CN115558448A - Epoxy heat-conducting structural adhesive and preparation method and application thereof - Google Patents
Epoxy heat-conducting structural adhesive and preparation method and application thereof Download PDFInfo
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- CN115558448A CN115558448A CN202211251878.3A CN202211251878A CN115558448A CN 115558448 A CN115558448 A CN 115558448A CN 202211251878 A CN202211251878 A CN 202211251878A CN 115558448 A CN115558448 A CN 115558448A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/78—Cases; Housings; Encapsulations; Mountings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/08—Cooling arrangements; Heating arrangements; Ventilating arrangements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application relates to the technical field of epoxy adhesives, and particularly discloses an epoxy heat-conducting structural adhesive and a preparation method and application thereof. An epoxy heat-conducting structural adhesive comprises the following components in parts by mass: 10-30 parts of epoxy resin, 5-20 parts of toughening agent, 20-600 parts of heat-conducting filler, 0.2-20 parts of curing agent, 1-10 parts of dispersing agent, 5-20 parts of viscosity reducer and 0.3-5 parts of stabilizing agent. The epoxy heat-conducting structural adhesive prepared by the application has the characteristics of excellent heat-conducting property, high bonding strength and chemical reagent resistance, can be widely applied to heat-conducting bonding of various components in new energy batteries and supercapacitors, comprises heat-conducting bonding of metal and components, PCB and heat-radiating aluminum substrates, and has strong practical significance.
Description
Technical Field
The application relates to the technical field of epoxy adhesives, in particular to an epoxy heat-conducting structural adhesive and a preparation method and application thereof.
Background
In daily industrial production, electronic components are usually fixed by adhering the electronic components to an adhesive. The adhesive used for bonding is various, such as acrylic resin adhesive, silicone resin adhesive, epoxy resin adhesive and the like. The epoxy resin structural adhesive has excellent mechanical property, chemical medium resistance, adhesive property and electrical insulation property, and is widely applied to pouring and encapsulating of machinery, electronic components and transformers.
However, as the power and the volume of electronic components such as surface mount components, inductors, transformers, and the like are increased and decreased, the technical requirements of the components on heat dissipation and packaging are increased. The packaging technology at the present stage mostly adopts an epoxy resin packaging process, after the electronic components are packaged, the epoxy resin is cured into a hard solid state, and the heat can not be led out in time due to poor heat-conducting property of the epoxy resin, so that the service life of the electronic components is shortened easily.
Therefore, the invention of the epoxy adhesive with better heat conduction performance is particularly important.
Disclosure of Invention
In order to obtain the epoxy heat-conducting structural adhesive with excellent heat-conducting property, the application provides the epoxy heat-conducting structural adhesive and a preparation method and application thereof.
First aspect, this application provides an epoxy heat conduction structure glues adopts following technical scheme:
an epoxy heat-conducting structural adhesive comprises the following components in parts by mass: 10-30 parts of epoxy resin, 5-20 parts of toughening agent, 20-600 parts of heat-conducting filler, 0.2-20 parts of curing agent, 1-10 parts of dispersing agent, 5-20 parts of viscosity reducer and 0.3-5 parts of stabilizing agent.
By adopting the technical scheme, the heat-conducting filler with good heat-conducting property is used as a heat-conducting improving substance of the epoxy resin, under the synergistic cooperation effect of other auxiliaries, the heat-conducting filler can be well dispersed in a system, a heat-conducting channel is formed in the system, and the heat-conducting coefficient of the finally obtained epoxy heat-conducting structural adhesive can reach about 0.5-4W/(m.K) on the basis that the bonding strength meets the requirement. Meanwhile, the obtained epoxy heat-conducting structural adhesive has excellent chemical reagent resistance, so that the epoxy heat-conducting structural adhesive can be in accordance with a special application scene that components are positioned in electrolyte.
And the addition amount of each component of the further preferable epoxy heat-conducting structural adhesive is as follows:
20-30 parts of epoxy resin, 10-15 parts of toughening agent, 100-300 parts of heat-conducting filler, 1-5 parts of curing agent, 4-8 parts of dispersing agent, 10-20 parts of viscosity reducer and 0.5-1 part of stabilizing agent.
The toughening agent is selected from at least one of propoxyglycerin triglycidyl ether, adipic acid diglycidyl ester, methyl tetrahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether. Further preferably, the toughening agent is composed of 1, 4-butanediol diglycidyl ether and methyl tetrahydrophthalic acid diglycidyl ester according to a mass ratio of 1.
The curing agent comprises at least one of aromatic diamine curing agent, imidazole curing agent, organic acid anhydride curing agent and Lewis acid salt curing agent.
In a specific embodiment, the epoxy resin includes at least one of a phenolic-modified epoxy resin, a cycloaliphatic epoxy resin, and an aromatic epoxy resin.
In a specific possible embodiment, the thermally conductive filler includes at least one of flake graphite, silicon carbide, aluminum nitride, boron nitride, aluminum oxide, carbon fiber, graphene.
In a specific possible embodiment, the heat conductive filler is prepared by mixing a nano alumina-carbon nanotube composition and flake graphite according to a mass ratio of (1.5-2.8): 1, preparing a composition; and the particle size of the flake graphite is 10-50 μm.
By adopting the technical scheme, the nano-alumina-carbon nano tube composition and the flake graphite are further selected to be compounded as the filler according to the proportion, the whole heat conducting performance of the heat conducting filler is excellent, and a stable heat conducting channel can be effectively formed after the nano-alumina-carbon nano tube composition and the flake graphite are added into a system, so that the heat conducting performance of the epoxy heat conducting structural adhesive can be effectively improved.
In a specific embodiment, the preparation method of the nano alumina-carbon nanotube composition comprises the following steps: adding carbon nanotubes with the diameter of 100-200nm into ethanol, adding nano alumina with the particle size of 10-50nm after ultrasonic dispersion, continuing ultrasonic dispersion for 1-2h, and centrifugally drying to obtain a nano alumina-carbon nanotube composition; wherein the mass ratio of the nano alumina to the carbon nano tube to the ethanol is 1: (10-20): (100-200).
By adopting the technical scheme, the particle size of the nano alumina is smaller than the diameter of the carbon nano tube, and the amount of the carbon nano tube is far larger than that of the nano alumina, namely, most of the nano alumina tends to be filled in the carbon nano tube in the dispersion process of the nano alumina and the carbon nano tube. Firstly, most of the nano-alumina is filled in the carbon nano-tube, so that the agglomeration phenomenon of the nano-alumina can be effectively reduced; the heat conductivity of the obtained nano aluminum oxide-carbon nanotube composition has an improvement effect of 1+1 to more than 2, and the heat conductivity of the epoxy heat-conducting structural adhesive can be effectively improved after the composition is applied to an epoxy heat-conducting structural adhesive system.
And in the curing process of the epoxy heat-conducting structural adhesive for bonding components, the nano alumina in the carbon nano tube can overflow to a certain extent under the influence of stress in the curing process, the overflowing nano alumina further perfects a heat-conducting channel, has positive significance for improving the continuity of the heat-conducting channel in the epoxy heat-conducting structural adhesive, and further contributes to further improving the heat-conducting performance of the epoxy heat-conducting structural adhesive.
In a specific embodiment, the carbon nanotube is obtained by modification treatment, and the modification treatment comprises the following steps:
and (3) soaking the carbon nano tube in an acid solution, and after ultrasonic soaking, sequentially filtering, washing and drying to obtain the modified carbon nano tube.
By adopting the technical scheme, after the carbon nano tube is soaked in the acid solution, the end of the carbon nano tube is oxidized and broken and is converted into carboxyl and hydroxyl, namely, functional groups such as hydroxyl, carboxyl and the like are introduced into the end of the carbon nano tube, so that the carbon nano tube has positive significance for improving the dispersibility of the carbon nano tube.
In addition, because carboxyl is introduced at the end of the carbon nano tube, and the carboxyl tends to show negative charge, and the nano alumina tends to show positive charge, the nano alumina in the system tends to gather at the end of the carbon nano tube in the preparation process of the nano alumina-carbon nano tube composition, so that the nano alumina can enter the interior of the carbon nano tube more easily, namely, the form of the nano alumina-carbon nano tube composition is better. In the subsequent curing process of the epoxy heat-conducting structural adhesive, under the influence of a charge effect, partial nano aluminum oxide can be assisted to overflow from the interior of the carbon nano tube to a certain extent, so that a more continuous heat-conducting channel is formed, and the epoxy heat-conducting structural adhesive has positive significance for further improving the heat-conducting property of the epoxy heat-conducting structural adhesive.
In a specific possible embodiment, the nano alumina-carbon nanotube composition and the flake graphite are obtained by modification treatment, and the modification treatment steps are as follows:
respectively adding the nano alumina-carbon nano tube composition and the flake graphite into a silane coupling agent, fully mixing under an ultrasonic condition, and sequentially filtering and drying to obtain the modified nano alumina-carbon nano tube composition and the modified flake graphite.
By adopting the technical scheme, the dispersibility of the nano alumina-carbon nanotube composition and the flake graphite treated by the silane coupling agent is further improved, and the adverse phenomena of agglomeration and the like can be effectively reduced; and the combination stability of the nano alumina-carbon nanotube composition and the flake graphite treated by the silane coupling agent and the epoxy resin is also greatly improved, and the epoxy resin has positive significance for improving the stability of a heat conduction channel in the epoxy heat conduction structural adhesive. Meanwhile, the negative influence of the influence on the bonding strength of the epoxy heat-conducting structural adhesive due to the addition of the heat-conducting filler can be reduced to a certain extent.
In a second aspect, the present application provides a method for preparing an epoxy heat-conducting structural adhesive, which adopts the following technical scheme:
a preparation method of an epoxy heat-conducting structural adhesive comprises the following steps:
and (2) mixing and stirring the epoxy resin, the toughening agent, the heat-conducting filler, the curing agent, the dispersing agent, the viscosity reducer and the stabilizing agent in a vacuum environment, controlling the rotating speed to be 400-1000rpm, stirring for 2-4h, and uniformly mixing to obtain the epoxy heat-conducting structural adhesive.
In a specific possible embodiment, the mixing and stirring temperature is < 40 ℃.
The third aspect, the epoxy heat-conducting structural adhesive provided by the application can be applied to heat-conducting bonding of various components in new energy batteries and super capacitors, including heat-conducting bonding of metals and components, PCB and heat-radiating aluminum substrates.
In summary, the present application has the following beneficial effects:
1. this application uses epoxy as the substrate, under the cooperation of each auxiliary agent, the heat conduction filler can form comparatively stable heat conduction passageway in the system, effectively improves the heat conductivility of system to the epoxy heat conduction structural adhesive who obtains has higher adhesive strength and excellent heat conductivility concurrently, has better chemical reagent resistance simultaneously, can adapt to special application scenarios such as electrolyte.
2. The nano-alumina-carbon nano tube composition and the flake graphite are compounded according to a certain proportion to be used as the heat-conducting filler, the nano-alumina in the nano-alumina-carbon nano tube composition tends to be positioned in the carbon nano tube, the composition in the form has excellent heat-conducting performance, and part of the nano-alumina overflowing from the carbon nano tube in the subsequent epoxy heat-conducting structural adhesive curing process has positive significance for improving the continuity of a heat-conducting channel.
3. The carbon nano tube is acidified in advance, functional groups such as carboxyl, hydroxyl and the like are introduced to the end of the carbon nano tube, the dispersibility of the carbon nano tube in a system is improved, the end of the carbon nano tube tends to show negative charges, nano alumina can be attracted into the carbon nano tube to a certain degree, and partial nano alumina can be assisted to overflow in the subsequent curing process.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples, and all of the starting materials referred to in the present application are commercially available.
Examples
Example 1
An epoxy heat-conducting structural adhesive comprises the following components in parts by mass: 20g of epoxy resin, 15g of toughening agent, 200g of heat-conducting filler, 1g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent;
wherein the epoxy resin is aliphatic epoxy resin;
the toughening agent is composed of 1, 4-butanediol diglycidyl ether and methyl tetrahydrophthalic acid diglycidyl ester according to the mass ratio of 1;
the heat conducting filler is alumina, and the grain diameter of the alumina is 5-150 mu m;
the curing agent is 2-ethyl-4-methylimidazole;
the dispersant is polyethylene glycol 2000;
the viscosity reducer is polydimethylsiloxane;
the stabilizer is 8-hydroxyquinoline.
The preparation method of the epoxy heat-conducting structural adhesive comprises the following steps:
adding epoxy resin, a toughening agent, a heat conduction filler, a curing agent, a dispersing agent, a viscosity reducer and a stabilizing agent into a planetary stirring kettle with a vacuumizing device, uniformly mixing and stirring, wherein the vacuum degree of the stirring kettle is 0.095MPa, the rotating speed is controlled to be 800rpm, stirring is carried out for 3 hours, the temperature of a mixed material is 30 +/-5 ℃, and uniformly mixing to obtain the epoxy heat conduction structural adhesive.
Example 2
This example differs from example 1 in that the components are added in the following amounts: 22g of epoxy resin, 17g of toughening agent, 200g of heat-conducting filler, 1g of curing agent, 1g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 3
This example differs from example 1 in that the components are added in the following amounts: 20g of epoxy resin, 15g of toughening agent, 200g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 4
This example differs from example 1 in that the components are added in the following amounts: 20g of epoxy resin, 15g of toughening agent, 300g of heat-conducting filler, 1g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 5
This example differs from example 1 in that the components are added in the following amounts: 20g of epoxy resin, 15g of toughening agent, 400g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 6
This example differs from example 1 in that the amounts of the components added are as follows: 20g of epoxy resin, 15g of toughening agent, 500g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 7
This example differs from example 1 in that the components are added in the following amounts: 20g of epoxy resin, 15g of toughening agent, 600g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 8
This example differs from example 1 in that the components are added in the following amounts: 20g of epoxy resin, 15g of toughening agent, 100g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 9
This example differs from example 1 in that the amounts of the components added are as follows: 20g of epoxy resin, 15g of toughening agent, 20g of heat-conducting filler, 0.7g of curing agent, 5g of dispersing agent, 15g of viscosity reducer and 0.5g of stabilizing agent.
Example 10
The present example is different from example 1 in that the heat conductive filler is a nano alumina-carbon nanotube composition and flake graphite in a mass ratio of 2.2:1, preparing a composition; the particle size of the flake graphite is 10-50 mu m, and the preparation method of the nano alumina-carbon nano tube composition comprises the following steps:
adding carbon nanotubes with the diameter of 100-200nm into ethanol, performing ultrasonic dispersion for 30min, adding nano alumina with the particle size of 10-50nm, continuing to perform ultrasonic dispersion for 2h, and performing centrifugal drying to obtain a nano alumina-carbon nanotube composition; wherein the mass ratio of the nano-alumina to the carbon nano-tube to the ethanol is 1:13:150.
example 11
The present example is different from example 10 in that the carbon nanotubes in the nano alumina-carbon nanotube composition are obtained by modification treatment, and the modification treatment steps are as follows:
and (2) soaking the carbon nano tube in 10wt% hydrochloric acid solution, ultrasonically soaking for 1h, and then sequentially filtering, washing and drying to obtain the modified carbon nano tube.
Example 12
The difference between this example and example 10 is that the nano alumina-carbon nanotube composition and the flake graphite are obtained by modification treatment, and the modification treatment steps are as follows:
respectively adding the nano alumina-carbon nanotube composition and the flake graphite into a silane coupling agent KH-560, fully mixing for 20min under an ultrasonic condition, and then sequentially filtering and drying to obtain the modified nano alumina-carbon nanotube composition and the modified flake graphite.
Example 13
The present example is different from example 10 in that the heat conductive filler is a nano alumina-carbon nanotube composition and flake graphite in a mass ratio of 1.5: 1.
Example 14
The present example is different from example 10 in that the heat conductive filler is a nano alumina-carbon nanotube composition and flake graphite in a mass ratio of 2.8: 1.
Example 15
This example differs from example 10 in that the thermally conductive filler is a nano alumina-carbon nanotube composition.
Example 16
This example is different from example 1 in that the heat conductive filler is flake graphite, and the particle diameter of the flake graphite is 10 to 50 μm.
Example 17
The difference between the embodiment and the embodiment 1 is that the heat conducting filler is nano alumina, carbon nanotubes and flake graphite according to a mass ratio of 1:6, preparing a mixture; the particle size of the flake graphite is 10-50 μm, the diameter of the carbon nano tube is 100-200nm, and the particle size of the nano aluminum oxide is 10-50nm.
Example 18
The present embodiment is different from embodiment 1 in that the heat conductive filler is nano alumina and flake graphite in a mass ratio of 1:6, preparing; the particle size of the flake graphite is 10-50 μm, and the particle size of the nano alumina is 10-50nm.
Example 19
The present embodiment is different from embodiment 1 in that the heat conductive filler is carbon nanotubes and graphite flakes according to a mass ratio of 13:6, preparing a mixture; the particle size of the flake graphite is 10-50 μm, and the diameter of the carbon nano tube is 100-200nm.
Example 20
The present embodiment is different from embodiment 1 in that the heat conductive filler is composed of nano alumina and carbon nanotubes in a mass ratio of 1; the diameter of the carbon nano tube is 100-200nm, and the particle size of the nano aluminum oxide is 10-50nm.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that no thermally conductive filler was added.
Performance detection test method
And (3) testing the heat conductivity coefficient: the epoxy thermal conductive structural adhesives prepared in examples 1 to 20 and comparative example 1 were tested according to astm d-5470 test method.
And (3) testing the peel strength: the epoxy heat-conducting structural adhesive prepared in examples 1-20 and comparative example 1 was tested according to the test method in GB/T7122-1996 peeling Strength test Standard for high Strength adhesive.
Chemical resistance test: the epoxy thermal conductive structural adhesives prepared in examples 1 to 20 and comparative example 1 were tested according to the test method in GB/T13353-1992, determination method of chemical resistance of adhesive.
TABLE 1 test data sheet
Through the analysis of the detection results in the table 1, the detection results of the embodiment 1 and the comparative example 1 are specifically combined, although the addition of the heat-conducting filler has a relatively obvious negative effect on the peel strength, the peel strength is still in the range capable of meeting the requirements, and meanwhile, the addition of the heat-conducting filler can greatly improve the heat-conducting performance of the epoxy heat-conducting structural adhesive, so that the requirement on the heat-conducting performance of the epoxy heat-conducting structural adhesive in the bonding of electronic components can be met. And from chemical reagent resistance test result, the epoxy heat-conducting structural adhesive prepared by the method is low in strength change rate, and the epoxy heat-conducting structural adhesive prepared by the method has excellent chemical reagent resistance and can meet the requirements of the epoxy heat-conducting structural adhesive in special scenes such as electrolyte.
According to the detection results of the embodiment 1 and the embodiment 10, the thermal conductivity and the peel strength of the prepared epoxy thermal conductive structural adhesive are obviously superior to those of the embodiment 1 by using the nano alumina-carbon nanotube composition and the flake graphite as the thermal conductive filler. The positive effect of compounding the nano-alumina-carbon nano-tube composition and the flake graphite is verified, and the positive significance of the heat conduction channel continuity after partial nano-alumina overflows from the carbon nano-tube in the curing process is also verified.
In combination with the detection results of the embodiments 10 and 11, the carbon nanotubes are subjected to the acid treatment in advance, so that the thermal conductivity and the peel strength of the epoxy thermal conductive structural adhesive are improved, on one hand, the improvement of the dispersibility of the carbon nanotubes after the acid treatment is verified, on the other hand, the positive effect of the acid treatment on the partial nanometer alumina overflowing the carbon nanotubes in the curing process is also demonstrated, and further, the continuity of the thermal conductive channel in the system is further promoted to be better, and finally, the thermal conductivity is reflected on the thermal conductivity of the epoxy thermal conductive structural adhesive.
In view of the results of the tests in examples 10 and 12, the dispersibility of the nano alumina-carbon nanotube composition treated with the silane coupling agent and the flake graphite is improved, and the bonding stability with the organic substance in the system is better, which is finally reflected in the thermal conductivity and peel strength of the epoxy thermal conductive structural adhesive.
In combination with the detection results of example 10 and examples 15-16, the improvement effect of the single nano alumina-carbon nanotube composition or the single flake graphite on the thermal conductivity of the system is obviously lower than that of the two compositions, which indicates that the two compositions have an obvious synergistic interaction effect.
The combination of the nano alumina and the carbon nanotubes in the form of the composition has a positive effect obviously superior to that of the combination added in a single form, namely the nano alumina-carbon nanotube composition has more excellent dispersibility and thermal conductivity, according to the detection results of the combination of the embodiments 1, 10 and 17-20. The method also proves that part of the nano alumina overflows the carbon nano tube under the stress action in the curing process of the nano alumina-carbon nano tube composition, and has obvious positive significance for the continuity of a heat conduction channel in the epoxy heat conduction structural adhesive.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The epoxy heat-conducting structural adhesive is characterized by comprising the following components in parts by mass: 10-30 parts of epoxy resin, 5-20 parts of toughening agent, 20-600 parts of heat-conducting filler, 0.2-20 parts of curing agent, 1-10 parts of dispersing agent, 5-20 parts of viscosity reducer and 0.3-5 parts of stabilizing agent.
2. The epoxy structural adhesive of claim 1, wherein the epoxy resin comprises at least one of a phenolic modified epoxy resin, an alicyclic epoxy resin, and an aromatic epoxy resin.
3. The epoxy structural adhesive of claim 1, wherein the heat conductive filler comprises at least one of graphite flakes, silicon carbide, aluminum nitride, boron nitride, aluminum oxide, carbon fiber, and graphene.
4. The epoxy structural adhesive as claimed in claim 1, wherein the heat conductive filler is prepared from a nano alumina-carbon nanotube composition and flake graphite according to a mass ratio of (1.5-2.8): 1, preparing a composition; and the particle size of the flake graphite is 10-50 mu m.
5. The epoxy structural adhesive of claim 4, wherein the preparation method of the nano alumina-carbon nanotube composition comprises the following steps:
adding carbon nanotubes with the diameter of 100-200nm into ethanol, adding nano aluminum oxide with the particle size of 10-50nm after ultrasonic dispersion, continuing ultrasonic dispersion for 1-2 hours, and performing centrifugal drying to obtain a nano aluminum oxide-carbon nanotube composition; wherein the mass ratio of the nano-alumina to the carbon nano-tube to the ethanol is 1: (10-20): (100-200).
6. The epoxy structural adhesive of claim 5, wherein the carbon nanotubes are obtained by modification, and the modification comprises the following steps:
and (3) soaking the carbon nano tube in an acid solution, and after ultrasonic soaking, sequentially filtering, washing and drying to obtain the modified carbon nano tube.
7. The epoxy structural adhesive of claim 5, wherein the nano alumina-carbon nanotube composition and the flake graphite are obtained by modification treatment, and the modification treatment comprises the following steps:
respectively adding the nano alumina-carbon nano tube composition and the flake graphite into a silane coupling agent, fully mixing under an ultrasonic condition, and sequentially filtering and drying to obtain the modified nano alumina-carbon nano tube composition and the modified flake graphite.
8. The preparation method of the epoxy heat-conducting structural adhesive according to any one of claims 1 to 7, characterized by comprising the following steps:
and (2) mixing and stirring the epoxy resin, the toughening agent, the heat-conducting filler, the curing agent, the dispersing agent, the viscosity reducer and the stabilizing agent in a vacuum environment, controlling the rotating speed to be 400-1000rpm, stirring for 2-4h, and uniformly mixing to obtain the epoxy heat-conducting structural adhesive.
9. The method for preparing the epoxy heat-conducting structural adhesive according to claim 8, wherein the mixing and stirring temperature is less than 40 ℃.
10. The application of the epoxy heat-conducting structural adhesive as claimed in any one of claims 1 to 7, wherein the epoxy heat-conducting structural adhesive is applied to heat-conducting adhesion of various components in new energy batteries and supercapacitors, including heat-conducting adhesion of metals and components, and heat-conducting adhesion of PCBs and heat-dissipating aluminum substrates.
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