CN111303703A - Graphene heating coating and preparation method thereof - Google Patents
Graphene heating coating and preparation method thereof Download PDFInfo
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- CN111303703A CN111303703A CN202010152418.XA CN202010152418A CN111303703A CN 111303703 A CN111303703 A CN 111303703A CN 202010152418 A CN202010152418 A CN 202010152418A CN 111303703 A CN111303703 A CN 111303703A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
- C09D101/286—Alkyl ethers substituted with acid radicals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/04—Starch derivatives
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a graphene heating coating and a preparation method thereof, wherein the graphene heating coating comprises the following components in percentage by weight: 40% -50% of graphene; 5% -14% of oxide; 20% of water-based resin; 20% -32% of adhesive; 0.1 to 0.5 percent of defoaming agent; 0.3 to 0.5 percent of coupling agent; 0.2 to 0.5 percent of flatting agent. The graphene heating coating provided by the invention has the advantages of high electrothermal conversion rate, rapid temperature rise, long service life and uniform heating temperature; the heating plate can be directly coated by roller or sprayed on the wall, the ground and other positions, so that the energy utilization rate is improved, and the heating plate is more energy-saving and power-saving than the traditional heating mode.
Description
Technical Field
The invention relates to the field of functional coatings, and particularly relates to a graphene heating coating and a preparation method thereof.
Background
At present, for southern areas which do not adopt central heating, the heating modes of the southern areas are generally air conditioners, floor heaters, electric heaters, coal furnaces and the like. The heating mode needs to be processed and molded, 220V mains supply is used, and the problems of complex installation, uneven heating, low heat efficiency, electric leakage danger, poor comfort degree and the like generally exist. For the heating of the profile body, the operation is complicated, and the use of carbon fiber is simple in forming but quite expensive.
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. Graphene has very good thermal conductivity. The pure defect-free single-layer graphene has the thermal conductivity coefficient as high as 5300W/mK, is the carbon material with the highest thermal conductivity coefficient, and is higher than that of a single-wall carbon nanotube (3500W/mK) and a multi-wall carbon nanotube (3000W/mK). When it is used as carrier, its thermal conductivity can be up to 600W/mK. Therefore, the graphene is applied to the heating heat conduction material, so that the heating efficiency is greatly improved. The invention patent with publication number CN 109370370A discloses a graphene heating coating and a preparation method thereof, wherein the graphene coating comprises the following components in percentage by weight: 2-7% of graphene, 20-40% of diluent, 0.15-2% of dispersant, 20-40% of epoxy resin, 1.6-6.6% of curing agent, 10-50% of filler and 0.2-1% of coupling agent, wherein the fineness of the graphene heating coating is 30-60um, and the solid content is 30-60%; the diluent is one or more of toluene, xylene, isopropanol, n-butanol and acetone. The graphene heating film prepared by the graphene coating has the heating resistance of only 0.4-9.5 omega, is extremely low in heat production efficiency, is not suitable for heating large spaces such as rooms and the like, and serious environmental pollution to the use space and harm to body health can be caused by adding a large amount of organic solvents such as toluene, xylene and the like as diluents in the formula of the graphene coating.
Disclosure of Invention
Aiming at the prior art, the technical problem to be solved by the invention is to provide the graphene heating coating and the preparation method thereof, wherein the graphene heating coating adopts liquid graphene as a main raw material, has the advantages of environmental protection, durability and quick drying, and is quick in temperature rise after being electrified, high in heat conversion efficiency, long in service life and uniform in heating temperature.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the graphene heating coating comprises the following components in percentage by weight:
40% -50% of graphene;
5% -14% of oxide;
20% of water-based resin;
20% -30% of adhesive;
0.1 to 0.5 percent of defoaming agent;
0.3 to 0.5 percent of coupling agent;
0.3 to 0.5 percent of flatting agent.
The number of layers of the graphene is 5-15, and the particle size is 10-15 microns.
The oxide is a metal oxide, and preferably, the oxide is one or more of gamma phase ferric oxide, aluminum oxide, zinc oxide and barium oxide. The oxide can enhance the hydrophilicity of the graphene and the dispersibility of the graphene in water, an organic solvent is not required to be added, and the oxide can reduce the sheet resistance of the graphene coating, so that the graphene coating can reach high enough power under a low safe voltage, and the requirements of heating safety and high efficiency are met.
The water-based resin is one or more of water-based polyurethane resin, water-based epoxy resin and water-based acrylic resin.
The adhesive is one or more of polyvinyl alcohol, carboxymethyl cellulose, polyvinyl acetate, modified starch and polyurethane glue. The modified starch further may preferably be an etherified starch, such as tertiary amine cationic starch, hydroxymethyl starch, hydroxyalkyl starch.
The defoaming agent is modified polysiloxane or non-silicon polymer, and the non-silicon polymer can be a defoaming agent of ByK051 of Bike company.
The coupling agent is one or more of siloxane, titanate coupling agent and polyterephthalate.
The leveling agent is one or more of polyether modified polydimethylsiloxane, polyether modified organic silicon and water-based acrylic ester copolymer, and more preferably, the water-based acrylic copolymer is a copolymer of methyl methacrylate butyl acrylate, glycidyl methacrylate and acrylic acid.
The preparation method of the graphene heating coating comprises the following steps:
(1) pulverizing the oxide into powder, sieving with 500-2000 mesh sieve;
(2) adding the oxide into a reaction kettle, adding the water-based resin, the graphene, the adhesive, the defoaming agent, the coupling agent and the flatting agent, and uniformly stirring;
(3) grinding the uniformly stirred slurry in the step (2) by a grinder until the granularity of the slurry is 80-100 mu m;
(4) deionized water with the weight of 40-60% of the slurry is added to adjust the thickness and the degree of dilution, and the graphene heating slurry is obtained.
Compared with the prior art, the graphene heating coating provided by the invention has the following beneficial effects:
(1) the graphene is adopted as a main raw material, so that the electrothermal conversion rate is high, the temperature rise is rapid, the service life is long, and the heating temperature is uniform;
(2) the paint can be directly coated on the wall, the ground and other positions by roller or sprayed, the original decoration is not required to be changed, the space is saved, the paint is suitable for curved surfaces, folded surfaces, special-shaped ground or wall surfaces, and the installation and the use are convenient;
(3) the graphene heating coating provided by the invention is supplied with power by using low voltage of 0-36V, so that a higher heating temperature can be achieved, the use is safe, and no electric shock or fire hazard exists;
(4) the coating components are all environment-friendly materials, and the solvent is free, so that secondary pollution to the environment is avoided;
(5) under the power-on state, carbon radicals in the graphene coating heating body generate Brownian motion, so that heat energy is transferred outwards in the form of far infrared and heat convection, the whole heating is uniform, the temperature rise is rapid, the temperature rise is mild, no wind exists, the drying is avoided, the far infrared radiation beneficial to the human body can be generated, the comfort as the sunlight irradiation is generated, and the comfort of the human body can be greatly improved.
Detailed Description
The following describes in detail embodiments of the present invention.
Example 1
The graphene heating coating in the embodiment comprises the following components (in percentage by weight):
| component name | Weight percent of |
| Graphene | 40％ |
| Gamma phase ferric oxide | 8.7％ |
| Aqueous polyurethane resin | 20％ |
| Polyvinyl alcohol | 30％ |
| Modified polysiloxanes | 0.5％ |
| Siloxane coupling agent | 0.5％ |
| Aqueous acrylate copolymers | 0.3％ |
The preparation method of the graphene heating coating in the embodiment comprises the following steps:
(1) crushing the gamma phase ferric oxide into powder, and sieving the powder with a 1000-mesh sieve;
(2) adding gamma-phase ferric oxide into a reaction kettle, adding waterborne polyurethane resin, graphene, adhesive polyvinyl alcohol, modified polysiloxane defoamer, siloxane coupling agent and flatting agent waterborne acrylate copolymer, and uniformly stirring;
(3) grinding the uniformly stirred slurry in the step (2) by a grinder until the granularity of the slurry is 80-100 mu m;
(4) and adding deionized water to adjust the viscosity of the slurry to be between 90 and 110KU, thus obtaining the graphene heating slurry.
The graphene heating slurry prepared by the formula is coated on the surface of a smooth ceramic tile in a scraping mode, the thickness of the film is about 200 mu m, after the graphene heating slurry is dried, the graphene heating slurry is switched on under 36V voltage and at room temperature of 20 ℃, and the test result is as follows:
| item | Test results |
| Average square resistance of paint (omega) | 100 |
| Specific power (W/m)2) | 180 |
| Average surface temperature (. degree. C.) after 30min | 42 |
Example 2
The graphene heating coating in the embodiment comprises the following components (in percentage by weight):
the preparation method of the graphene heating coating in the embodiment comprises the following steps:
(1) crushing the alumina into powder, sieving the powder by a sieve with the mesh number of 800 meshes;
(2) adding alumina into a reaction kettle, adding waterborne epoxy resin, graphene, an adhesive carboxymethyl cellulose, a modified polysiloxane antifoaming agent, a polyterephthalate compound coupling agent and a flatting agent polyether modified polydimethylsiloxane, and uniformly stirring;
(3) grinding the uniformly stirred slurry in the step (2) by a grinder until the particle size of the slurry is 85-95 μm;
(4) and adding deionized water to adjust the viscosity of the slurry to be between 100 and 120KU, so as to obtain the graphene heating slurry.
The graphene heating slurry prepared by the formula is coated on the surface of a smooth ceramic tile in a scraping mode, the thickness of the film is about 200 mu m, after the graphene heating slurry is dried, the graphene heating slurry is switched on under 24V voltage and at room temperature of 20 ℃, and the test result is as follows:
| item | Test results |
| Average square resistance of paint (omega) | 80 |
| Specific power (W/m)2) | 150 |
| Average surface temperature (. degree. C.) after 30min | 40 |
Example 3
The graphene heating coating in the embodiment comprises the following components (in percentage by weight):
| component name | Weight percent of |
| Graphene | 50％ |
| Zinc oxide | 5％ |
| Water-based acrylic resin | 20％ |
| Modified starch | 24.1％ |
| Non-silicon polymer defoaming agent | 0.1％ |
| Titanate esters | 0.5％ |
| Acrylate copolymer | 0.3％ |
The preparation method of the graphene heating coating in the embodiment comprises the following steps:
(1) crushing zinc oxide into powder, sieving with 1250 meshes;
(2) adding zinc oxide into a reaction kettle, adding aqueous acrylic resin, graphene, adhesive modified starch, a non-silicon polymer defoaming agent, a titanate coupling agent and a flatting agent acrylate copolymer, and uniformly stirring;
(3) grinding the uniformly stirred slurry in the step (2) by a grinder until the granularity of the slurry is 80-95 mu m;
(4) and adding deionized water to adjust the viscosity of the slurry to be between 110 and 120KU, so as to obtain the graphene heating slurry.
The graphene heating slurry prepared by the formula is coated on the surface of a smooth ceramic tile in a scraping mode, the thickness of the film is about 200 mu m, after the graphene heating slurry is dried, the graphene heating slurry is switched on under 36V voltage and at room temperature of 20 ℃, and the test result is as follows:
| item | Test results |
| Average square resistance of paint (omega) | 100 |
| Specific power (W/m)2) | 230 |
| Average surface temperature (. degree. C.) after 30min | 45 |
The embodiment shows that the graphene heating coating prepared by the method has low requirement on coating thickness, uniform overall heating after electrification and rapid temperature rise, can be coated on floors and walls, is applied to room heating, and is safe and environment-friendly.
Claims (10)
1. The graphene heating coating comprises the following components in percentage by weight:
40% -50% of graphene;
5% -14% of oxide;
20% of water-based resin;
20% -30% of adhesive;
0.1 to 0.5 percent of defoaming agent;
0.3 to 0.5 percent of coupling agent;
0.3 to 0.5 percent of flatting agent.
2. The graphene heating paint according to claim 1, wherein: the number of layers of the graphene is 5-15, and the particle size is 10-15 microns.
3. The graphene heating paint according to claim 2, wherein: the oxide is a metal oxide.
4. The graphene heating paint according to claim 3, wherein: the oxide is one or more of gamma phase ferric oxide, aluminum oxide, zinc oxide and barium oxide.
5. The graphene heating paint according to claim 4, wherein: the water-based resin is one or more of water-based polyurethane resin, water-based epoxy resin and water-based acrylic resin.
6. The graphene heating paint according to claim 5, wherein: the adhesive is one or more of polyvinyl alcohol, carboxymethyl cellulose, polyvinyl acetate, modified starch and polyurethane glue.
7. The graphene heating paint according to claim 6, wherein: the defoaming agent is modified polysiloxane or non-silicon polymer.
8. The graphene heating paint according to claim 7, wherein: the coupling agent is one or more of siloxane, titanate coupling agent and polyterephthalate.
9. The graphene heating paint according to claim 8, wherein: the leveling agent is one or more of polyether modified polydimethylsiloxane, polyether modified organic silicon and water-based acrylate copolymer.
10. The preparation method of the graphene heating coating is characterized by comprising the following steps:
(1) pulverizing the oxide into powder, sieving with 500-2000 mesh sieve;
(2) adding the oxide into a reaction kettle, adding the water-based resin, the graphene, the adhesive, the defoaming agent, the coupling agent and the flatting agent, and uniformly stirring;
(3) grinding the uniformly stirred slurry in the step 2 by a grinder until the granularity of the slurry is 80-100 mu m;
(4) deionized water with the weight of 40-60% of the slurry is added to adjust the thickness and the degree of dilution, and the graphene heating slurry is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375480A (en) * | 2020-11-17 | 2021-02-19 | 厦门海洋南方特种光电材料有限公司 | Water-based graphene coating for heating plate and preparation method thereof |
| CN112376318A (en) * | 2020-11-18 | 2021-02-19 | 无锡海博源包装科技有限公司 | Anti-counterfeiting coating, anti-counterfeiting label printing process and anti-counterfeiting label |
| CN112694774A (en) * | 2021-01-21 | 2021-04-23 | 湖南翰坤实业有限公司 | Environment-friendly energy-saving nano graphene heating coating and preparation method thereof |
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| KR20170027969A (en) * | 2015-09-03 | 2017-03-13 | 김승묵 | A method and electrical conducting heating loess board containing graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112375480A (en) * | 2020-11-17 | 2021-02-19 | 厦门海洋南方特种光电材料有限公司 | Water-based graphene coating for heating plate and preparation method thereof |
| CN112376318A (en) * | 2020-11-18 | 2021-02-19 | 无锡海博源包装科技有限公司 | Anti-counterfeiting coating, anti-counterfeiting label printing process and anti-counterfeiting label |
| CN112694774A (en) * | 2021-01-21 | 2021-04-23 | 湖南翰坤实业有限公司 | Environment-friendly energy-saving nano graphene heating coating and preparation method thereof |
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Application publication date: 20200619 |