CN116042039B - Graphene heat dissipation damping coating and preparation method thereof - Google Patents
Graphene heat dissipation damping coating and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The application relates to the technical field of damping paint, and particularly discloses a graphene heat dissipation damping paint and a preparation method thereof. The graphene heat dissipation damping coating is mainly prepared from the following raw materials in parts by weight: 20-50 parts of graphene modified aqueous acrylic emulsion, 9-23 parts of modified graphene oxide, 20-38 parts of damping filler, 1-3 parts of film forming auxiliary agent, 1-2 parts of functional auxiliary agent and 10-15 parts of deionized water. The graphene heat dissipation damping coating takes graphene modified aqueous acrylic emulsion as a main film forming component, and cooperates with the synergistic effect of modified graphene oxide, so that the heat conductivity coefficient and the composite loss factor are obviously improved, the wear rate is also obviously reduced, the graphene heat dissipation damping coating has the advantages of high heat dissipation, high wear resistance and high damping, and the graphene heat dissipation damping coating has good comprehensive performance and meets market demands.
Description
Technical Field
The application relates to the technical field of damping paint, in particular to graphene heat dissipation damping paint and a preparation method thereof.
Background
The damping paint is prepared by adding a proper amount of filler and auxiliary agent into polymer resin, is generally coated on the surface of a metal structure to form a dry film, has the function of converting the mechanical vibration of solid into heat to be dissipated, so as to achieve the effects of shock absorption and noise reduction, and is widely studied and applied to the fields of airplanes, ships, vehicles, machinery, transformers and the like.
The commercially available damping paint mainly comprises acrylic resin emulsion, filler, auxiliary agent and water, and has excellent damping and noise reduction effects. When damping material is applied to equipment such as transformer, the long-time work of transformer can produce more heat, and heat transfer reaches the dry film surface that damping material formed, because the heat dispersion on dry film surface is relatively poor, at this moment, gathers the heat on dry film surface and is difficult to distribute away, leads to the transformer high temperature to take place harm easily.
Disclosure of Invention
In order to increase the heat dissipation of the damping coating and enable the damping coating to have the functions of damping, noise reduction and heat dissipation, the application provides a graphene heat dissipation damping coating and a preparation method thereof.
In a first aspect, the application provides a graphene heat dissipation damping coating, which adopts the following technical scheme:
the graphene heat dissipation damping coating is mainly prepared from the following raw materials in parts by weight: 20-50 parts of graphene modified aqueous acrylic emulsion, 9-23 parts of modified graphene oxide, 20-38 parts of damping filler, 1-3 parts of film forming auxiliary agent, 1-2 parts of functional auxiliary agent and 10-15 parts of deionized water.
According to the graphene heat dissipation damping coating disclosed by the application, through the mutual matching of raw materials, the heat conductivity coefficient is more than 10W/m.K, the wear rate is less than 2.5%, the water resistance is more than 50d, the composite loss factor is more than 0.05 at the temperature of 0 ℃ and is more than 0.11 at the temperature of 40 ℃, so that the graphene heat dissipation damping coating has the advantages of high heat dissipation, high wear resistance, high damping and long-term use stability, has good comprehensive performance, and meets market demands.
Optionally, the graphene modified aqueous acrylic emulsion is mainly prepared from the following raw materials in parts by weight: 70-80 parts of deionized water, 30-40 parts of methyl methacrylate, 60-70 parts of diethylaminoethyl methacrylate, 35-45 parts of trimethylolpropane triacrylate, 2-4 parts of an initiator, 8-12 parts of an emulsifier, 4-6 parts of a graphene aqueous solution, and the mass concentration of graphene in the graphene aqueous solution is 3-5wt%.
Methyl methacrylate contains a carbon-carbon double bond, diethylaminoethyl methacrylate contains a carbon-carbon double bond, diethylamino group and trimethylolpropane triacrylate contains three branches, each branch contains a carbon-carbon double bond, and the three branches are polymerized to form a polymer under the action of an initiator, and the performance of the polymer is effectively improved through the mutual coordination of the three branches. Meanwhile, when the three materials undergo polymerization reaction, graphene aqueous solution is added, and graphene is dispersed in deionized water in advance, so that graphene can be uniformly dispersed in the polymer, the heat dissipation performance of the polymer is effectively improved, and the heat dissipation performance, the damping performance and the wear resistance of the graphene heat dissipation damping coating are also improved.
Optionally, the graphene modified aqueous acrylic emulsion is prepared by the following method: adding an emulsifier into deionized water at 80-90 ℃, stirring for 20-40min, adding graphene aqueous solution, stirring for 20-40min, adding methyl methacrylate, diethylaminoethyl methacrylate and trimethylolpropane triacrylate, stirring for 1-3h, adding an initiator, stirring for 7-9h, and cooling to obtain graphene modified aqueous acrylic emulsion.
By adopting the technical scheme, the preparation of the graphene modified aqueous acrylic emulsion is facilitated.
Further, the initiator is ammonium persulfate. The emulsifier is one or more of sodium dodecyl sulfate, surfactant AEO-9 and emulsifier OP-10.
Still further, the emulsifier is three of sodium dodecyl sulfate, surfactant AEO-9 and emulsifier OP-10, and the weight ratio of the sodium dodecyl sulfate, the surfactant AEO-9 and the emulsifier OP-10 is 1 (1-3). In one embodiment, the weight ratio of sodium dodecyl sulfate, surfactant AEO-9, emulsifier OP-10 is 1:2:2, which can also be adjusted to 1:1:1, 1:3:3, 1:2:3, 1:3:2, etc. as desired.
Optionally, the graphene aqueous solution is prepared by the following method: adding graphene into tetrahydrofuran, carrying out ultrasonic treatment for 1-3h, then adding 3-methacryloxypropyl trimethoxy silane, stirring for 50-70min, then adding deionized water, stirring for 20-40min, heating to 70-75 ℃, removing tetrahydrofuran, cooling, and adopting deionized water to fix the volume to obtain a graphene aqueous solution;
wherein the weight ratio of the graphene to the 3-methacryloxypropyl trimethoxy silane is 8 (0.5-1.5).
Compared with tetrahydrofuran and deionized water, the graphene is easier to disperse in tetrahydrofuran, but tetrahydrofuran has certain volatility, and if the tetrahydrofuran is applied to the graphene heat dissipation damping paint, VOC is increased. According to the application, graphene is added into tetrahydrofuran, and ultrasonic treatment is matched, so that the graphene can be uniformly dispersed, and the condition of graphene agglomeration is reduced. 3-methacryloxypropyl trimethoxysilane was then added, which was able to be grafted onto graphene. Then deionized water is added, tetrahydrofuran and deionized water are mutually dissolved, then the temperature is raised to remove the tetrahydrofuran, and at the moment, the graphene is uniformly dispersed in the deionized water, and a graphene aqueous solution is formed. By dispersing graphene in tetrahydrofuran in advance and then removing the tetrahydrofuran, not only is the dispersibility of the graphene in deionized water maintained and the agglomeration condition reduced, but also the influence of VOC increase caused by the tetrahydrofuran in the graphene aqueous solution is reduced. Meanwhile, 3-methacryloxypropyl trimethoxy silane is added, and the 3-methacryloxypropyl trimethoxy silane contains carbon-carbon double bonds, can participate in polymerization reaction in the subsequent process, so that the bonding strength and dispersibility of graphene and a polymer are improved, and the heat dissipation, damping and wear resistance of the graphene heat dissipation damping coating are enhanced.
In one embodiment, the weight ratio of graphene to 3-methacryloxypropyl trimethoxysilane is 8:1, which can also be adjusted to 8:0.5, 8:1.5, etc. as desired.
Optionally, the modified graphene oxide is prepared by the following method:
s1, adding graphene oxide into deionized water, performing ultrasonic treatment for 20-40min, then adding N-hydroxysuccinimide sodium sulfonate and 3-methacryloxypropyl trimethoxy silane, stirring for 50-70min, then adding carbon tetrachloride, stirring for 50-70min, and standing for layering to obtain a lower layer liquid;
s2, centrifuging the lower layer liquid to obtain particles;
s3, adding particles into acetonitrile at the temperature of 35-45 ℃, stirring for 20-40min, then adding trivinyl diol, stirring for 1-3h, heating to 70-80 ℃, then adding sodium carbonate and 1, 8-diamino-3, 6-dioxaoctane, stirring for 20-25h, cooling, centrifuging, washing with glycerol, and drying to constant weight to obtain the modified graphene oxide.
According to the modified graphene oxide disclosed by the application, firstly, graphene oxide is dispersed in deionized water, then, N-hydroxysuccinimide sodium sulfonate and 3-methacryloxypropyl trimethoxy silane are added, the graphene oxide is activated, and active groups on the surface of the graphene oxide are increased. And adding carbon tetrachloride, wherein the carbon tetrachloride and the deionized water are insoluble, standing to effectively stratify, the deionized water is positioned on the upper layer, the carbon tetrachloride is positioned on the lower layer, and the graphene oxide is positioned on the carbon tetrachloride layer, and centrifuging to obtain particles, so that the agglomeration condition of the graphene oxide in the centrifuging process can be effectively reduced, and the granularity and the dispersibility of the graphene oxide are maintained. Meanwhile, acetonitrile and deionized water can realize mutual dissolution, but in the presence of sodium carbonate, acetonitrile and deionized water have obvious layering, and centrifugation is carried out after carbon tetrachloride is added, so that the water content in particulate matters can be effectively reduced, and the layering condition of acetonitrile and deionized water is reduced. And then under the catalysis of acetonitrile environment and sodium carbonate, the trivinyl glycol and the 1, 8-diamino-3, 6-dioxaoctane react on the surfaces of the particles and in the pores to form aminopolyether, so that the dispersion stability and the bonding strength of graphene oxide are effectively improved, and the use stability of the graphene heat dissipation damping coating is improved. Meanwhile, sodium carbonate is easy to dissolve in glycerol, and the glycerol is adopted for washing, so that the sodium carbonate can be effectively removed, and the influence of the sodium carbonate on the modified graphene oxide and the graphene heat dissipation damping coating is reduced.
Optionally, the weight ratio of the graphene oxide to the sodium N-hydroxysuccinimide sulfonate to the 3-methacryloxypropyl trimethoxy silane to the triethylene glycol to the 1, 8-diamino-3, 6-dioxaoctane is 5 (0.5-1.5) (10-20) (1-3).
By adopting the technical scheme, the raw material proportion in the preparation of the modified graphene oxide is optimized, so that the preparation of the modified graphene oxide is facilitated.
In one embodiment, the weight ratio of graphene oxide, sodium N-hydroxysuccinimide sulfonate, 3-methacryloxypropyl trimethoxysilane, trivinyl diol, 1, 8-diamino-3, 6-dioxaoctane is 5:1:1:15:2, which can also be adjusted to 5:0.5:1.5:15:2, 5:1.5:0.5:15:2, 5:0.5:1.5:10:3, 5:1.5:0.5:20:1, etc. as desired.
In the step S1 of the preparation method of the modified graphene oxide, the weight ratio of deionized water, graphene oxide and carbon tetrachloride is (18-22) 1 (50-70). In one embodiment, the weight ratio of deionized water, graphene oxide, carbon tetrachloride is 20:1:60, which can also be adjusted to 18:1:60, 22:1:70, etc. as desired.
In the step S3 of the preparation method of the modified graphene oxide, the weight ratio of acetonitrile to 1, 8-diamino-3, 6-dioxaoctane is (250-350) (1-3). In one embodiment, the weight ratio of acetonitrile, 1, 8-diamino-3, 6-dioxaoctane is 150:1, which can also be adjusted to 250:1, 350:3, etc. as desired.
Optionally, the damping filler is one or more of calcium carbonate, mica powder, zinc oxide and titanium dioxide. And the damping filler is optimized, so that the damping filler is convenient to select.
Further, the damping filler is four kinds of calcium carbonate, mica powder, zinc oxide and titanium dioxide, and the weight ratio of the calcium carbonate, the mica powder, the zinc oxide and the titanium dioxide is (0.5-1.5): 2-3): 0.5-1.5): 1.5-2.5. In one embodiment, the weight ratio of the calcium carbonate, the mica powder, the zinc oxide and the titanium dioxide is 1:2.5:1:2, and the weight ratio of the calcium carbonate, the mica powder, the zinc oxide and the titanium dioxide can be adjusted to be 0.5:3:0.5:2.5, 1.5:3:1.5:2.5, 1.5:2:1.5:1.5, 0.5:2:0.5:1.5 and the like according to the requirement.
Optionally, the functional auxiliary agent is one or more of an adhesion promoter, a dispersing agent, a leveling agent and a defoaming agent. The functional auxiliary agent is optimized, so that the functional auxiliary agent is convenient to select.
Further, the functional auxiliary agents comprise four kinds of adhesion promoters, dispersing agents, leveling agents and defoaming agents, and the weight ratio of the adhesion promoters, the dispersing agents, the leveling agents and the defoaming agents is (1.5-2.5): 1-2): 0.5-1.5. In one embodiment, the weight ratio of the calcium carbonate, the mica powder, the zinc oxide and the titanium dioxide is 2:1.5:1.5:1:1, and the weight ratio of the calcium carbonate, the mica powder, the zinc oxide and the titanium dioxide can be adjusted to be 1.5:1:1.5:1.5, 1.5:2:2:1.5:1.5, 2.5:2:0.5:0.5 and the like according to the requirement.
Further, the film forming aid is propylene glycol ether film forming aid DALPAD D. The adhesion promoter is adhesion promoter SY-5622. The dispersant is an aqueous dispersant Silok 7111W. The leveling agent is a leveling agent BYK-307. The defoaming agent is organosilicon defoaming agent AKN-3801.
Optionally, the construction dry film thickness of the graphene heat dissipation damping coating is 1-3mm.
When the construction dry film thickness is too thick, the heat dissipation effect is affected, and when the construction dry film thickness is too thin, the damping effect is affected. According to the application, the thickness of the construction dry film is optimized, and when the thickness of the construction dry film is 1-3mm, the graphene heat dissipation damping coating maintains good comprehensive performance, and the market demand is met.
In a second aspect, the present application provides a preparation method of the graphene heat dissipation damping coating, which adopts the following technical scheme:
the preparation method of the graphene heat dissipation damping coating comprises the following steps: adding graphene modified aqueous acrylic emulsion into deionized water, mixing, adding modified graphene oxide and damping filler, mixing, and adding a film forming additive and a functional additive, mixing to obtain the graphene heat dissipation damping coating.
By adopting the technical scheme, the preparation of the graphene heat dissipation damping coating is facilitated.
In summary, the application has the following beneficial effects:
1. according to the graphene heat dissipation damping coating disclosed by the application, the graphene modified aqueous acrylic emulsion is used as a main film forming component, and the graphene modified aqueous acrylic emulsion is matched with the synergistic effect of modified graphene oxide, so that the heat conductivity coefficient and the composite loss factor are obviously improved, the wear rate is also obviously reduced, the graphene heat dissipation damping coating has the advantages of high heat dissipation, high wear resistance and high damping, and the graphene heat dissipation damping coating has good comprehensive performance and meets market demands.
2. In the preparation method of the graphene modified water-based acrylic emulsion, methyl methacrylate, diethylaminoethyl methacrylate and trimethylolpropane triacrylate are utilized to form a polymer, and the polymer is matched with a graphene aqueous solution, so that the heat dissipation, damping and wear resistance of the graphene heat dissipation damping coating are improved. In addition, in the graphene aqueous solution, graphene is dispersed in tetrahydrofuran in advance, and then tetrahydrofuran is removed, so that not only is the dispersibility of the graphene in deionized water maintained and the agglomeration condition reduced, but also the influence of VOC (volatile organic compounds) increase due to the tetrahydrofuran in the graphene aqueous solution is reduced.
3. In the preparation method of the modified graphene oxide, N-hydroxysuccinimide sodium sulfonate and 3-methacryloxypropyl trimethoxy silane are utilized to increase active groups of the graphene oxide, carbon tetrachloride and deionized water are not mutually dissolved, separation of particles and deionized water is realized, moisture in the particles is reduced, and amino polyether is formed by reacting triethylene glycol, 1, 8-diamino-3, 6-dioxaoctane on the surfaces of the particles and pores in an acetonitrile environment, so that the dispersibility and the bonding strength of the graphene oxide are effectively improved, further glycerin washing is adopted to effectively remove sodium carbonate, and the influence of sodium carbonate on the modified graphene oxide and the graphene heat dissipation damping coating is reduced.
Detailed Description
In order that the application may be more readily understood, the application will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Preparation example
TABLE 1 graphene modified waterborne acrylic emulsion raw material contents (Unit: kg)
| Preparation example | Preparation example I-1 | PREPARATION EXAMPLE I-2 | Preparation examples I1 to 3 |
| Deionized water | 75 | 70 | 80 |
| Methyl methacrylate | 35 | 40 | 30 |
| Diethylaminoethyl methacrylate | 65 | 60 | 70 |
| Trimethylolpropane triacrylate | 40 | 45 | 35 |
| Initiator(s) | 3 | 4 | 2 |
| Emulsifying agent | 10 | 12 | 8 |
| Aqueous graphene solution | 5 | 4 | 6 |
Preparation example I-1
The raw material ratio of the graphene modified aqueous acrylic emulsion is shown in table 1.
Wherein the initiator is ammonium persulfate; the mass concentration of graphene in the graphene aqueous solution is 4wt%;
the emulsifier is composed of three components of sodium dodecyl sulfate, surfactant AEO-9 and emulsifier OP-10, wherein the weight ratio of the sodium dodecyl sulfate to the surfactant AEO-9 to the emulsifier OP-10 is 1:2:2.
The preparation method of the graphene modified aqueous acrylic emulsion comprises the following steps:
deionized water is added into the reaction tank a at the temperature of 85 ℃ and the rotating speed of 500r/min, then an emulsifying agent is added, and stirring treatment is carried out for 30min. And adding the graphene aqueous solution, and stirring for 60min. Then methyl methacrylate, diethylaminoethyl methacrylate and trimethylolpropane triacrylate are added and stirred for 2h. Then adding the initiator, and stirring for 8 hours. And then cooling to 25 ℃ to obtain the graphene modified aqueous acrylic emulsion.
The graphene aqueous solution is prepared by the following method: adding 20kg of tetrahydrofuran into a premixed ultrasonic stirring tank, then adding 0.8kg of graphene, starting ultrasonic treatment, performing ultrasonic treatment for 2 hours at the ultrasonic frequency of 30KHz, and closing ultrasonic treatment. Then, 0.1kg of 3-methacryloxypropyl trimethoxysilane was added and the mixture was stirred for 60 minutes. Then 15kg of deionized water was added thereto and stirred for 30 minutes. Then, the temperature was raised to 70℃and the mixture was stirred for 30 minutes, at which time tetrahydrofuran was volatilized and removed. And then cooling to 25 ℃, and then adopting deionized water to fix the volume to 20kg to obtain the graphene aqueous solution. At this time, the mass concentration of graphene in the graphene aqueous solution was 4wt%.
The graphene is a Forsman technology (Beijing) limited company.
Preparation examples I-2 to I-3
The graphene modified aqueous acrylic emulsion is different from the preparation example I-1 in that the raw material ratio of the graphene modified aqueous acrylic emulsion is different, and the raw material ratio is shown in table 1.
PREPARATION EXAMPLE I-4
A graphene modified aqueous acrylic emulsion is different from the preparation example I-1 in that the same amount of methyl methacrylate is used for replacing trimethylolpropane triacrylate in the raw material of the graphene modified aqueous acrylic emulsion.
PREPARATION EXAMPLE I-5
The difference between the graphene modified aqueous acrylic emulsion and the preparation example I-1 is that the preparation method of the graphene aqueous solution is different from that of the raw material of the graphene modified aqueous acrylic emulsion.
The graphene aqueous solution is prepared by the following method: 15kg of deionized water is added into a premixed ultrasonic stirring tank, then 0.8kg of graphene is added, ultrasonic treatment is started, ultrasonic treatment is performed for 2 hours under the ultrasonic frequency of 30KHz, and ultrasonic treatment is stopped. Then adding 0.1kg of 3-methacryloxypropyl trimethoxy silane, stirring for 60min, and then adopting deionized water to fix the volume to 20kg to obtain the graphene aqueous solution. At this time, the mass concentration of graphene in the graphene aqueous solution was 4wt%.
Preparation example II-1
A modified graphene oxide prepared by the following method:
s1, adding 100kg of deionized water into an ultrasonic stirring tank at the rotating speed of 500r/min, then adding 5kg of graphene oxide, starting ultrasonic treatment, performing ultrasonic treatment for 30min at the ultrasonic frequency of 30KHz, and closing ultrasonic treatment. Then, 1kg of sodium N-hydroxysuccinimide sulfonate and 1kg of 3-methacryloxypropyl trimethoxysilane were added and the mixture was stirred for 60 minutes. Then 300kg of carbon tetrachloride was added thereto and the mixture was stirred for 60 minutes. Standing and layering to obtain a lower layer liquid.
Among them, graphene oxide is a company of fosman technology (beijing).
S2, centrifuging the lower layer liquid by adopting a centrifuge to obtain particles.
S3, adding 300kg of acetonitrile into the reaction tank b at the temperature of 40 ℃ and the rotating speed of 500r/min, then adding the particles obtained in the step S2, and stirring for 30min. Then 15kg of trivinyldiol was added thereto and stirred for 2 hours. Then, the temperature was raised to 75℃and 10kg of sodium carbonate and 2kg of 1, 8-diamino-3, 6-dioxaoctane were added thereto and the mixture was stirred for 23 hours. Then cooling to 25 ℃. Centrifugation was performed using a centrifuge. And then, washing with glycerol for three times, wherein the usage amount of the glycerol is 500kg each time, and drying to constant weight to obtain the modified graphene oxide.
Preparation example II-2
The modified graphene oxide differs from the preparation example II-1 in that the preparation method of the modified graphene oxide is different from the preparation method of the modified graphene oxide in step S1 and step S2.
The steps S1 and S2 specifically comprise: 100kg of deionized water is added into an ultrasonic stirring tank at the rotating speed of 500r/min, then 5kg of graphene oxide is added, ultrasonic treatment is started, ultrasonic treatment is performed for 30min at the ultrasonic frequency of 30KHz, and ultrasonic treatment is stopped. Then, 1kg of sodium N-hydroxysuccinimide sulfonate and 1kg of 3-methacryloxypropyl trimethoxysilane were added and the mixture was stirred for 60 minutes. And then adopting a centrifugal machine to carry out centrifugation to obtain the particulate matters.
Preparation example II-3
A modified graphene oxide differs from preparation example II-1 in that step S3 is different in the preparation method of the modified graphene oxide.
The step S3 specifically comprises the following steps: 300kg of acetonitrile was added to the reaction tank b at 40℃and 500r/min, followed by addition of 20kg of triethylene glycol and stirring treatment for 2 hours. Then, the temperature was raised to 75℃and 10kg of sodium carbonate and 1kg of 1, 8-diamino-3, 6-dioxaoctane were added thereto and the mixture was stirred for 23 hours. Then cooling to 25 ℃. Then adding the particles obtained in the step S2, and stirring for 30min. Centrifugation was performed using a centrifuge. Then the mixture is washed three times by glycerol, the usage amount of each glycerol is 500kg, and the mixture is dried to constant weight, thus obtaining the modified graphene oxide
Examples
TABLE 2 graphene Heat dissipation damping coating raw material content (Unit: kg)
| Examples | Example 1 | Example 2 | Example 3 |
| Graphene modified aqueous acrylic emulsion | 35 | 20 | 50 |
| Modified graphene oxide | 15 | 9 | 23 |
| Damping filler | 30 | 38 | 20 |
| Film forming aid | 2 | 3 | 1 |
| Deionized water | 1.5 | 2 | 1 |
| Functional auxiliary agent | 13 | 15 | 10 |
Example 1
The raw material proportions of the graphene heat dissipation damping paint are shown in table 2.
Wherein the film forming additive is propylene glycol ether film forming additive DALPAD D; the graphene modified aqueous acrylic emulsion is prepared by adopting a preparation example I-1; the modified graphene oxide is prepared by adopting a preparation example II-1;
the damping filler is four kinds of calcium carbonate, mica powder, zinc oxide and titanium dioxide, and the weight ratio of the calcium carbonate to the mica powder to the zinc oxide to the titanium dioxide is 1:2.5:1:2;
the functional auxiliary agents comprise four kinds of adhesion promoters, dispersing agents, leveling agents and defoaming agents, wherein the weight ratio of the adhesion promoters to the dispersing agents to the leveling agents to the defoaming agents is 2:1.5:1:1, and the adhesion promoters are adhesion promoters SY-5622; the dispersant is an aqueous dispersant Silok 7111W; the leveling agent is a leveling agent BYK-307; the defoaming agent is organosilicon defoaming agent AKN-3801.
A preparation method of graphene heat dissipation damping paint comprises the following steps:
at the rotating speed of 1000r/min, deionized water is added into a mixing tank, then graphene modified aqueous acrylic emulsion is added, and stirring treatment is carried out for 10min. And then adding the modified graphene oxide and the damping filler, stirring for 60min, and then adding the film forming auxiliary agent and the functional auxiliary agent, and stirring for 30min to obtain the graphene heat dissipation damping coating.
Examples 2 to 3
The difference between the graphene heat dissipation damping paint and the embodiment 1 is that the raw material ratio of the graphene heat dissipation damping paint is different, and the raw material ratio is shown in table 2.
Examples 4 to 7
The difference between the graphene heat dissipation damping coating and the embodiment 1 is that the graphene modified aqueous acrylic emulsion sources are different in raw materials of the graphene heat dissipation damping coating, and the graphene modified aqueous acrylic emulsion of the embodiment 4-7 is prepared by adopting preparation examples I-2 to I-5 in sequence.
Examples 8 to 9
The difference between the graphene heat dissipation damping coating and the embodiment 1 is that the sources of the modified graphene oxide in the raw materials of the graphene heat dissipation damping coating are different, and the modified graphene oxide in the embodiments 8-9 are prepared by adopting the preparation examples II-2 to II-3 in sequence.
Comparative example
Comparative example 1
A graphene heat dissipation damping coating is different from example 1 in that the graphene aqueous solution is replaced by the same amount of deionized water in the raw material of the graphene modified aqueous acrylic emulsion.
Comparative example 2
The difference between the graphene heat dissipation damping paint and the embodiment 1 is that the graphene modified aqueous acrylic emulsion is used for replacing the modified graphene oxide with the same amount of graphene in the raw materials of the graphene heat dissipation damping paint.
Comparative example 3
The difference between the graphene heat dissipation damping paint and the embodiment 1 is that the graphene heat dissipation damping paint is prepared by replacing modified graphene oxide with equivalent graphene oxide in raw materials of the graphene heat dissipation damping paint.
Comparative example 4
A graphene heat dissipation damping paint is different from example 1 in that the modified graphene oxide is replaced by equal amount of zinc oxide in raw materials of the graphene heat dissipation damping paint.
Performance detection
The graphene heat dissipation damping paint obtained in examples 1 to 9 and comparative examples 1 to 4 was taken respectively, then a layer of graphene heat dissipation damping paint was coated on a metal copper plate, a dry film with a thickness of 2mm was obtained, the dry film was taken as a sample, and the following performance tests were performed, and the test results are shown in table 3.
Wherein the thermal conductivity of the test specimen is measured according to ASTM E1530-19. And the higher the heat conductivity coefficient is, the better the heat dissipation effect of the graphene heat dissipation damping material is.
The abrasion resistance is achieved by the following method; the surface of the sample is rubbed by adopting a sanding machine and is characterized by the abrasion rate, and the smaller the abrasion rate is, the better the abrasion resistance of the graphene heat dissipation damping material is. Abrasion ratio= (mass before dry film abrasion-mass after dry film abrasion)/mass before dry film abrasion x 100%.
The water resistance is achieved by the following method: the sample was added to water at 25℃and allowed to soak completely, and left to stand for 60 days to observe the time during which the sample had foamed and softened. And the longer the days, the better the water resistance of the graphene heat dissipation damping material is shown.
According to GB/T16406-1996, composite loss factors of samples at different temperatures are detected, and the larger the composite loss factors are, the better the damping effect of the graphene heat dissipation damping material is shown.
TABLE 3 detection results
As can be seen from Table 3, the graphene heat dissipation damping coating provided by the application has a relatively high heat conductivity coefficient, the heat conductivity coefficient is 10.23-18.42W/m.K, and a high heat dissipation effect is shown. It also has low abrasion rate, high water washing resistance, abrasion rate of 0.76-2.46%, no foaming and softening after soaking in water at 25deg.C for 50d, high abrasion resistance and long-term use stability. The composite loss factor is 0.052-0.079 at the temperature of 0 ℃, and 0.117-0.173 at the temperature of 40 ℃ and shows high damping effect. The graphene heat-dissipation damping coating has the advantages of shock absorption, noise reduction, heat dissipation, wear resistance and stable use, shows good comprehensive performance, and meets market demands.
Comparing example 1 with comparative example 1-2, it can be seen that graphene modified aqueous acrylic emulsion and modified graphene oxide are added into raw materials of the graphene heat dissipation damping coating at the same time, and the heat conductivity coefficient and the composite loss factor can be obviously improved through mutual cooperation between the graphene modified aqueous acrylic emulsion and the modified graphene oxide, so that the heat dissipation effect and the damping effect of the graphene heat dissipation damping coating can be improved. Meanwhile, the wear rate is obviously reduced, and the wear resistance of the graphene heat dissipation damping coating is enhanced.
Comparing comparative examples 3-4, it can be seen that the effect of adding graphene oxide to the raw material of the graphene heat-dissipating damping coating is significantly better than that of adding zinc oxide. By combining with the embodiment 1, the graphene oxide is modified, so that the use effect of the graphene oxide can be further improved, and the dispersion uniformity and the bonding strength of the graphene oxide can be effectively improved due to the modification of the graphene oxide, so that the use effect of the graphene oxide is improved, and the heat dissipation, damping and wear resistance of the graphene heat dissipation damping paint are further improved.
Comparing example 1 with example 8, it can be seen that in the preparation method of modified graphene oxide, the insolubility of carbon tetrachloride and deionized water is adopted, so that the particles enter carbon tetrachloride, and then the particles are obtained by centrifugation, so that the heat conductivity coefficient and the composite loss factor can be increased, and the wear rate can be reduced, which is probably due to the fact that carbon tetrachloride keeps the dispersibility of the particles, agglomeration is reduced, and therefore the use effect of graphene oxide and the performance of the graphene heat dissipation damping coating are improved. In the preparation method of the modified graphene oxide, in combination with example 9, the trivinyl glycol, the 1, 8-diamino-3, 6-dioxaoctane and the amino polyether are added into the mixture of acetonitrile and the particles, and react on the surfaces and in the pores of the particles to form the amino polyether, so that the use effect of the graphene oxide, and the heat dissipation, the damping and the wear resistance of the graphene thermal damping coating can be enhanced.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
Claims (3)
1. A graphene heat dissipation damping coating is characterized in that: the traditional Chinese medicine is mainly prepared from the following raw materials in parts by weight: 20-50 parts of graphene modified aqueous acrylic emulsion, 9-23 parts of modified graphene oxide, 20-38 parts of damping filler, 1-3 parts of film forming auxiliary agent, 1-2 parts of functional auxiliary agent and 10-15 parts of deionized water; the graphene modified aqueous acrylic emulsion is mainly prepared from the following raw materials in parts by weight: 70-80 parts of deionized water, 30-40 parts of methyl methacrylate, 60-70 parts of diethylaminoethyl methacrylate, 35-45 parts of trimethylolpropane triacrylate, 2-4 parts of an initiator, 8-12 parts of an emulsifier, 4-6 parts of a graphene aqueous solution, and the mass concentration of graphene in the graphene aqueous solution is 3-5wt%; the damping filler is composed of four components of calcium carbonate, mica powder, zinc oxide and titanium dioxide, wherein the weight ratio of the calcium carbonate to the mica powder is (0.5-1.5), the weight ratio of the zinc oxide to the titanium dioxide is (2-3), the weight ratio of the calcium carbonate to the mica powder is (0.5-1.5), and the weight ratio of the zinc oxide to the titanium dioxide is (1.5-2.5); the functional auxiliary agent comprises four components of an adhesion promoter, a dispersing agent, a leveling agent and a defoaming agent, wherein the weight ratio of the adhesion promoter to the dispersing agent to the leveling agent to the defoaming agent is (1.5-2.5): 1-2): 0.5-1.5;
the graphene modified aqueous acrylic emulsion is prepared by the following method: adding an emulsifier into deionized water at 80-90 ℃, stirring for 20-40min, adding graphene aqueous solution, stirring for 20-40min, adding methyl methacrylate, diethylaminoethyl methacrylate and trimethylolpropane triacrylate, stirring for 1-3h, adding an initiator, stirring for 7-9h, and cooling to obtain graphene modified aqueous acrylic emulsion;
the graphene aqueous solution is prepared by the following method: adding graphene into tetrahydrofuran, carrying out ultrasonic treatment for 1-3h, then adding 3-methacryloxypropyl trimethoxy silane, stirring for 50-70min, then adding deionized water, stirring for 20-40min, heating to 70-75 ℃, removing tetrahydrofuran, cooling, and adopting deionized water to fix the volume to obtain a graphene aqueous solution; wherein, the weight ratio of the graphene to the 3-methacryloxypropyl trimethoxy silane is 8 (0.5-1.5);
the modified graphene oxide is prepared by the following method:
s1, adding graphene oxide into deionized water, performing ultrasonic treatment for 20-40min, then adding N-hydroxysuccinimide sodium sulfonate and 3-methacryloxypropyl trimethoxy silane, stirring for 50-70min, then adding carbon tetrachloride, stirring for 50-70min, and standing for layering to obtain a lower layer liquid;
s2, centrifuging the lower layer liquid to obtain particles;
s3, adding particles into acetonitrile at the temperature of 35-45 ℃, stirring for 20-40min, then adding trivinyl diol, stirring for 1-3h, heating to 70-80 ℃, then adding sodium carbonate and 1, 8-diamino-3, 6-dioxaoctane, stirring for 20-25h, cooling, centrifuging, washing with glycerol, and drying to constant weight to obtain modified graphene oxide;
the weight ratio of the graphene oxide to the sodium N-hydroxysuccinimide sulfonate to the 3-methacryloxypropyl trimethoxy silane to the triethylene glycol to the 1, 8-diamino-3, 6-dioxaoctane is 5 (0.5-1.5), 0.5-1.5, 10-20 and 1-3.
2. The graphene heat dissipation damping coating according to claim 1, wherein: the thickness of a construction dry film of the graphene heat dissipation damping coating is 1-3mm.
3. A method for preparing the graphene heat dissipation damping paint as claimed in any one of claims 1-2, which is characterized in that: the method comprises the following steps: adding graphene modified aqueous acrylic emulsion into deionized water, mixing, adding modified graphene oxide and damping filler, mixing, and adding a film forming additive and a functional additive, mixing to obtain the graphene heat dissipation damping coating.
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