by using polyol, diisocyanate and chain extender.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the diisocyanate to the acrylic resin is 1:1.0-2.0; and / or the molar ratio of the diisocyanate to the amine compound is 1:1.05-1.

5.

6. The preparation method according to claim 4, characterized in that: At least one selected from the following (a)-(c): (a) the polyol is selected from one or both of polyether polyol and polyester polyol; (b) the diisocyanate is selected from one or both of aromatic diisocyanate and aliphatic diisocyanate; (c) The chain extender is selected from one or more of 2,2-dimethylolpropionic acid, ethylenediamine, and diethylenetriamine.

7. The hyperbranched waterborne polyurea acrylic resin prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the hyperbranched waterborne polyurea acrylic resin according to claim 7 in an adhesive or in a carbon-coated aluminum foil.

9. A carbon coating slurry, characterized in that: It comprises a conductive agent, a dispersant, an adhesive and a solvent; the adhesive is the hyperbranched waterborne polyurea acrylic resin according to claim 7.

10. A carbon-coated aluminum foil, characterized in that: The carbon coating slurry according to claim 9 is applied on an aluminum foil and dried.

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