CN117965065A - Heat-conducting water-based acrylic paint and preparation method and application thereof - Google Patents
Heat-conducting water-based acrylic paint and preparation method and application thereof Download PDFInfo
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003973 paint Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 291
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 164
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 71
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 35
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 66
- 239000010439 graphite Substances 0.000 claims description 59
- 239000006185 dispersion Substances 0.000 claims description 54
- 238000000227 grinding Methods 0.000 claims description 40
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 30
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 15
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- 229920005614 potassium polyacrylate Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 6
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- 239000011734 sodium Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004122 cyclic group Chemical group 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
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- 239000002002 slurry Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the field of acrylic acid coatings, and relates to a heat-conducting water-based acrylic acid coating, and a preparation method and application thereof. The heat-conducting water-based acrylic coating comprises an acrylic resin emulsion and water-soluble acrylic polymer edge grafting modified graphene, wherein the content of the acrylic resin is 80-99 parts by weight, and the content of the edge grafting modified graphene is 1-20 parts by weight, based on 100 parts by weight of the total weight of solids in the heat-conducting water-based acrylic coating; the edge grafting modified graphene comprises graphene and a water-soluble acrylic polymer grafted at the edge of the graphene, and the mass content of the grafted acrylic polymer in the modified graphene is 2-30% based on the total mass of the edge grafting modified graphene. The heat-conducting acrylic acid aqueous coating has the characteristics of environment friendliness and environmental friendliness, has heat conduction and blocking effects, can provide a better working environment for equipment, and reduces performance degradation caused by factors such as unsmooth conduction of ambient temperature.
Description
Technical Field
The invention belongs to the field of acrylic acid coatings, and particularly relates to a heat-conducting water-based acrylic acid coating, and a preparation method and application thereof.
Background
A large amount of solvents volatilize in the production, use and drying processes of the traditional solvent coating, and most of the solvents are toxic and harmful gases, so that serious threats are formed to human health and environment. As social concerns about personal health and environmental safety continue to increase, solvent coatings are increasingly replaced with aqueous coatings. The water-based paint takes water as a solvent, has better safety and environmental friendliness, is nontoxic and odorless, and meets the requirements of modern society on the paint. Currently, the major waterborne coatings in the market place are acrylic, epoxy, waterborne alkyd, and the like, and also include some complex water-soluble emulsion coating systems, such as polyurethane-acrylic emulsions, and the like. The water paint is nontoxic and harmless, is simple to process, becomes an important matrix of the functional paint, and can realize the performances of wave absorption, electric conduction, heat resistance and the like through modification. For example She Cailin et al modified acrylic coatings to give fast-curing wave-absorbing coatings (She Cailin, zhang Linbo, fan Jing, etc.), the preparation of fast-curing radar wave-absorbing coatings and their performance studies [ J ], chinese coatings, 2019, 34 (2): 46-51.). Similarly, researchers have also prepared water-based paints with heat dissipation properties by adding thermally conductive fillers such as boron nitride, magnesium oxide, carbon nanotubes, etc., such as Liu Fengwen et al developed water-based paints using carbon nanotubes and boron nitride (Liu Fengwen, zhang Hao, even, etc., preparation and performance studies of carbon nanotubes/boron nitride water-based paints [ J ], chemical new materials 2016, 44 (12): 134-136.). The heat-dissipating coating is a coating capable of improving the heat-dissipating efficiency of the surface of an object and reducing the temperature of the system, and is generally composed of a coating and a filler, and the filler systems mainly used in the prior art can be classified into oxide systems (such as magnesium oxide, aluminum oxide, etc.), nitride systems (such as boron nitride, silicon nitride, etc.), carbon-based and carbide systems (such as carbon nanotubes, graphite, graphene, silicon carbide, etc.). The matrix in the water paint is polymer material, and the heat conduction mechanism is mainly phonon heat conduction, and the phonon vibrates in crystal lattice to transfer heat. However, the crystallization of the polymer is incomplete, so phonon scattering, namely interface thermal resistance, occurs at the interface of the crystallization, and the heat conduction performance of the polymer material is poor. And by adding the heat-conducting filler, the heat-conducting filler forms a heat-conducting network in the matrix, so that the phonon transfer efficiency in the material is enhanced, and the overall heat-conducting performance of the material is improved.
The graphene material has excellent heat conduction performance, and is regarded as excellent heat conduction filler by researchers, but strong van der Waals force exists between graphene sheets, so that the graphene material is difficult to disperse and extremely easy to agglomerate, and the graphene material can be uniformly dispersed in a matrix after being modified, so that a certain heat conduction effect is achieved. In reference literature (Liu Jialiang, university of south China, academic paper, 2019), graphene oxide and self-made graphite hollow microspheres are used for jointly modifying acrylic resin, when the addition amount reaches 1.5wt%, the heat conduction coating with the heat conductivity reaching 4.8W/m.K is obtained, and when the addition amount is increased, the heat conductivity is not improved, and the heat conductivity is caused by the fact that graphene cannot be well dispersed and agglomeration occurs. Meanwhile, a large amount of acid and alkali are used in the preparation process of graphene oxide, so that a great amount of waste water is generated, and the preparation method has great challenges on environment and production safety, and also has high cost. On the other hand, holes or vacancy defects can be formed in the lamellar layers in the preparation process of the graphene oxide, so that phonon transfer is interrupted, the heat conduction capacity of the material is affected, and the heat conduction performance is lower than that of conventional graphene. Therefore, the product using graphene as the heat-conducting filler of the water-soluble coating in the prior art still has the difficulties of difficult dispersion or high cost and difficult industrialization at present.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a heat-conducting acrylic coating, and a preparation method and application thereof. According to the heat-conducting acrylic acid coating, the graphene material is grafted on the edge of the acrylic acid coating emulsion matrix, so that good dispersion of graphene in the matrix is realized. Meanwhile, the edge grafted graphene material is superior to graphene oxide in heat conduction performance because the edge grafted graphene material is not subjected to oxidation treatment, and a good heat conduction effect is achieved.
The first aspect of the invention provides a heat-conducting water-based acrylic coating, which comprises an acrylic resin emulsion and water-soluble acrylic polymer edge grafting modified graphene, wherein the content of the acrylic resin is 80-99 parts by weight, and the content of the edge grafting modified graphene is 1-20 parts by weight, based on 100 parts by weight of the total weight of solids in the heat-conducting water-based acrylic coating; the edge grafting modified graphene comprises graphene and a water-soluble acrylic polymer grafted on the edge of the graphene, and the mass content of the grafted acrylic polymer in the modified graphene is 2-30%, preferably 3-25%, based on the total mass of the edge grafting modified graphene.
The second aspect of the invention provides a preparation method of the heat-conducting water-based acrylic paint, which comprises the following steps:
and mixing the acrylic resin emulsion with the water-soluble acrylic polymer edge grafting modified graphene aqueous dispersion liquid to obtain the heat-conducting water-based acrylic coating.
A third aspect of the present invention provides the use of the thermally conductive aqueous acrylic paint described above in chemical or electronic equipment.
The heat-conducting acrylic acid aqueous coating has the characteristics of environment friendliness and environmental friendliness, has heat conduction and blocking effects, can provide a better working environment for equipment, and reduces performance degradation caused by factors such as unsmooth conduction of ambient temperature. The acrylic polymer grafted graphene used in the invention has the advantages of simple preparation process, no chemical reagents such as strong acid, easy realization of industrial production, low cost, suitability for serving as a heat conduction filler for mass use and good development prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of an apparatus for preparing an aqueous dispersion of grafted graphene according to an embodiment of the present invention;
FIG. 2 is a photograph of a stable aqueous dispersion of edge grafted sodium polyacrylate graphene prepared in preparation examples 1-5;
FIG. 3 is a scanning electron micrograph of edge grafted sodium polyacrylate graphene prepared in preparation example 1;
FIG. 4 is a transmission electron micrograph of edge grafted sodium polyacrylate graphene prepared in preparation example 1;
FIG. 5 is an infrared spectrum of edge-grafted sodium polyacrylate graphene prepared in preparation example 1;
FIG. 6 is a thermogravimetric analysis of pure flake graphite and polyacrylic edge grafted graphene.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a heat-conducting water-based acrylic acid coating, which comprises acrylic acid resin emulsion and water-soluble acrylic acid polymer edge grafting modified graphene, wherein the content of the acrylic acid resin is 80-99 parts by weight, and the content of the edge grafting modified graphene is 1-20 parts by weight, based on 100 parts by weight of the total weight of solids in the heat-conducting water-based acrylic acid coating; the edge grafting modified graphene comprises graphene and a water-soluble acrylic polymer grafted on the edge of the graphene, wherein the mass content of the grafted acrylic polymer in the modified graphene is 2-30%, preferably 3-25%, such as 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% based on the total mass of the edge grafting modified graphene.
In the invention, the mass content of the grafted acrylic polymer part in the edge grafting modified graphene can be measured by a thermogravimetric analysis method. For example, the loss mass of the acrylic polymer edge grafted graphene sample, i.e., the mass content of the acrylic polymer grafted to graphene, was measured from 50.00 ℃ at a heating rate of 20.00 ℃/min to 800.00 ℃ under conditions of a sample nitrogen flow rate of 20.0ml/min and an equilibrium nitrogen flow rate of 40.0 ml/min.
As used herein, the term "grafting" refers to the reaction of a functional group or polymer at the edges of graphene, rendering the edges of graphene functionalized.
In the present invention, the "acrylic polymer" may refer to both the compound form and the group form, for example, the acrylic polymer in the "acrylic polymer grafted to graphene edge" is the group form, and the acrylic polymer in the preparation method is the compound form. Those skilled in the art will be able to distinguish between the meaning explicitly according to the context.
According to the heat-conducting water-based acrylic coating provided by the invention, the acrylic resin emulsion is used as a matrix material, the edge grafting graphene material is used as a heat-conducting filler, the acrylic resin emulsion matrix has good barrier property, the edge grafting graphene has good heat-conducting property, the barrier property and the mechanical property can be combined, the heat-conducting property of the coating is comprehensively considered to be improved, and the barrier property of the matrix is maintained, and the content of the acrylic resin is 82-95 parts by weight, preferably 85-90 parts by weight, and the content of the edge grafting modified graphene is 5-18 parts by weight, preferably 10-15 parts by weight, based on 100 parts by weight of the total weight of solids in the heat-conducting water-based acrylic coating.
Specifically, the content of the edge grafting modified graphene may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight; accordingly, the content of the acrylic resin may be 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight.
The coating disclosed by the invention contains the acrylic polymer grafted graphene, and the graphene can be uniformly dispersed in water, does not precipitate after being kept for 30 days or even more than 180 days, and has excellent water dispersibility. In the work of the inventor, the solution with the water-soluble polymer is added into a system for preparing graphene by peeling graphite from a grinding disc, so that the viscosity of the system can be increased, the peeling efficiency is increased, meanwhile, the polymer is grafted to the edge of the graphene, the structure is different from that of graphene oxide, the functionalization of the graphene is realized on the premise that carbon-carbon bonds in graphene sheets are not broken, and experiments show that compared with other grafting modification, the acrylic polymer grafting modified graphene has better dispersibility in acrylic paint and has a remarkable improvement effect.
The acrylic polymer modified graphene reported in the literature is mostly based on grafting reaction of oxygen-containing groups of graphene oxide with an acrylic polymer, followed by reduction. Although many documents report acrylic polymer grafted graphene oxide and a preparation method thereof, the acrylic polymer edge grafted graphene prepared by the method is significantly different from the acrylic polymer edge grafted graphene prepared by the method in the aspects of structure, raw materials, preparation method and the like.
From the structural point of view, the national standard GB/T30544.13-2018 independently defines graphene oxide and reduced graphene oxide, wherein the graphene oxide is chemically modified graphene obtained by oxidizing and stripping graphite, and the surface of the graphene oxide is subjected to strong oxidation modification, so that the oxygen content is high; the reduced graphene oxide is the graphene oxide with reduced oxygen content, part of oxygen-containing functional groups still remain in practice, and the SP 3 chemical bond cannot be completely reduced to the SP 2 chemical bond, so that a plurality of topological defects are left. Therefore, the structure of graphene oxide and reduced graphene oxide is greatly different from that of graphene. The invention adopts graphene, but not graphene oxide and reduced graphene oxide.
From the aspect of properties, the modified graphene reported in the literature is prepared by grafting reaction of oxygen-containing groups of graphene oxide and a modifier and then reduction. The polarity of the grafted graphene oxide prepared by the method is reduced after reduction, and the grafted graphene oxide cannot exist in water stably, so that the subsequent use is not facilitated.
The preparation raw materials adopted by the invention are graphene, but not graphene oxide and reduced graphene oxide.
The acrylic resin has water dispersibility, and the acrylic resin emulsion is an aqueous dispersion of acrylic resin, namely a dispersion of acrylic polymer in water; the acrylic resin is a homopolymer of an acrylic monomer or a copolymer of an acrylic monomer and a vinyl monomer; the acrylic monomer is preferably at least one of acrylonitrile, acrylamide, acrylic acid ester and itaconic acid; the acrylic ester is preferably at least one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, ethylhexyl acrylate and hydroxyethyl acrylate; the vinyl monomer is preferably at least one of styrene, alpha-methylstyrene and vinyl acetate.
According to a preferred embodiment of the invention, the acrylic resin emulsion has a solids content of 30-70%, preferably 35-60%. The inventors found in experiments that as the solid content of the emulsion increases, the viscosity of the emulsion increases, which adversely affects the dispersion of graphene, while too low a solid content affects the film forming effect of the emulsion after drying, so that a suitable solid content interval needs to be selected.
The water-soluble acrylic polymer of the present invention may be at least one of a water-soluble polymer containing an acrylic acid structural unit and/or a methacrylic acid structural unit and a salt thereof; the salt comprises alkali metal salt and ammonium salt, and preferably the water-soluble acrylic polymer is at least one of polyacrylic acid, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, lithium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, ammonium polymethacrylate and lithium polymethacrylate.
According to the invention, the edge-grafted modified graphene sheet is large and thin, and specifically, the average sheet diameter of the edge-grafted modified graphene is 1-5 μm.
The average sheet diameter of the edge grafting modified graphene can be obtained by randomly measuring the size of more than 10 pieces of graphene to calculate the average value after imaging by a Scanning Electron Microscope (SEM) or an atomic force microscope. The measurement method of the single-chip graphene size comprises the following steps: and (3) drawing three lines on the surface of the graphene sheet as far as possible through the center of the sheet, forming an included angle of about 60 degrees between the lines, measuring the lengths of the graphene on the three lines, and calculating an average value as the size of the graphene sheet.
The edge grafting modified graphene used in the invention has higher heat conductivity coefficient, so that the heat-conducting acrylic coating has good heat conductivity, and particularly, the heat conductivity coefficient of the water-soluble acrylic polymer edge grafting modified graphene can reach 200-400W/m.K, preferably 220-320W/m.K. After the acrylic polymer grafted graphene is added into the heat-conducting acrylic coating, the heat-conducting efficiency of the dry solid of the heat-conducting acrylic coating can reach 1-15W/m.K, and is preferably 4.5-10W/m.K. After the grafted graphene is added, the heat conduction performance of the dry solid is obviously improved, but after the addition amount is increased to a certain amount, a heat conduction network is formed in the matrix, the performance of the heat conduction network meets the use requirement, the mechanical and film forming performance can be reduced due to the more addition amount, and the cost can be increased.
According to a preferred embodiment of the invention, the heat-conducting water-based acrylic coating is obtained by mixing an acrylic resin emulsion with an aqueous dispersion of water-soluble acrylic polymer edge grafting modified graphene.
According to the invention, the modified graphene aqueous dispersion comprises water and the water-soluble acrylic polymer edge-grafted modified graphene stably dispersed therein; the mass fraction of the water-soluble acrylic polymer edge grafting modified graphene in the modified graphene aqueous dispersion is 1-20%, preferably 1-15%.
The stability time of the modified graphene aqueous dispersion liquid provided by the invention under the conditions of room temperature and normal pressure can exceed 10 months. The stabilization time means that no macroscopic precipitation occurs during this period, and specifically, the precipitation amount is less than 1%.
The invention adopts the millstone stripping process assisted by the acrylic polymer aqueous solution, thereby obviously reducing the damage to graphite lattices. The viscosity increasing effect of the acrylic polymer on the dispersion system enables the shearing force between the fixed millstone and the movable millstone to be more effectively acted on the graphite flake in the slurry, and the stripping preparation of graphene is realized. During the exfoliation process, the acrylic polymer edge grafts to the graphene, enabling the modified graphene to be stably dispersed in the aqueous phase.
According to a preferred embodiment of the present invention, the aqueous dispersion of water-soluble acrylic polymer edge-grafted modified graphene is prepared by a process comprising the steps of:
And uniformly mixing the water-soluble acrylic polymer, water and graphite, grinding in a millstone kettle, standing after finishing grinding, and removing sediment to obtain the water dispersion liquid of the graphene modified by grafting the edge of the water-soluble acrylic polymer.
According to a more specific embodiment, a proper amount of water-soluble acrylic polymer is dissolved in deionized water, then graphite powder is added, the mixture is stirred to prepare graphite slurry, the graphite slurry is circularly stripped by a millstone for a certain time, and finally, the precipitate is filtered off, so that the stable acrylic polymer edge grafted graphene aqueous dispersion is obtained.
The invention relates to a grinding disc graphite stripping simultaneous in-situ grafting technology based on water-soluble acrylic polymer aqueous solution assistance, and the prepared water-soluble acrylic polymer is grafted on the edge of graphene and stably dispersed in the aqueous solution.
According to a preferred embodiment of the invention, the grinding adopts circulating grinding, and the mechanical stripping equipment used consists of a millstone and circulating two parts, and the structural schematic diagram of the mechanical stripping equipment is shown in figure 1. The millstone part comprises a movable millstone, a fixed millstone and a rotating device, and the circulating part comprises a circulating pump, a slurry storage tank and a stirring device. Wherein the grinding disc is made of metal, ceramic, glass, plastic, etc., preferably metal.
During the millstone stripping process, the moving/stationary millstones transmit shear forces to the graphite sheets between the millstones through the aqueous solution of the water-soluble acrylic polymer. The graphite flakes are first oriented in the rotational direction of the millstone under the action of shear stress, then slowly exfoliated into thinner graphite flakes, and finally exfoliated into graphene. In the stripping process, a plurality of new edges are generated, the activity of carbon atoms of the new edges is higher, and the new edges react with the water-soluble acrylic polymer in the aqueous solution to generate the water-soluble acrylic polymer edge grafting graphene. The method of the invention significantly reduces damage to the graphite lattice. The viscosity increasing effect of the water-soluble acrylic polymer on the dispersion system, and the shearing force between the fixed millstone and the movable millstone more effectively acts on the graphite flake in the slurry, so that the stripping preparation of graphene is realized. During the exfoliation process, the water-soluble acrylic polymer is grafted to the edges of the graphene, thereby stably dispersing the prepared graphene in water.
The grinding of the invention can be carried out in a closed or open system, the preparation process can be cyclic grinding at room temperature and normal pressure, and no specific requirement is imposed on the atmosphere of the system.
In order to obtain the edge grafted graphene material, the grinding disc cycle stripping process mainly controls the rotating speed and cycle stripping time, and according to the characteristics of the edge grafted graphene, the cycle stripping time can be 5-200 hours, and in order to improve the efficiency or the grafting rate, the cycle stripping time can be preferably 10-150 hours, more preferably 30-120 hours, and further preferably 70-100 hours; similarly, the peeling efficiency is improved with the increase of the rotational speed, but the peeling time is not significantly affected, that is, the change of the size with the rotational speed is small in a certain range of the rotational speed. The effects of the invention can be realized when the rotating speed is 10-300 rpm in a certain cycle time, and the invention has better repeatability and stability; the repeatability and stability of the sheet diameter are better when the rotation speed is controlled to be 50-200 rpm, preferably 70-100 rpm, within a certain cycle time.
The water-soluble acrylic polymer in the system of the present invention has two functions: (1) The viscosity of the dispersion system is increased, the stripping effect of the grinding disc on the graphite sheet is improved, and (2) the graphene is grafted to the graphene, so that the graphene is stably dispersed in the aqueous solution.
The water-soluble acrylic polymer edge grafted graphene aqueous dispersion is prepared by mechanically stripping graphite through a millstone, wherein optional graphite can be natural graphite and/or artificial graphite, the natural graphite can be one or more selected from flake graphite, block graphite and aphanitic graphite, the artificial graphite can be one or more selected from thermal cracking graphite and high-orientation thermal cracking graphite, and the graphite is preferably flake graphite; the particle size of the graphite may be 5 to 8000 mesh, preferably 35 to 3000 mesh, more preferably 50 to 1600 mesh, and even more preferably 50 to 300 mesh.
According to a preferred embodiment of the present invention, the water-soluble acrylic polymer and water are mixed first, and then graphite is added, the mass fraction of the water-soluble acrylic polymer being 1 to 50%, preferably 1 to 40%, based on the total weight of the water-soluble acrylic polymer and water.
The mixing method of the acrylic resin emulsion and the edge grafting graphene aqueous dispersion liquid can be any dispersion method of the aqueous dispersion liquid, and is preferably any one or more of stirring, vibration and ultrasound. The dispersion method does not significantly differ from the dispersion state after blending of the two. The specific conditions of the various mixing modes are not particularly limited, and the present invention can achieve sufficient dispersion. The temperature of the stirring can be 60-90 ℃, the rotating speed can be 80-200 rpm, and the time can be 10-60 minutes. The conditions of the ultrasound may include: the frequency is 20-30kHz, the power is 200-300W, and the time is 10-60 minutes.
The invention also provides a preparation method of the heat-conducting water-based acrylic coating, which comprises the following steps:
and mixing the acrylic resin emulsion with the water-soluble acrylic polymer edge grafting modified graphene aqueous dispersion liquid to obtain the heat-conducting water-based acrylic coating.
The heat-conducting water-based acrylic coating can be used in chemical equipment or electronic equipment. For example, the coating can be widely applied to precise instruments, LED radiating fins and vacuum furnaces, and particularly applied to the surfaces of pipelines, kettles and electronic packaging components needing heat dissipation, and can be used as a coating to realize the functions of blocking and heat dissipation.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
The experimental reagents in the following examples are commercially available except for labeling homemade, such as acrylic emulsion and flake graphite.
The millstone used in the examples was self-made.
The infrared spectrum model used in the examples was the Siemens Feicolet IS5.
The scanning electron microscope used in the examples was of the type Japanese Hitachi S4800.
The heat conduction performance of the coating is tested by using a German relaxation-resistant laser heat conduction testing instrument LFA 467.
The graphene heat conductivity coefficient testing method comprises the following steps: the LFA 467 laser heat conduction instrument is adopted, and the heat conduction coefficient (K) of a test sample can be calculated by referring to GB/T22588-2008 test standard through the following formula: k=α×cp×ρ, where α is the thermal diffusivity, cp is the specific heat capacity, ρ is the density. The mechanism is that a beam of light pulse is emitted instantly by a laser source at a certain set temperature, and uniformly irradiates on the surface of a sample, so that the temperature is instantly raised after the surface layer absorbs light energy, and the energy is transmitted to a plane and a vertical direction in a heat conduction mode as a hot end, the corresponding temperature raising process of the central part of the surface of the sample is continuously measured by using an infrared detector, a relation curve of a detector signal (temperature) and time is obtained, and a correction curve is obtained by correcting by a proper mathematical model, so that the thermal diffusion coefficient is calculated.
Preparation example 1
20.0 G of sodium polyacrylate (national pharmaceutical systems and chemical reagent Co., ltd., weight average molecular weight: about 45 ten thousand) was dissolved in 1000 ml of deionized water, and 150g of 100 mesh flake graphite (Qingdao Sanhe graphite Co., ltd.) was added thereto and stirred uniformly. The rotating speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 72 hours, the graphene suspension processed by the grinding disc is poured into a beaker, after the grinding disc is kept stand for 10 hours, the sediment is removed by filtration, and the stable aqueous dispersion of the sodium polyacrylate edge grafted graphene is obtained, wherein the mass fraction of the grafted graphene is 3.1%. The graphene yield was about 21% of the mass of the flake graphite added. Sample No. 1 in fig. 2 is a sodium polyacrylate edge grafted graphene which can be stably dispersed in water after standing for 10 months, mainly because sodium polyacrylate grafted at the edge of the graphene plays a role in stable dispersion. The mass content of the grafted sodium polyacrylate in the grafted modified graphene is 6.9%.
Adding 10mL of sodium polyacrylate grafted graphene aqueous dispersion into 200mL of deionized water for dilution, then adopting a microporous filter membrane with a pore diameter of 0.22 micrometer for reduced pressure filtration, finally using 2L of deionized water for filtering out free sodium polyacrylate, and drying to obtain purified sodium polyacrylate grafted graphene.
Fig. 3 is a scanning electron micrograph of the prepared sodium polyacrylate grafted graphene, with the average size of the sheets of grafted graphene being about 2.8 microns.
Fig. 4 is a transmission electron micrograph of the edge of the prepared sodium polyacrylate edge grafted graphene, showing the prepared monolayer graphene.
Fig. 5 is an infrared spectrum of the prepared sodium polyacrylate edge grafted graphene. The absorption peak at 3450cm -1 in the figure is assigned to the extensional vibration mode of-OH on the unneutralized acid in the grafted sodium polyacrylate; the absorption peak at 1700cm -1 is attributed to c=o stretching vibrations, shifting to low wavenumbers due to the associative effect; 1581cm -1 and 1435cm -1 are asymmetric and symmetric telescopic vibrations of carboxylate anions COO -. The infrared spectrum shows that the sodium polyacrylate is grafted to the graphene. However, the infrared spectrogram of the crystalline flake graphite has no characteristic absorption peak of sodium polyacrylate nor characteristic peaks of other active functional groups. This indicates that the surface of the flake graphite does not contain the relevant functional groups. In the millstone stripping process, the graphite sheets are broken, and the newly generated graphite edges have a plurality of high-activity carbon free radicals and react with sodium polyacrylate in the solution to finally obtain the sodium polyacrylate edge grafted graphene.
The thermal conductivity coefficient of the sodium polyacrylate edge grafted graphene is 288W/m.K.
Preparation example 2
150.0 G of sodium polymethacrylate (national pharmaceutical systems chemical Co., ltd., weight average molecular weight: about 30000) was dissolved in 1000 ml of deionized water, and 150 g of 100-mesh flake graphite (Qingdao Sanhe graphite Co., ltd.) was added thereto and stirred uniformly. The rotating speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 100 hours, the graphene suspension processed by the grinding disc is poured into a beaker, after the grinding disc is kept stand for 10 hours, the sediment is removed by filtration, and the stable aqueous dispersion of the edge grafted graphene of the sodium polymethacrylate is obtained, wherein the mass fraction of the grafted graphene is 2.7%. The preparation method is carried out according to the method of example 1 to obtain the sodium polymethacrylate grafted graphene, wherein the average size of the prepared grafted graphene sheet is about 2.7 microns, and the mass content of the grafted sodium polymethacrylate in the grafted modified graphene is 4.7%. The yield of the grafted modified graphene is about 18% of the mass of the added crystalline flake graphite. Sample No. 2 in fig. 2 is a stable dispersion after 10 months of standing. The thermal conductivity of the grafted graphene is 265W/mK.
Preparation example 3
150.0 G of potassium polyacrylate (average molecular weight: about 30000, national medicine group chemical Co., ltd.) was dissolved in 1000 ml of deionized water, and 150 g of 100 mesh flake graphite (Qingdao Sanhe graphite Co., ltd.) was added thereto and stirred uniformly. The rotating speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 50 hours, the graphene suspension processed by the grinding disc is poured into a beaker, after the grinding disc is kept stand for 10 hours, the sediment is removed by filtration, and the stable aqueous dispersion of the grafted graphene at the edge of the potassium polyacrylate is obtained, wherein the mass fraction of the grafted graphene is 3.3%. The preparation method is carried out according to the method of the example 1, so that the potassium polyacrylate grafted graphene is obtained, the average size of the prepared grafted graphene sheet is about 2.1 microns, and the mass content of the grafted potassium polyacrylate in the graphene is 6.7%. The yield of the grafted modified graphene is about 22% of the mass of the added crystalline flake graphite. Sample No. 3 in fig. 2 is a stable dispersion after 10 months of standing. The thermal conductivity of the grafted graphene is 273W/m.K.
Preparation example 4
300G of sodium polyacrylate (national medicine group chemical reagent Co., ltd., weight average molecular weight of 3000-5000) was dissolved in 1000 ml of deionized water, and 200 g of 100 mesh flake graphite (Qingdao Sanhe graphite Co., ltd.) was added thereto and stirred uniformly. The rotating speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 72 hours, the graphene suspension processed by the grinding disc is poured into a beaker, after the grinding disc is kept stand for 10 hours, the sediment is removed by filtration, and the stable aqueous dispersion of the sodium polyacrylate edge grafted graphene is obtained, wherein the mass fraction of the grafted graphene is 4.1%. The sodium polyacrylate grafted graphene is obtained by purifying according to the method of the example 1, wherein the average size of the prepared sheet layer of the grafted graphene is about 2.0 microns, and the mass content of the grafted sodium polyacrylate in the grafted modified graphene is 7.1%. The yield of the grafted modified graphene is about 20.5% of the mass of the added crystalline flake graphite. Sample No. 4 in fig. 2 is a stable dispersion after 10 months of standing. The thermal conductivity of the grafted graphene is measured to be 238W/mK.
Preparation example 5
100.0 G of sodium polyacrylate (weight average molecular weight about 15 ten thousand, guangzhou perphenda chemical Co., ltd.) was dissolved in 1000 ml of deionized water, and 150 g of 100 mesh expanded graphite (Qingdao Sanhe graphite Co., ltd.) was added thereto and stirred uniformly. The rotating speed of the grinding disc is set to be 50rpm, after the grinding disc is circularly ground for 72 hours, the graphene suspension processed by the grinding disc is poured into a beaker, after the grinding disc is kept stand for 10 hours, the sediment is removed by filtration, and the stable aqueous dispersion of the sodium polyacrylate edge grafted graphene is obtained, wherein the mass fraction of the grafted graphene is 3.8%. The potassium polyacrylate grafted graphene is obtained by purifying according to the method of the example 1, wherein the average size of the prepared sheet layer of the grafted graphene is about 2.0 microns, and the mass content of the grafted sodium polyacrylate in the grafted modified graphene is 7.1%. The yield of the grafted modified graphene is about 20.5% of the mass of the added crystalline flake graphite. Sample No.5 in fig. 2 is a stable dispersion after 10 months of standing. The thermal conductivity of the grafted graphene is 295W/m.K.
Preparation example 6
300 G of polyacrylic acid (national medicine group chemical agent Co., ltd., weight average molecular weight 5000-7000) was dissolved in 1000 ml of deionized water, 200 g of 100 mesh flake graphite (Qingdao Sanhe graphite Co., ltd.) was added, and stirred uniformly. The rotating speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 72 hours, the graphene suspension processed by the grinding disc is poured into a beaker, and after standing for 10 hours, the sediment is removed by filtration, so that the stable aqueous dispersion of the polyacrylic acid edge grafted graphene is obtained, wherein the mass fraction of the grafted graphene is 3.5%. Purification was performed according to the method of example 1 to obtain polyacrylic acid grafted graphene, and the average size of the prepared sheets of grafted graphene was about 2.7 μm. The yield of the grafted modified graphene is about 17.5% of the mass of the added crystalline flake graphite. The dispersion was stable after 10 months of sample rest.
FIG. 6 is a thermogravimetric analysis of pure flake graphite and polyacrylic edge grafted graphene. The test result of the thermogravimetric analysis curve shows that the crystalline flake graphite has almost no weight loss; the weight loss of the polyacrylic acid edge grafted graphene at the temperature is 6.63%, which shows that the mass content of the polyacrylic acid grafted by the modified graphene is 6.63%. The thermal conductivity of the grafted graphene is 277W/m.K.
Comparative preparation example 1
150 G of 100 mesh flake graphite (Qingdao Santong graphite Co., ltd.) was added to 1000 ml of deionized water and stirred well. The rotation speed of the grinding disc is set to be 100rpm, after the grinding disc is circularly ground for 100 hours, the graphene suspension processed by the grinding disc is poured into a beaker, and after standing for 10 hours, sediment is removed by filtration. Only a very small amount of graphene can be obtained, which is less than 0.5% of the mass of the added crystalline flake graphite. The graphene suspension can be stably stored for only a few days, obvious precipitation can be observed after a few days, and almost all precipitation is observed after one week. The resulting graphene was subjected to a thermal conductivity test according to the method of preparation example 1, and the thermal conductivity coefficient of the graphene was found to be 321W/m·k.
The following examples are preparation examples of acrylic coatings, and the grafted graphene used was the graphene material in preparation examples 1-6.
Example 1
The edge grafted graphene aqueous dispersion in preparation example 1 was blended with an acrylic resin emulsion in an ultrasonic mode at a frequency of 22kHz at a power of 250W for 20 minutes. The formulation is shown in Table 1.
Example 2
The edge grafting graphene aqueous dispersion liquid in the preparation example 2 is adopted to be mixed with the acrylic resin emulsion, the mixing mode is stirring, the temperature is 85 ℃, the rotating speed is 100 revolutions per minute, and the time is 30 minutes. The formulation is shown in Table 1.
Example 3
The edge grafting graphene aqueous dispersion liquid in the preparation example 3 is adopted to be mixed with the acrylic resin emulsion, the mixing mode is stirring, the water temperature is 85 ℃, the rotating speed is 100 revolutions per minute, and the time is 30 minutes. The formulation is shown in Table 1.
Example 4
The edge grafting graphene aqueous dispersion liquid in preparation example 4 is adopted to be mixed with the acrylic resin emulsion, the mixing mode is stirring, the temperature is 85 ℃, the rotating speed is 100 revolutions per minute, and the time is 30 minutes. The formulation is shown in Table 1.
Example 5
The edge grafting graphene aqueous dispersion liquid in preparation example 5 is adopted to be mixed with the acrylic resin emulsion, the mixing mode is stirring, the temperature is 85 ℃, the rotating speed is 100 revolutions per minute, and the time is 30 minutes. The formulation is shown in Table 1.
Example 6
The edge grafting graphene aqueous dispersion liquid in preparation example 6 is adopted to be mixed with the acrylic resin emulsion, the mixing mode is stirring, the temperature is 85 ℃, the rotating speed is 100 revolutions per minute, and the time is 30 minutes. The formulation is shown in Table 1.
Comparative examples 1 to 5
Comparative examples 1 to 2 are comparative examples using only an acrylic resin emulsion, comparative example 3 is comparative example using graphene oxide instead of the grafted graphene in example 3, comparative example 4 is comparative example in which the weight ratio of acrylic resin to graphene in example 1 was adjusted, the formulation is shown in table 1, and comparative example 5 is comparative example in which graphene is grafted by comparative preparation example 1 graphene instead of the example, ungrafted graphene may precipitate, stable dispersion may not be achieved, and delamination may be caused, and overall heat conductive properties may not be measured.
Test case
The coatings prepared in the above examples and comparative examples were coated on glass sheets using a film coater with a film thickness controlled at 100.+ -.5. Mu.m, and the films were removed and subjected to thermal conductivity testing, and the results are shown in Table 1.
Table 1 formulation and thermal conductivity test results
The data comparison of the embodiment and the comparative example shows that the coating obtained by using the edge grafted graphene modified acrylic emulsion coating can achieve better heat conduction effect, and compared with the coating prepared by adding the same amount of the commercially available graphene oxide, the coating prepared by using the coating has better heat conduction effect and better application prospect.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (17)
1. The heat-conducting water-based acrylic coating is characterized by comprising acrylic resin emulsion and water-soluble acrylic polymer edge grafting modified graphene, wherein the content of the acrylic resin is 80-99 parts by weight, and the content of the edge grafting modified graphene is 1-20 parts by weight, based on 100 parts by weight of the total weight of solids in the heat-conducting water-based acrylic coating; the edge grafting modified graphene comprises graphene and a water-soluble acrylic polymer grafted on the edge of the graphene, and the mass content of the grafted acrylic polymer in the modified graphene is 2-30%, preferably 3-25%, based on the total mass of the edge grafting modified graphene.
2. The thermally conductive aqueous acrylic coating according to claim 1, wherein the acrylic resin is contained in an amount of 82 to 95 parts by weight, preferably 85 to 90 parts by weight, and the edge-grafted modified graphene is contained in an amount of 5 to 18 parts by weight, preferably 10 to 15 parts by weight, based on 100 parts by weight of the total weight of solids in the thermally conductive aqueous acrylic coating.
3. The thermally conductive aqueous acrylic coating of claim 1, wherein the acrylic emulsion is an aqueous dispersion of acrylic; the acrylic resin is a homopolymer of an acrylic monomer or a copolymer of an acrylic monomer and a vinyl monomer; the acrylic monomer is preferably at least one of acrylic acid, acrylonitrile, acrylamide, acrylic acid ester and itaconic acid; the acrylic ester is preferably at least one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, ethylhexyl acrylate and hydroxyethyl acrylate; the vinyl monomer is preferably at least one of styrene, alpha-methylstyrene and vinyl acetate.
4. The thermally conductive aqueous acrylic coating according to claim 1, wherein the acrylic resin emulsion has a solids content of 30-70%, preferably 35-60%.
5. The thermally conductive aqueous acrylic coating according to claim 1, wherein the water-soluble acrylic polymer is at least one of a water-soluble polymer containing an acrylic structural unit and/or a methacrylic structural unit and a salt thereof; preferably at least one of polyacrylic acid, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, lithium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, ammonium polymethacrylate and lithium polymethacrylate.
6. The thermally conductive aqueous acrylic coating of claim 1, wherein the average sheet diameter of the water-soluble acrylic polymer edge-grafted modified graphene is 1-5 μιη.
7. The thermally conductive aqueous acrylic coating of claim 1, wherein the thermally conductive coefficient of the water-soluble acrylic polymer edge grafted modified graphene is 200-400W/m-K, preferably 220-320W/m-K; the heat conductivity coefficient of the solid obtained after the heat conducting water-based acrylic coating is 1-15W/m.K, preferably 4.5-10W/m.K.
8. The thermally conductive aqueous acrylic coating of any one of claims 1-7, wherein the thermally conductive aqueous acrylic coating is obtained from an acrylic resin emulsion mixed with an aqueous dispersion of a water-soluble acrylic polymer edge graft modified graphene.
9. The thermally conductive aqueous acrylic coating of claim 8, wherein the modified graphene aqueous dispersion comprises water and the water-soluble acrylic polymer edge-grafted modified graphene stably dispersed therein; the mass fraction of the water-soluble acrylic polymer edge grafting modified graphene in the modified graphene aqueous dispersion is 1-20%, preferably 1-15%.
10. The thermally conductive aqueous acrylic coating of claim 9, wherein the modified graphene aqueous dispersion is stable for more than 10 months at room temperature and atmospheric pressure.
11. The thermally conductive aqueous acrylic coating of claim 8, wherein the aqueous dispersion of water-soluble acrylic polymer edge graft modified graphene is prepared by a process comprising:
And uniformly mixing the water-soluble acrylic polymer, water and graphite, grinding in a millstone kettle, standing after finishing grinding, and removing sediment to obtain the water dispersion liquid of the graphene modified by grafting the edge of the water-soluble acrylic polymer.
12. The thermally conductive aqueous acrylic coating according to claim 11, wherein the graphite is natural graphite selected from one or more of flake graphite, bulk graphite, aphanitic graphite, and/or artificial graphite selected from one or more of thermally cracked graphite, highly oriented thermally cracked graphite; the graphite is preferably flake graphite; the particle size of the graphite is 5 to 8000 mesh, preferably 35 to 3000 mesh, more preferably 50 to 1600 mesh, and still more preferably 50 to 300 mesh.
13. The thermally conductive aqueous acrylic coating according to claim 11, wherein the milling is performed in an open or closed system, preferably cyclic milling at room temperature and pressure; the grinding conditions include: the rotation speed is 10 to 300 rpm, preferably 50 to 200 rpm, more preferably 70 to 100 rpm; the time is 5 to 200 hours, preferably 10 to 150 hours, more preferably 30 to 120 hours, still more preferably 70 to 100 hours.
14. The thermally conductive aqueous acrylic coating according to claim 11, wherein the mass fraction of the water-soluble acrylic polymer is 1-50%, preferably 1-40% based on the total mass of the water-soluble acrylic polymer and water.
15. The thermally conductive aqueous acrylic coating of claim 8, wherein the mixing is by any one or more of stirring, shaking, and ultrasound.
16. The method for preparing the heat conductive aqueous acrylic paint according to any one of claims 1 to 15, comprising the steps of:
and mixing the acrylic resin emulsion with the water-soluble acrylic polymer edge grafting modified graphene aqueous dispersion liquid to obtain the heat-conducting water-based acrylic coating.
17. Use of the thermally conductive aqueous acrylic paint of any one of claims 1-15 in chemical or electronic equipment.
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