Low-temperature-resistant epoxy resin adhesive and preparation method thereof

Abstract

The invention relates to a low-temperature-resistant epoxy resin adhesive and a preparation method thereof, and belongs to the technical field of high polymer materials. The modified epoxy resin adhesive comprises the following components in parts by weight: 90-120 parts of epoxy resin, 8-24 parts of a curing agent, 1-3 parts of a diluent, 0.5-5 parts of a curing accelerator, 4-18 parts of graphite, 1-4 parts of a hyperbranched polymerization flexibilizer and 10-30 parts of conductive filler, polyimide in the hyperbranched polymerization flexibilizer is difficult to crystallize, has no interchain winding, and cooperates with a flexible Si-O-Si chain segment with high bond energy and large bond angle to enhance low-temperature tensile strength and toughness, and chloroprene rubber effectively improves impact resistance and bending resistance; according to the low-temperature-resistant epoxy resin adhesive disclosed by the invention, a conductive network is constructed by indium tin oxide, good conductivity and chemical corrosion resistance are given to a matrix, a polyaniline layer is used for modifying a structural body and enhancing interface adhesion, and the prepared low-temperature-resistant epoxy resin adhesive not only has good low-temperature-resistant toughening and conductive effects, but also has excellent corrosion-resistant and flame-retardant effects.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a low-temperature resistant epoxy resin adhesive and a preparation method thereof. Background Art

[0002] Epoxy resin glue is an engineering adhesive made of epoxy resin base, curing agent, diluent, accelerator and filler. Due to its excellent bonding performance, good functionality, relatively low price and simple bonding process, it has been widely used in home appliances, automobiles, water conservancy and transportation, electronic appliances and aerospace industries in recent decades.

[0003] However, with the continuous advancement of science and technology and the development needs of the industry, epoxy resin glue has poor toughness at low temperatures, and will crack and peel off. In some areas with low temperatures in winter, the epoxy resin matrix is ​​difficult to cure at low temperatures. The cured epoxy resin has a highly cross-linked three-dimensional network structure, which leads to stress concentration, and it will also be brittle and have low toughness, which limits its application. In addition, although epoxy resin glue has certain electrical conductivity, with the increase in actual application needs, the electrical conductivity of epoxy resin glue itself no longer meets the needs. Therefore, modifying these deficiencies to expand the application field of epoxy resin glue has become an important direction for the current development of the industry. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a modified epoxy resin adhesive and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A low temperature resistant epoxy resin adhesive, comprising the following raw materials in parts by weight: 90-120 parts of epoxy resin, 8-24 parts of curing agent, 1-3 parts of diluent, 0.5-5 parts of curing accelerator, 4-18 parts of graphite, 1-4 parts of hyperbranched polymer toughening agent, and 10-30 parts of conductive filler; The curing agent is 4,4'-diaminodiphenylmethane; The diluent is butyl glycidyl ether; The curing accelerator is 2-methylimidazole.

[0006] The hyperbranched polymer toughening agent is prepared by the following method: Step A1: Tetrakis(4-aminophenyl)methane, 2-chloro-1,3-butadiene, acetone and triethylamine were mixed, stirred at room temperature for 2-3 hours, rotary evaporated, washed, dried, and methylmercaptotrimethoxysilane and methanol were added under nitrogen protection and mixed evenly, the pH was adjusted to 8-9, and the reaction was carried out for 4 hours to obtain an intermediate; Further, the usage ratio of tetrakis(4-aminophenyl)methane, 2-chloro-1,3-butadiene, acetone, triethylamine, methylmercaptotrimethoxysilane, and methanol is 0.5-1.2 g: 1.85-2.53 g: 20 mL: 0.5-0.6 mL: 1-2.5 g: 10-20 mL; Step A2: The intermediate, diphenyldimethoxysilane and 3-(2,3-epoxypropyloxy)propyltrimethoxysilane are mixed, the temperature is raised to 60° C., dilute hydrochloric acid with a pH of 2 is added, the mixture is kept at 60° C. for 12 h, and the mixture is distilled under reduced pressure at 80° C. to obtain a prepolymer; Further, the usage ratio of the intermediate, diphenyldimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and dilute hydrochloric acid is 0.1-0.2 mol: 0.05 mol: 0.1-0.2 mol: 22.5 mL; Step A3: mixing the prepolymer and N-methylpyrrolidone at 0° C. under nitrogen protection, stirring evenly, adding 4,4'-carbonylbis(isobenzofuran-1,3-dione), and stirring at 0-15° C. for 1 hour to obtain a hyperbranched polymer toughening agent; Furthermore, the usage ratio of the prepolymer, N-methylpyrrolidone, and 4,4'-carbonylbis(isobenzofuran-1,3-dione) is 0.442-0.584 g: 5 mL: 0.5-1 mol.

[0007] The conductive filler is prepared by the following method: Step B1: Indium, hydrochloric acid and tin tetrachloride pentahydrate are stirred for 2 hours, centrifuged, washed, calcined at 500°C for 3 hours, and then graphene oxide, polyvinyl alcohol and deionized water are added and stirred, ultrasonicated at room temperature for 3 hours, kept in a constant temperature water bath at 95°C for 1 hour, cooled to room temperature, frozen at -25°C for 24 hours, dried, and treated in a vacuum oven at 200°C for 2 hours to obtain a graphene-indium tin oxide three-dimensional structure; Further, the dosage ratio of indium, hydrochloric acid, tin tetrachloride pentahydrate, graphene oxide, polyvinyl alcohol, and deionized water is 0.3-0.75 g: 4.5-9 mL: 0.4-0.75 g: 4-6 g: 6 g: 150-300 mL; Step B2: magnetically stirring the aniline monomer and sulfuric acid for 1 hour, then adding the graphene-indium tin oxide three-dimensional structure and ammonium persulfate, reacting at room temperature for 4 hours, washing, and drying at 45° C. to obtain a conductive filler; Furthermore, the usage ratio of aniline monomer, sulfuric acid, graphene-indium tin oxide three-dimensional structure, and ammonium persulfate is 0.5 g: 120-150 mL: 0.2-0.6 g: 1.25 g, and the concentration of sulfuric acid is 1 mol / L.

[0008] A method for preparing low-temperature resistant epoxy resin adhesive specifically comprises the following steps: S1: Weigh epoxy resin, curing agent, diluent, curing accelerator, graphite, hyperbranched polymerization toughening agent, and conductive filler in parts by weight and mix them at room temperature and pressure to obtain a mixed material; S2: putting the mixed material into a high-speed mixer to stir and prepare glue, the speed is 500-1000r / min, and the glue is scraped synchronously with the rotation of the stirring plate to obtain glue liquid; S3: The above glue liquid is sanded for 3-4 hours to obtain low temperature resistant epoxy resin glue.

[0009] Beneficial effects of the present invention: The hyperbranched polymerization toughening agent prepared by the invention comprises the following steps: firstly, under the catalysis of acetone and triethylamine, the amino group of tetrakis(4-aminophenyl)methane and the chlorine atom of 2-chloro-1,3-butadiene are reacted, and then the mercapto group of methylmercaptotrimethoxysilane and the carbon-carbon double bond of 2-chloro-1,3-butadiene are reacted to generate an intermediate; secondly, the intermediate and the silicon-oxygen bonds of diphenyldimethoxysilane and 3-(2,3-epoxypropyloxy)propyltrimethoxysilane are polymerized to obtain a prepolymer; and finally, under the catalysis of N-methylpyrrolidone, the acyl group of 4,4'-carbonylbis(isobenzofuran-1,3-dione) and the amino group of the prepolymer are hyperbranched and polymerized to form a polyimide group to synthesize the hyperbranched polymerization toughening agent. Among the hyperbranched polymerization toughening agents, the polyimide structure hyperbranched polymer generated by the reaction of the prepolymer and 4,4'-carbonylbis(isobenzofuran-1,3-dione) has a highly branched structure, is difficult to crystallize, has no entanglement between chains, and has a large molecular free volume, thus exhibiting excellent toughness and mobility at ultra-low temperatures, avoiding embrittlement at low temperatures, and further improving the low-temperature toughness of the epoxy resin; in addition, the flexible -Si-O-Si- segments in the hyperbranched polymer have high bond energy and large bond angles, which can not only remain stable at low temperatures, but also relieve the thermal stress generated inside the resin due to temperature drop, thereby improving the low-temperature tensile strength of the resin and comprehensively optimizing the toughness and impact resistance of the epoxy resin glue; at the same time, the introduced chloroprene rubber has good compatibility with the epoxy resin and can be evenly dispersed in the epoxy resin to form a stable mixed system. The chloroprene rubber not only improves the impact resistance and reduces the brittleness of the epoxy resin, but also improves the bending resistance, further improving the comprehensive performance of the material. ‌‌ The conductive filler prepared by the invention comprises the following steps: firstly, using a hydrothermal method to dissolve metal indium in a hydrochloric acid environment, reacting with tin tetrachloride pentahydrate to generate indium tin oxide, then using ultrasound to peel off graphene oxide, using polyvinyl alcohol as a crosslinking agent, combining with freeze-drying technology, constructing a graphene oxide-indium tin oxide three-dimensional structure, and then performing high-temperature heat treatment to obtain the graphene-indium tin oxide three-dimensional structure; secondly, using a chemical oxidation polymerization method, immersing the three-dimensional structure in an acidic solution containing aniline monomers, using ammonium persulfate as an initiator, promoting the polymerization of aniline monomers on the surface of the structure to form a polyaniline layer, performing surface modification, and obtaining a polyaniline-modified graphene-indium tin oxide three-dimensional structure. Indium tin oxide itself has excellent conductivity, optical properties and chemical stability, and has low resistivity. As a conductive filler for epoxy resin glue, it is evenly dispersed in epoxy resin to build a conductive network. At the same time, its good chemical corrosion resistance also enhances the durability of epoxy resin glue. When the epoxy resin glue is cured, the dispersed indium tin oxide forms a continuous conductive path, thereby giving the epoxy resin glue conductivity, significantly improving its optical properties and chemical stability, and thus broadening the application range of epoxy resin glue. In addition, aniline molecules polymerize into a polyaniline layer on the surface of the low-density, porous three-dimensional graphene pore wall, modifying the surface of the graphene-indium tin oxide three-dimensional structure, optimizing the interface properties of the conductive filler, enhancing the interface adhesion with the epoxy resin glue, promoting the close bonding of the materials, and comprehensively improving the overall performance. In addition, the filler also exhibits good flame retardant properties, further improving its use value.

[0010] The low-temperature resistant epoxy resin adhesive prepared by the present invention not only has a good toughening effect and reduces brittleness, but also has excellent conductivity, impact resistance and corrosion resistance, thereby effectively extending the service life of the material. The prepared epoxy resin adhesive has excellent low-temperature resistance and can maintain excellent properties in a low-temperature environment, which is of great significance for application scenarios requiring low-temperature conditions. DETAILED DESCRIPTION

[0011] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0012] A method for preparing low-temperature resistant epoxy resin adhesive specifically comprises the following steps: S1: Weigh the raw materials by weight, including 90 parts of epoxy resin, 8 parts of curing agent, 1 part of diluent, 0.5 parts of curing accelerator, 4 parts of graphite, 1 part of hyperbranched polymerization toughening agent (prepared in this embodiment), and 10 parts of conductive filler (prepared in this embodiment), and mix the epoxy resin, 4,4'-diaminodiphenylmethane, butyl glycidyl ether, 2-methylimidazole, graphite, hyperbranched polymerization toughening agent, and conductive filler at room temperature and pressure to obtain a mixed material; S2: Put the mixed material into a high-speed mixer to stir and prepare glue, the speed is 500r / min, and the glue is scraped synchronously with the rotation of the stirring plate to obtain glue liquid; S3: grinding the above glue liquid with a sand grinder for 3-4 hours to obtain low-temperature resistant epoxy resin glue; The hyperbranched polymer toughening agent is prepared by the following method: Step A1: 0.5 g of tetrakis(4-aminophenyl)methane, 1.85 g of 2-chloro-1,3-butadiene, 20 mL of acetone and 0.5 mL of triethylamine were mixed, stirred at room temperature for 2 h, rotary evaporated, washed, dried, and 1 g of methylmercaptotrimethoxysilane and 10 mL of methanol were added and mixed evenly under nitrogen protection, the pH was adjusted to 8, and the reaction was carried out for 4 h to obtain an intermediate; Step A2: 0.1 mol of the intermediate, 0.05 mol of diphenyldimethoxysilane and 0.1 mol of 3-(2,3-epoxypropyloxy)propyltrimethoxysilane were mixed, the temperature was raised to 60° C., 22.5 mL of dilute hydrochloric acid with a pH of 2 was added, the mixture was kept at 60° C. for 12 h, and the mixture was distilled under reduced pressure at 80° C. to obtain a prepolymer; Step A3: 0.442 g of prepolymer and 5 mL of N-methylpyrrolidone were mixed at 0° C. under nitrogen protection, stirred evenly, and then 0.5 mol of 4,4'-carbonylbis(isobenzofuran-1,3-dione) was added, and stirred at 0° C. for 1 hour to obtain a hyperbranched polymer toughening agent; The conductive filler is prepared by the following method: Step B1: 0.3 g of indium, 4.5 mL of hydrochloric acid and 0.4 g of tin tetrachloride pentahydrate were stirred for 2 h, centrifuged, washed, calcined at 500 ° C for 3 h, and then 4 g of graphene oxide, 6 g of polyvinyl alcohol and 150 mL of deionized water were added and stirred, ultrasonicated at room temperature for 3 h, and kept in a constant temperature water bath at 95 ° C for 1 h, cooled to room temperature, frozen at -25 ° C for 24 h, dried, and treated at 200 ° C in a vacuum oven for 2 h to obtain a graphene-indium tin oxide three-dimensional structure; Step B2: 0.5 g of aniline monomer and 120 mL of 1 mol / L sulfuric acid were magnetically stirred for 1 h, and then 0.2 g of graphene-indium tin oxide three-dimensional structure and 1.25 g of ammonium persulfate were added, reacted at room temperature for 4 h, washed, and dried at 45° C. to obtain a conductive filler. Example

[0013] A method for preparing low temperature resistant epoxy resin adhesive, specifically comprising the following steps: S1: Weigh the raw materials by weight, including 105 parts of epoxy resin, 16 parts of curing agent, 2 parts of diluent, 3 parts of curing accelerator, 11 parts of graphite, 2 parts of hyperbranched polymerization toughening agent (prepared in this embodiment), and 20 parts of conductive filler (prepared in this embodiment), and mix the epoxy resin, 4,4'-diaminodiphenylmethane, butyl glycidyl ether, 2-methylimidazole, graphite, hyperbranched polymerization toughening agent, and conductive filler at room temperature and pressure to obtain a mixed material; S2: Put the mixed material into a high-speed mixer to stir and prepare glue, the speed is 750r / min, and the glue is scraped synchronously with the rotation of the stirring plate to obtain glue liquid; S3: grinding the above glue liquid with a sand grinder for 3-4 hours to obtain low-temperature resistant epoxy resin glue; The hyperbranched polymer toughening agent is prepared by the following method: Step A1: 0.85 g of tetrakis(4-aminophenyl)methane, 2.25 g of 2-chloro-1,3-butadiene, 20 mL of acetone and 0.55 mL of triethylamine were mixed, stirred at room temperature for 2.5 h, rotary evaporated, washed, dried, 1.75 g of methylmercaptotrimethoxysilane and 15 mL of methanol were added under nitrogen protection, mixed evenly, the pH was adjusted to 8.5, and the reaction was carried out for 4 h to obtain an intermediate; Step A2: 0.15 mol of the intermediate, 0.05 mol of diphenyldimethoxysilane and 0.15 mol of 3-(2,3-epoxypropyloxy)propyltrimethoxysilane were mixed, the temperature was raised to 60° C., 22.5 mL of dilute hydrochloric acid with a pH of 2 was added, the mixture was kept at 60° C. for 12 h, and the mixture was distilled under reduced pressure at 80° C. to obtain a prepolymer; Step A3: 0.511 g of prepolymer and 5 mL of N-methylpyrrolidone were mixed at 0° C. under nitrogen protection, stirred evenly, and then 0.75 mol of 4,4'-carbonylbis(isobenzofuran-1,3-dione) was added, and stirred at 7° C. for 1 hour to obtain a hyperbranched polymer toughening agent; The conductive filler is prepared by the following method: Step B1: 0.52 g of indium, 6.7 mL of hydrochloric acid and 0.57 g of tin tetrachloride pentahydrate were stirred for 2 h, centrifuged, washed, calcined at 500 ° C for 3 h, and then 5 g of graphene oxide, 6 g of polyvinyl alcohol and 225 mL of deionized water were added and stirred, ultrasonicated at room temperature for 3 h, and kept in a constant temperature water bath at 95 ° C for 1 h, cooled to room temperature, frozen at -25 ° C for 24 h, dried, and treated at 200 ° C in a vacuum oven for 2 h to obtain a graphene-indium tin oxide three-dimensional structure; Step B2: 0.5 g of aniline monomer and 135 mL of 1 mol / L sulfuric acid were magnetically stirred for 1 h, and then 0.4 g of graphene-indium tin oxide three-dimensional structure and 1.25 g of ammonium persulfate were added, reacted at room temperature for 4 h, washed, and dried at 45° C. to obtain a conductive filler. Example

[0014] A method for preparing low temperature resistant epoxy resin adhesive, specifically comprising the following steps: S1: Weigh the raw materials by weight, including 120 parts of epoxy resin, 24 parts of curing agent, 3 parts of diluent, 5 parts of curing accelerator, 18 parts of graphite, 4 parts of hyperbranched polymerization toughening agent (prepared in this embodiment), and 30 parts of conductive filler (prepared in this embodiment), and mix the epoxy resin, 4,4'-diaminodiphenylmethane, butyl glycidyl ether, 2-methylimidazole, graphite, hyperbranched polymerization toughening agent, and conductive filler at room temperature and pressure to obtain a mixed material; S2: putting the mixed material into a high-speed mixer to stir and prepare glue, the speed is 1000r / min, and the glue is scraped synchronously with the rotation of the stirring plate to obtain glue liquid; S3: grinding the above glue liquid with a sand grinder for 3-4 hours to obtain low-temperature resistant epoxy resin glue; The hyperbranched polymer toughening agent is prepared by the following method: Step A1: 1.2 g of tetrakis(4-aminophenyl)methane, 2.53 g of 2-chloro-1,3-butadiene, 20 mL of acetone and 0.6 mL of triethylamine were mixed, stirred at room temperature for 3 h, rotary evaporated, washed, dried, and 2.5 g of methylmercaptotrimethoxysilane and 20 mL of methanol were added and mixed evenly under nitrogen protection, the pH was adjusted to 9, and the reaction was carried out for 4 h to obtain an intermediate; Step A2: 0.2 mol of the intermediate, 0.05 mol of diphenyldimethoxysilane and 0.2 mol of 3-(2,3-epoxypropyloxy)propyltrimethoxysilane were mixed, the temperature was raised to 60°C, 22.5 mL of dilute hydrochloric acid with a pH of 2 was added, the mixture was kept at 60°C for 12 h, and the mixture was distilled under reduced pressure at 80°C to obtain a prepolymer; Step A3: 0.584 g of prepolymer and 5 mL of N-methylpyrrolidone were mixed at 0° C. under nitrogen protection, stirred evenly, and then 1 mol of 4,4'-carbonylbis(isobenzofuran-1,3-dione) was added, and stirred at 15° C. for 1 hour to obtain a hyperbranched polymer toughening agent; The conductive filler is prepared by the following method: Step B1: 0.75 g of indium, 9 mL of hydrochloric acid and 0.75 g of tin tetrachloride pentahydrate were stirred for 2 h, centrifuged, washed, calcined at 500 ° C for 3 h, and then 6 g of graphene oxide, 6 g of polyvinyl alcohol and 300 mL of deionized water were added for stirring, ultrasonicated at room temperature for 3 h, and placed in a constant temperature water bath at 95 ° C for 1 h, cooled to room temperature, frozen at -25 ° C for 24 h, dried, and treated at 200 ° C in a vacuum oven for 2 h to obtain a graphene-indium tin oxide three-dimensional structure; Step B2: 0.5 g of aniline monomer and 150 mL of 1 mol / L sulfuric acid were magnetically stirred for 1 h, and then 0.6 g of graphene-indium tin oxide three-dimensional structure and 1.25 g of ammonium persulfate were added, reacted at room temperature for 4 h, washed, and dried at 45° C. to obtain a conductive filler.

[0015] Comparative Example 1 This comparative example is a low-temperature resistant epoxy resin adhesive, which differs from Example 3 in that the modified toughening agent prepared in Example 3 is an equal amount of polybutadiene, and the rest are the same.

[0016] Comparative Example 2 This comparative example is a low-temperature resistant epoxy resin adhesive, which differs from Example 3 in that an equal amount of conductive mica powder is used to replace the conductive filler prepared in Example 3, and the rest are the same.

[0017] Performance test: The low-temperature resistant epoxy resin glue prepared in Examples 1-3 and Comparative Examples 1-2 was made into a standard test size, and the tensile strength was tested using the standard GB / T 1040.1-2006, the bending test was performed using GB1042-79, the impact strength was tested using GB / T2567-2008, the volume resistivity was tested using ASTM D2739 (the smaller the value, the better the conductive effect), the combustion performance was tested using GB / T 31293-2014, and the chemical corrosion resistance time test was performed; the test results are shown in the following table:

[0018] It can be seen from the test data in the table that the low-temperature resistant epoxy resin glue prepared in Example 1 not only has a good low-temperature toughening effect and reduces brittleness, but also has excellent impact resistance and conductivity, and extends the service life of the material. It can also be seen from the above table that the low-temperature resistant epoxy resin glue prepared by the present invention has excellent chemical corrosion resistance and flame retardant effects, thereby improving the comprehensive performance of the low-temperature resistant epoxy resin glue.

[0019] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing low temperature resistant epoxy resin adhesive, characterized in that: The following steps are involved: S1: mixing epoxy resin, curing agent, diluent, curing accelerator, graphite, hyperbranched polymerization toughening agent, and conductive filler at room temperature and pressure to obtain a mixed material; S2: putting the mixed material into a high-speed mixer to stir and prepare glue, the speed is 500-1000r / min, and the glue is scraped synchronously with the rotation of the stirring plate to obtain glue liquid; S3: The above glue liquid is sanded for 3-4 hours to obtain low temperature resistant epoxy resin glue.

2. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The hyperbranched polymer toughening agent is prepared by the following method: Step A1: Tetrakis(4-aminophenyl)methane, 2-chloro-1,3-butadiene, acetone and triethylamine were mixed, stirred at room temperature for 2-3 hours, rotary evaporated, washed, dried, and methylmercaptotrimethoxysilane and methanol were added under nitrogen protection and mixed evenly, the pH was adjusted to 8-9, and the reaction was carried out for 4 hours to obtain an intermediate; Step A2: The intermediate, diphenyldimethoxysilane and 3-(2,3-epoxypropyloxy)propyltrimethoxysilane are mixed, the temperature is raised to 60° C., dilute hydrochloric acid with a pH of 2 is added, the mixture is kept at 60° C. for 12 h, and the mixture is distilled under reduced pressure at 80° C. to obtain a prepolymer; Step A3: Mix the prepolymer and N-methylpyrrolidone at 0°C under nitrogen protection, stir evenly, then add 4,4'-carbonylbis(isobenzofuran-1,3-dione), and stir at 0-15°C for 1 hour to obtain a hyperbranched polymer toughening agent.

3. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 2, characterized in that: In step A1, the usage ratio of tetrakis(4-aminophenyl)methane, 2-chloro-1,3-butadiene, acetone, triethylamine, methylmercaptotrimethoxysilane and methanol is 0.5-1.2 g:1.85-2.53 g:20 mL:0.5-0.6 mL:1-2.5 g:10-20 mL.

4. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 2, characterized in that: In step A2, the usage ratio of the intermediate, diphenyldimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and dilute hydrochloric acid is 0.1-0.2 mol: 0.05 mol: 0.1-0.2 mol: 22.5 mL.

5. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 2, characterized in that: In step A3, the usage ratio of the prepolymer, N-methylpyrrolidone, and 4,4'-carbonylbis(isobenzofuran-1,3-dione) is 0.442-0.584 g: 5 mL: 0.5-1 mol.

6. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The conductive filler is prepared by the following method: Step B1: Indium, hydrochloric acid and tin tetrachloride pentahydrate are stirred for 2 hours, centrifuged, washed, calcined at 500°C for 3 hours, and then graphene oxide, polyvinyl alcohol and deionized water are added and stirred, ultrasonicated at room temperature for 3 hours, kept in a constant temperature water bath at 95°C for 1 hour, cooled to room temperature, frozen at -25°C for 24 hours, dried, and treated in a vacuum oven at 200°C for 2 hours to obtain a graphene-indium tin oxide three-dimensional structure; Step B2: The aniline monomer and sulfuric acid are magnetically stirred for 1 hour, and then the graphene-indium tin oxide three-dimensional structure and ammonium persulfate are added, reacted at room temperature for 4 hours, washed, and dried at 45° C. to obtain a conductive filler.

7. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 6, characterized in that: In step B1, the dosage ratio of indium, hydrochloric acid, tin tetrachloride pentahydrate, graphene oxide, polyvinyl alcohol, and deionized water is 0.3-0.75 g: 4.5-9 mL: 0.4-0.75 g: 4-6 g: 6 g: 150-300 mL.

8. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 6, characterized in that: In step B2, the usage ratio of aniline monomer, sulfuric acid, graphene-indium tin oxide three-dimensional structure, and ammonium persulfate is 0.5g:120-150mL:0.2-0.6g:1.25g, and the concentration of sulfuric acid is 1mol / L.

9. The method for preparing a low temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The curing agent is 4,4'-diaminodiphenylmethane, the diluent is butyl glycidyl ether, and the curing accelerator is 2-methylimidazole.

10. A low temperature resistant epoxy resin adhesive, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

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