CN107868409B - Graphite/epoxy resin conductive composite material and preparation method thereof - Google Patents
Graphite/epoxy resin conductive composite material and preparation method thereof Download PDFInfo
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- CN107868409B CN107868409B CN201711167224.1A CN201711167224A CN107868409B CN 107868409 B CN107868409 B CN 107868409B CN 201711167224 A CN201711167224 A CN 201711167224A CN 107868409 B CN107868409 B CN 107868409B
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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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
- C08K2201/001—Conductive additives
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Abstract
The invention relates to an epoxy resin composite material, in particular to a composite material which is compounded by epoxy resin and graphite and has conductive performance, and a preparation method and application of the composite material. In the preparation process of the graphite/epoxy resin composite material, graphite subjected to imidazole non-covalent bond surface modification is subjected to ultrasonic treatment for a certain time in a certain mode by a solution method, modified graphite micro-sheets are uniformly dispersed in epoxy resin to form a conductive network, and the graphite/epoxy resin conductive composite material is obtained by curing and molding after a solvent in a system is removed. The product with the conductive performance prepared by the composite material through a conventional process can be used in the fields of electronic appliances, stealth wave absorption and the like.
Description
Technical Field
The invention relates to a composite material of epoxy resin, in particular to a composite material with conductive performance, which is compounded by graphite modified by non-covalent bonds and epoxy resin, and a preparation method of the material.
Background
The epoxy resin has excellent mechanical property, thermal stability, bonding property, processing property and the like, can be used as a coating material, a composite material matrix and an adhesive, and is widely applied to the fields of machinery, chemical industry, electronic and electric appliances, aerospace and the like. Due to the relatively high volume resistivity of epoxy resins (around 10)13～1015Ω · cm) have been used for a long time as an insulating material. However, with the development of miniaturization and portability of electronic products, the application of epoxy resin composite materials with certain conductive properties in the fields of electronic information industry, aviation industry, public facilities and the like is more and more strongly demanded. The prepared epoxy resin conductive composite material can enlarge the application range of epoxy resin, and simultaneously provides more selection space for people in the selection of conductive materials.
The epoxy resin conductive composite material is a composite material system obtained by adding a curing agent, a conductive filler and other additives into epoxy resin serving as a matrix, dispersing the filler and curing resin. At present, the conductive filler is mainly classified into a metal filler and a carbon-based filler. The metal conductive filler is applied to the conductive composite material at first, but has the defects of high price (gold and silver), easiness in oxidation, high density and the like. As a typical representative of carbon-based conductive fillers, graphite not only has excellent conductivity, but also has the advantages of small thermal expansion coefficient, stable chemical properties, high temperature resistance, acid and alkali resistance, good dispersibility and the like, and is an ideal filler for preparing epoxy resin conductive composite materials. In addition, the graphite in China has abundant resources and low cost, and has absolute price advantage compared with the metal conductive filler.
With the wide application of the existing electronic and electric products, a conductive composite material which is simple and convenient to prepare, low in price and good in performance inevitably has great market demand, and meanwhile, the existence of the novel material also has important significance for widening the selection range of the conductive material.
Disclosure of Invention
The invention aims to provide a graphite/epoxy resin composite material and a preparation method thereof, wherein the composite material has good conductivity.
The graphite/epoxy resin conductive composite material comprises graphite, a graphite stabilizer, epoxy resin and an epoxy resin curing agent, wherein the graphite accounts for 13-40 wt% of the total mass of the composite material, and the graphite stabilizer accounts for 2-45 wt% of the total mass of the composite material;
the graphite is 80-mesh expanded graphite, the expansion rate is 300 times, and the carbon content is 99.95%;
the graphite stabilizer is imidazole and is chemically pure;
the epoxy resin is epoxy resin E51, and the epoxy value is 0.51;
the epoxy resin curing agent is D400, a polyether amine type curing agent.
The preparation method of the graphite/epoxy resin conductive composite material comprises the following steps:
adding graphite and a graphite stabilizer in a certain mass ratio into a round-bottom flask containing a certain amount of organic solvent, and fully mixing and dispersing;
step (2) placing the round-bottom flask containing the mixed solution obtained in the step (1) in an ultrasonic oscillator for ultrasonic treatment, adding a certain mass of epoxy resin curing agent into the mixed solution after a period of time, stirring and dispersing uniformly, and continuing the ultrasonic treatment for a period of time to obtain the required modified graphite dispersion solution;
step (3) transferring the modified graphite dispersion liquid obtained in the step (2) to a beaker filled with a certain amount of epoxy resin, then placing the beaker in an electric heating jacket for heating and stirring, so that the system is fully mixed on one hand, and a large amount of solvent in the system is removed on the other hand;
step (4) transferring the mixed system obtained in the step (3) from the beaker to a mould, then placing the mould in a blast oven, heating to remove residual solvent in the system, and then placing the mould in a vacuum oven for defoaming;
and (5) placing the system obtained in the step (4) and subjected to removal of all solvents and removal of bubbles in a forced air oven, curing and forming at a certain temperature, naturally cooling to room temperature, and demolding to obtain the graphite/epoxy resin composite material.
In the preparation method of the composite material of the present invention, in the step (1), preferably, the graphite is 80-mesh expanded graphite, the expansion rate is 300 times, the graphite stabilizer is imidazole, and the organic solvent is ethanol.
In the preparation method of the composite material, in the step (1), preferably, the amount of the expanded graphite is 15 wt% -40 wt% of the resin system (the total mass of the epoxy E51 and the curing agent D400), the amount of the graphite stabilizer imidazole is 30 wt% -350 wt% of the expanded graphite, and the initial concentration of the graphite in ethanol is 10mg/ml, so as to calculate the amount of the organic solvent ethanol.
In the method for preparing the composite material of the present invention, in the step (1), the mixed system is preferably sufficiently mixed and dispersed for 1 hour by using mechanical stirring.
In the preparation method of the composite material, in the step (2), preferably, the time of the front ultrasonic (first-stage ultrasonic) is 0.25-1.5 hours, and the time of the back ultrasonic (second-stage ultrasonic) is 0.25-2 hours. The mass ratio of the epoxy resin to the curing agent thereof is 100:59 or 100:128, namely E51: and D400 is 100:59 or 100:128, and the amount of the added epoxy resin curing agent is calculated according to the formula, and the epoxy resin curing agent is mechanically stirred for 15-20 minutes after being added into the system.
In the preparation method of the composite material, in the step (3), preferably, the heating temperature of the electric heating jacket is controlled to be 80-90 ℃, when the system is changed from a liquid state to a viscous state, most of the solvent is removed, and the heating is stopped.
In the preparation method of the composite material, in the step (4), preferably, the temperature of the air-blast oven is set to 70 ℃, the temperature of the vacuum oven is set to 60 ℃, and the vacuum degree is about-0.1 MPa.
In the method for preparing the composite material of the present invention, in the step (5), preferably, the curing conditions are: curing at 75 ℃ for 1-2 hours, curing at 110 ℃ for 1-2 hours, and curing at 150 ℃ for 1-2 hours.
The technical scheme adopted by the invention has the following advantages: the composite material not only maintains the excellent properties of the epoxy resin to a certain extent, but also greatly improves the conductivity (the conductivity is 10)-14The s/cm is increased to 0.1-16 s/cm), so that the method has wider application prospect in various fields.
Detailed Description
Example 1
(1) 0.342g of 80 mesh expanded graphite and 0.051g of imidazole were put in a 500ml round bottom flask containing 35ml of ethanol, and mechanically stirred for 1 hour to sufficiently mix and disperse the materials.
(2) And (3) placing the round-bottom flask containing the mixed solution in an ultrasonic oscillator, carrying out ultrasonic treatment for 0.5 hour, taking out the round-bottom flask, adding 1.28g of epoxy resin curing agent D400 into the mixed solution system, and mechanically stirring for 15 minutes. And then placing the round-bottom flask in an ultrasonic oscillator, and carrying out ultrasonic treatment for 0.5 hour to obtain the required modified graphite dispersion liquid.
(3) The modified graphite dispersion thus obtained was transferred to a 100ml beaker containing 1g of epoxy resin E51, and the beaker was heated in an electric mantle at 90 ℃ under continuous stirring to remove the ethanol solvent from the system while thoroughly mixing the epoxy resin with the graphite dispersion. When the system in the beaker changed from liquid to viscous paste, the heating was stopped and the beaker was removed from the mantle.
(4) The mixed system with the bulk of the solvent removed in the beaker was transferred to a teflon mold, which was placed in a forced air oven at a temperature of 70 ℃ until all residual solvent in the system was removed. The system is transferred from a blast oven to a vacuum oven for defoaming, the temperature of the vacuum oven is set to be 60 ℃, the vacuum degree is negative one atmosphere, and the defoaming time is 20 minutes.
(5) The resulting system, from which all the solvent had been removed and the bubbles had been removed, was cured in a forced air oven at 75 ℃ for 1 hour, at 110 ℃ for 1 hour and at 150 ℃ for 1 hour. Naturally cooling the cured material to room temperature, demolding to obtain the graphite/epoxy resin composite material, wherein the conductive filler graphite accounts for 15 wt% of the epoxy resin matrix, and the graphite stabilizer imidazole accounts for 15 wt% of the 80-mesh expanded graphite.
The composite material in example 1 was subjected to a conductivity test using an RTS-9 type dual electrical test four-probe tester, the average conductivity was 0.167s/cm, and the test results are shown in the following table:
example 2
(1) 0.912g of 80 mesh expanded graphite and 0.136g of imidazole were put in a 500ml round bottom flask containing 90ml of ethanol, and mechanically stirred for 1 hour to sufficiently mix and disperse the components.
(2) And (3) placing the round-bottom flask containing the mixed solution in an ultrasonic oscillator, carrying out ultrasonic treatment for 1 hour, taking out the round-bottom flask, adding 0.84g of epoxy resin curing agent D400 into the mixed solution system, and mechanically stirring for 15 minutes. And then placing the round-bottom flask in an ultrasonic oscillator, and carrying out ultrasonic treatment for 0.5 hour to obtain the required modified graphite dispersion liquid.
(3) The modified graphite dispersion thus obtained was transferred to a small 100ml beaker containing 1.44g of epoxy resin E51, and the beaker was heated in an electric mantle while stirring at 90 ℃ to remove the ethanol solvent from the system while thoroughly mixing the epoxy resin with the graphite dispersion. When the system in the beaker changed from liquid to viscous paste, the heating was stopped and the beaker was removed from the mantle.
(4) The mixed system with the bulk of the solvent removed in the beaker was transferred to a teflon mold, which was placed in a forced air oven at a temperature of 70 ℃ until all residual solvent in the system was removed. The system is transferred from a blast oven to a vacuum oven for defoaming, the temperature of the vacuum oven is set to be 60 ℃, the vacuum degree is negative one atmosphere, and the defoaming time is 20 minutes.
(5) The resulting system, from which all the solvent had been removed and the bubbles had been removed, was cured in a forced air oven at 75 ℃ for 1.5 hours, at 110 ℃ for 1.5 hours and at 150 ℃ for 1.5 hours. Naturally cooling the cured material to room temperature, demolding to obtain the graphite/epoxy resin composite material, wherein the conductive filler graphite accounts for 40 wt% of the epoxy resin matrix, and the content of the graphite stabilizer imidazole is 15 wt% of the content of 80-mesh expanded graphite.
The composite material of example 2 was tested for conductivity using an RTS-9 type dual electrical four-probe tester, with an average conductivity of 1.771s/cm, and the results are shown in the following table:
example 3
(1) 0.690g of 80 mesh expanded graphite and 2.415g of imidazole were put in a 500ml round bottom flask containing 70ml of ethanol, and mechanically stirred for 1 hour to sufficiently mix and disperse the components.
(2) And (3) placing the round-bottom flask containing the mixed solution in an ultrasonic oscillator, carrying out ultrasonic treatment for 0.5 hour, taking out the round-bottom flask, adding 1.28g of epoxy resin curing agent D400 into the mixed solution system, and mechanically stirring for 15 minutes. And then placing the round-bottom flask in an ultrasonic oscillator, and carrying out ultrasonic treatment for 0.5 hour to obtain the required modified graphite dispersion liquid.
(3) The modified graphite dispersion thus obtained was transferred to a 100ml beaker containing 1g of epoxy resin E51, and the beaker was heated in an electric mantle at 90 ℃ under continuous stirring to remove the ethanol solvent from the system while thoroughly mixing the epoxy resin with the graphite dispersion. When the system in the beaker changed from liquid to viscous paste, the heating was stopped and the beaker was removed from the mantle.
(4) The mixed system with the bulk of the solvent removed in the beaker was transferred to a teflon mold, which was placed in a forced air oven at a temperature of 70 ℃ until all residual solvent in the system was removed. The system is transferred from a blast oven to a vacuum oven for defoaming, the temperature of the vacuum oven is set to be 60 ℃, the vacuum degree is negative one atmosphere, and the defoaming time is 20 minutes.
(5) The resulting system, from which all the solvent had been removed and the bubbles had been removed, was cured in a forced air oven at 75 ℃ for 2 hours, at 110 ℃ for 2 hours and at 150 ℃ for 2 hours. Naturally cooling the cured material to room temperature, demolding to obtain the graphite/epoxy resin composite material, wherein the conductive filler graphite accounts for 30 wt% of the epoxy resin matrix, and the content of the graphite stabilizer imidazole is 350 wt% of the content of 80-mesh expanded graphite.
The composite material of example 3 was tested for conductivity using an RTS-9 dual electrical four-probe tester, with an average conductivity of 4.217s/cm, and the test results are shown in the following table:
the results show that the graphite/epoxy resin composite material has conductivity and can be used for general industrial or commercial electronic products.
Claims (8)
1. A preparation method of a graphite/epoxy resin conductive composite material is characterized in that the composite material is composed of graphite, a graphite stabilizer, epoxy resin and an epoxy resin curing agent, wherein the graphite accounts for 13 wt% -40 wt% of the total mass of the composite material, and the graphite stabilizer accounts for 2 wt% -45 wt% of the total mass of the composite material; the graphite is expanded graphite, the mesh number is 80 meshes, the expansion rate is 300 times, the carbon content is 99.95 percent, and the graphite stabilizer is imidazole;
the preparation method comprises the following steps:
(1) adding graphite and a graphite stabilizer in a certain mass ratio into a round-bottom flask containing a certain amount of organic solvent, and fully mixing and dispersing;
(2) placing the round-bottom flask containing the mixed solution obtained in the step (1) in an ultrasonic oscillator for ultrasonic treatment, adding a certain mass of epoxy resin curing agent into the mixed solution after a period of time, uniformly stirring and dispersing, and continuing the ultrasonic treatment for a period of time to obtain the required modified graphite dispersion solution;
(3) transferring the modified graphite dispersion liquid obtained in the step (2) into a beaker filled with a certain amount of epoxy resin, then placing the beaker into an electric heating jacket for heating and stirring, so that the system is fully mixed on one hand, and a large amount of solvent in the system is removed on the other hand;
(4) transferring the mixed system obtained in the step (3) from the beaker to a mould, then placing the mould in a blast oven, heating to remove residual solvent in the system, and then placing the mould in a vacuum oven to remove bubbles;
(5) and (4) placing the system obtained in the step (4) and subjected to removal of all solvents and removal of bubbles in a blast oven, curing and forming at a certain temperature, naturally cooling to room temperature, and demolding to obtain the graphite/epoxy resin composite material.
2. The method according to claim 1, wherein the epoxy resin is E51, and the curing agent is polyether amine D400.
3. The preparation method of claim 1, wherein the amount of the expanded graphite is 15 wt% to 40 wt% of the total mass of the resin system, namely epoxy E51 and curing agent D400, the amount of the graphite stabilizer imidazole is 30 wt% to 350 wt% of the expanded graphite, and the initial concentration of the graphite in ethanol is 10 mg/ml.
4. The production method according to claim 1, wherein the dispersion mixing method used in the step (1) is mechanical stirring.
5. The method according to claim 1, wherein the ultrasonic time in the step (2) is controlled by: performing pre-ultrasonic treatment for 0.25-1.5 hours, performing post-ultrasonic treatment for 0.25-2 hours, adding a curing agent, and then mechanically stirring for 15-20 minutes, wherein the mass ratio of the epoxy resin to the curing agent is 100:59 or 100: 128.
6. The preparation method according to claim 1, wherein the heating temperature of the electric jacket in the step (3) is controlled to be 80 to 90 ℃, and when the system changes from a liquid state to a viscous state, most of the solvent is removed, and the heating is stopped.
7. The production method according to claim 1, wherein the temperature of the forced draft oven in the step (4) is set to 70 ℃, the temperature of the vacuum oven is set to 60 ℃, and the degree of vacuum is-0.1 MPa.
8. The method according to claim 1, wherein the curing conditions in the step (5) are as follows: curing at 75 ℃ for 1-2 hours, curing at 110 ℃ for 1-2 hours, and curing at 150 ℃ for 1-2 hours.
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| CN102585259B (en) * | 2012-01-20 | 2013-10-09 | 苏州大学 | Preparation method of expanded graphite flake/thermosetting resin composite material |
| CN105566853A (en) * | 2015-12-01 | 2016-05-11 | 陕西易阳科技有限公司 | Preparation method of epoxy resin/graphite microsheet composite conductive material |
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