1. The high-temperature-resistant epoxy resin adhesive is characterized by consisting of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 50-67 parts of epoxy resin, 5-10 parts of a toughening agent, 3-6 parts of a diluent, 0.5-1 part of a coupling agent and 25-35 parts of a high-temperature-resistant filler; wherein the toughening agent is boron-doped organic silicon resin;

the component B comprises the following raw materials in parts by weight: 60-70 parts of an acid anhydride curing agent, 0-40 parts of DMP-3030 and 0.2-1 part of a thixotropic agent.

2. The high temperature resistant epoxy adhesive of claim 1, wherein the boron doped silicone resin is prepared by: adding diphenyldimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, boric acid and ethanol into a reaction vessel, heating in an oil bath at 60-70 ℃, then dropwise adding deionized water, stirring and reacting for 2-3 h, then heating to 90-100 ℃, continuing stirring and reacting for 2-3 h, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the high-performance liquid crystal.

3. The high-temperature-resistant epoxy resin adhesive as claimed in claim 2, wherein the weight ratio of the diphenyldimethoxysilane, the phenyltrimethoxysilane, the dimethyldimethoxysilane and the boric acid is 100: 24-30: 15-20: 6 to 10.

4. The high-temperature-resistant epoxy resin adhesive as claimed in claim 1, wherein the diluent is phenyl glycidyl ether or ethylene glycol diglycidyl ether, and the ratio of the phenyl glycidyl ether to the ethylene glycol diglycidyl ether is 2-3: 2 to 3 by weight.

5. The high-temperature-resistant epoxy resin adhesive as claimed in claim 1, wherein the high-temperature-resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 7-20: 80-93 wt%.

6. The high-temperature-resistant epoxy resin adhesive according to claim 1, wherein the acid anhydride curing agent is pyromellitic dianhydride or maleic anhydride, and the ratio of the acid anhydride curing agent to the maleic anhydride is 70-80: 20-30 wt% of a mixture, or diphenyl ether tetracarboxylic dianhydride.

7. The high temperature resistant epoxy adhesive of claim 1, wherein the thixotropic agent is thixotropic agent R972.

8. The high-temperature-resistant epoxy resin adhesive as claimed in claim 1, wherein the weight ratio of the component A to the component B is 1.0-1.2: 1.

9. the preparation method of the high-temperature-resistant epoxy resin adhesive based on any one of claims 1 to 8 is characterized by comprising the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the component A and the component B are mixed and stirred to obtain the epoxy resin adhesive.

Background

The epoxy resin is a general term for a polymer containing more than two epoxy groups in a molecule, has excellent comprehensive mechanical property, strong adhesive force, small shrinkage rate and good stability, and is called as a universal adhesive, so that the epoxy resin is widely used for bonding substrates such as metal, wood, plastic and the like. However, the epoxy resin adhesives themselves have disadvantages of brittleness, poor heat resistance, and the like, so that the applications thereof are limited, and the disadvantages of heat resistance, brittleness, and the like need to be improved. With the development of industrial science and technology, the application fields and objects are continuously expanded, higher requirements are put on the heat resistance and the like of the epoxy resin adhesive, and particularly, a high-temperature-resistant adhesive with the heat resistance of more than 200-250 ℃ is developed to meet the requirements of certain specific fields. In addition, for the two-component epoxy resin adhesive, the A, B component often has the problems of difficult glue mixing and the like due to inconsistent thixotropy and viscosity.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a high-temperature-resistant epoxy resin adhesive and a preparation method thereof.

The invention provides a high-temperature-resistant epoxy resin adhesive which consists of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 50-67 parts of epoxy resin, 5-10 parts of a toughening agent, 3-6 parts of a diluent, 0.5-1 part of a coupling agent and 25-35 parts of a high-temperature-resistant filler; wherein the toughening agent is boron-doped organic silicon resin;

the component B comprises the following raw materials in parts by weight: 60-70 parts of an acid anhydride curing agent, 0-40 parts of DMP-3030 and 0.2-1 part of a thixotropic agent.

Preferably, the boron-doped silicone resin is prepared as follows: adding diphenyldimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, boric acid and ethanol into a reaction vessel, heating in an oil bath at 60-70 ℃, then dropwise adding deionized water, stirring and reacting for 2-3 h, then heating to 90-100 ℃, continuing stirring and reacting for 2-3 h, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the high-performance liquid crystal.

Preferably, the weight ratio of the diphenyl dimethoxysilane, the phenyl trimethoxysilane, the dimethyl dimethoxysilane and the boric acid is 100: 24-30: 15-20: 6 to 10.

Preferably, the diluent is phenyl glycidyl ether or ethylene glycol diglycidyl ether according to the ratio of 2-3: 2 to 3 by weight.

Preferably, the high-temperature-resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 7-20: 80-93 wt%.

Preferably, the acid anhydride curing agent is pyromellitic dianhydride and maleic anhydride, and the ratio of the acid anhydride curing agent to the maleic anhydride is 70-80: 20-30 wt% of a mixture, or diphenyl ether tetracarboxylic dianhydride.

Preferably, the thixotropic agent is thixotropic agent R972.

Preferably, the weight ratio of the component A to the component B is 1.0-1.2: 1.

the invention also provides a preparation method of the high-temperature-resistant epoxy resin adhesive, which comprises the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the component A and the component B are mixed and stirred to obtain the epoxy resin adhesive.

Has the advantages that: the invention provides a high-temperature-resistant epoxy resin adhesive, wherein a sizing material adopts boron-doped organic silicon resin as a toughening agent, the toughness of the epoxy resin is improved, and simultaneously, a heat-resistant heteroatom B is introduced and matched with a high-temperature-resistant filler, so that the high-temperature-resistant performance, the toughness and other performances of the sizing material are further improved; a reactive diluent, namely phenyl glycidyl ether and ethylene glycol diglycidyl ether, is selected to be matched, so that the temperature resistance and toughness of the epoxy resin are improved; the curing agent containing aromatic anhydride is adopted, and the obtained cured product has good mechanical property and thermal stability. The raw materials are matched, the prepared epoxy resin adhesive has good mechanical property and toughness, keeps higher shear strength and thermal aging resistance at high temperature, has a simple preparation method, and has good adhesive property for various materials.

Thixotropic agents are generally added to the a component or to the A, B component in the prior art, which leads to difficulties in mixing due to the large difference in viscosity of the A, B component; compared with the prior art, the thixotropic agent is only added into the component B, so that the A, B component alone does not have thixotropy, thixotropy occurs during mixed rubber shearing, uniform mixing and demixing are easier to realize, and the problem that two-component rubber materials are difficult to mix is effectively solved; the thixotropic agent is optimally selected to be R972, so that the adhesive is ensured to have good stability and good construction performance.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to specific examples.

Example 1

The invention provides a high-temperature-resistant epoxy resin adhesive which consists of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 50 parts of epoxy resin, 5 parts of toughening agent, 3 parts of diluent, 1 part of coupling agent and 35 parts of high-temperature-resistant filler;

wherein the toughening agent is boron-doped organic silicon resin, and is prepared by the following steps: adding 100 parts of diphenyl dimethoxysilane, 24 parts of phenyl trimethoxy silane, 20 parts of dimethyl dimethoxysilane, 6 parts of boric acid and a proper amount of ethanol into a reaction vessel, heating in an oil bath at 60 ℃, then dropwise adding deionized water, stirring and reacting for 2 hours, then heating to 90 ℃, continuing stirring and reacting for 2 hours, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the boron-doped organic silicon resin;

the diluent is phenyl glycidyl ether or ethylene glycol diglycidyl ether according to the weight ratio of 1: 1 in a weight ratio; the high-temperature resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 7: 93 by weight percent;

the component B comprises the following raw materials in parts by weight: 60 parts of anhydride curing agent, DMP-3040 parts and 9721 parts of thixotropic agent R; wherein, the anhydride curing agent is pyromellitic dianhydride and maleic anhydride according to the weight ratio of 70: 30 weight percent of the composition.

The preparation method of the high-temperature-resistant epoxy resin adhesive comprises the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the component A and the component B are mixed according to the ratio of 1: 1, and stirring to obtain the epoxy resin adhesive.

Example 2

The invention provides a high-temperature-resistant epoxy resin adhesive which consists of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 55 parts of epoxy resin, 6 parts of toughening agent, 4 parts of diluent, 0.8 part of coupling agent and 32 parts of high-temperature-resistant filler;

wherein the toughening agent is boron-doped organic silicon resin, and is prepared by the following steps: adding 100 parts of diphenyl dimethoxysilane, 26 parts of phenyl trimethoxy silane, 18 parts of dimethyl dimethoxysilane, 7 parts of boric acid and a proper amount of ethanol into a reaction vessel, heating in an oil bath at 65 ℃, then dropwise adding deionized water, stirring and reacting for 2.5h, then heating to 95 ℃, continuing stirring and reacting for 2h, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the boron-doped organic silicon resin;

the diluent is phenyl glycidyl ether or ethylene glycol diglycidyl ether according to the weight ratio of 1: 1 in a weight ratio; the high-temperature resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 12: 88 weight percent;

the component B comprises the following raw materials in parts by weight: 65 parts of anhydride curing agent, 3035 parts of DMP-3035 parts of thixotropic agent R9720.8 parts; wherein the anhydride curing agent is diphenyl ether tetracarboxylic dianhydride.

The preparation method of the high-temperature-resistant epoxy resin adhesive comprises the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the component A and the component B are mixed according to the ratio of 1: 1, and stirring to obtain the epoxy resin adhesive.

Example 3

The invention provides a high-temperature-resistant epoxy resin adhesive which consists of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 62 parts of epoxy resin, 8 parts of toughening agent, 5 parts of diluent, 0.7 part of coupling agent and 28 parts of high-temperature-resistant filler;

wherein the toughening agent is boron-doped organic silicon resin, and is prepared by the following steps: adding 100 parts of diphenyl dimethoxysilane, 28 parts of phenyl trimethoxy silane, 17 parts of dimethyl dimethoxysilane, 8 parts of boric acid and a proper amount of ethanol into a reaction vessel, heating in an oil bath at 70 ℃, then dropwise adding deionized water, stirring and reacting for 2.5h, then heating to 100 ℃, continuing stirring and reacting for 3h, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the boron-doped organic silicon resin;

the diluent is phenyl glycidyl ether, ethylene glycol diglycidyl ether according to the weight ratio of 2: 3 in a weight ratio; the high-temperature resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 16: 84 weight percent;

the component B comprises the following raw materials in parts by weight: 68 parts of anhydride curing agent, DMP-3032 parts and 9720.5 parts of thixotropic agent R; wherein, the anhydride curing agent is pyromellitic dianhydride and maleic anhydride according to the ratio of 80: 20 weight percent of the composition.

The preparation method of the high-temperature-resistant epoxy resin adhesive comprises the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the A component and the B component are mixed according to the ratio of 1.2: 1, and stirring to obtain the epoxy resin adhesive.

Example 4

The invention provides a high-temperature-resistant epoxy resin adhesive which consists of a component A and a component B;

the component A comprises the following raw materials in parts by weight: 67 parts of epoxy resin, 10 parts of toughening agent, 6 parts of diluent, 0.5 part of coupling agent and 25 parts of high-temperature-resistant filler;

wherein the toughening agent is boron-doped organic silicon resin, and is prepared by the following steps: adding 100 parts of diphenyl dimethoxysilane, 30 parts of phenyl trimethoxy silane, 15 parts of dimethyl dimethoxysilane, 10 parts of boric acid and ethanol into a reaction vessel, heating in an oil bath at 70 ℃, then dropwise adding deionized water, stirring and reacting for 3 hours, then heating to 100 ℃, continuing stirring and reacting for 3 hours, and removing the solvent and low molecular weight substances by reduced pressure distillation to obtain the boron-doped organic silicon resin;

the diluent is phenyl glycidyl ether or ethylene glycol diglycidyl ether according to the weight ratio of 3: 2 in a weight ratio; the high-temperature resistant filler is prepared from silicon nitride and kaolin according to the weight ratio of 20: 80 weight percent;

the component B comprises the following raw materials in parts by weight: 70 parts of anhydride curing agent, 3030 parts of DMP-3030 parts of thixotropic agent R9720.2 parts; wherein the anhydride curing agent is diphenyl ether tetracarboxylic dianhydride.

The preparation method of the high-temperature-resistant epoxy resin adhesive comprises the following steps: mixing epoxy resin, a toughening agent, a diluent, a coupling agent and a high-temperature-resistant filler, and shearing and dispersing to prepare a component A; mixing an anhydride curing agent, DMP-30 and a thixotropic agent, and stirring and dispersing to prepare a component B; when in use, the A component and the B component are mixed according to the ratio of 1.2: 1, and stirring to obtain the epoxy resin adhesive.

The properties of the epoxy resin adhesives prepared in examples 1 to 4 of the present invention were examined.

Sample preparation: mixing the component A and the component B, stirring uniformly, then vacuumizing for 1h, pouring into a mold, curing in an oven at 200 ℃ for 2h, taking out, and cutting into sample samples of 10X 2 mm.

The test method comprises the following steps: 1. shear strength: respectively testing the shear strength at 20 ℃ and 250 ℃;

2. thermal aging resistance: aging at 200 deg.C for 1000 hr in air medium, and measuring shear strength;

shear strength was tested according to GB7124-86 and the results are shown in Table 1.

Table 1 performance data for epoxy adhesives

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.