CN116589878B - Long-acting self-cleaning graphene ceramic water paint and preparation method and application thereof - Google Patents
Long-acting self-cleaning graphene ceramic water paint and preparation method and application thereof Download PDFInfo
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- CN116589878B CN116589878B CN202310885463.XA CN202310885463A CN116589878B CN 116589878 B CN116589878 B CN 116589878B CN 202310885463 A CN202310885463 A CN 202310885463A CN 116589878 B CN116589878 B CN 116589878B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 239000003973 paint Substances 0.000 title claims abstract description 71
- 239000000919 ceramic Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000004140 cleaning Methods 0.000 title claims abstract description 41
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- RRKXGHIWLJDUIU-UHFFFAOYSA-N 5-bromo-8-chloroisoquinoline Chemical group C1=NC=C2C(Cl)=CC=C(Br)C2=C1 RRKXGHIWLJDUIU-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N 1-dodecanol group Chemical group C(CCCCCCCCCCC)O LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 238000005096 rolling process Methods 0.000 abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000036561 sun exposure Effects 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/63—Additives non-macromolecular organic
Abstract
The application relates to the technical field of water-based paint, in particular to a long-acting self-cleaning graphene ceramic water paint and a preparation method and application thereof; the application discloses a long-acting self-cleaning graphene ceramic water paint which comprises the following raw materials in parts by weight: modified silica sol: 134-195 parts of modified graphene oxide: 96-122 parts of coupling agent: 10-15 parts of grafting agent: 5-8 parts of dispersing agent: 3-5 parts. The long-acting self-cleaning graphene ceramic water paint provided by the application has the advantages that the cured coating has high contact angle, low rolling angle and high adhesion level, and has a long-acting self-cleaning function.
Description
Technical Field
The application relates to the technical field of water-based paint, in particular to a long-acting self-cleaning graphene ceramic water paint and a preparation method and application thereof.
Background
At present, common paint is not resistant to high temperature and can crack, foam and fall off under intense sun exposure for a long time; the common paint is easy to be stained with ash, needs to be cleaned frequently, and is not easy to be cleaned after being dried by intense sun exposure for a long time; therefore, how to improve the super-weatherability and self-cleaning of the coating is the research direction in the current coating field.
The ceramic paint is essentially an organic-inorganic hybrid paint with methyl silicone resin as a main film forming material. The coating of the ceramic coating has a series of properties similar to ceramics after curing, such as high hardness, abrasion resistance, high temperature resistance, flame retardance, aging resistance, good contact safety and the like, and the coating is named as the ceramic coating.
However, the current conventional ceramic coating has the defects of poor weather resistance of the coating, obviously reduced self-cleaning capability with long-time use, poor matching property with the conventional organic coating and difficult recoating and repairing.
Therefore, it is necessary to provide a graphene ceramic water paint with long-acting self-cleaning function, and a preparation method and application thereof.
Disclosure of Invention
In order to overcome the defects of the prior art, the application provides a long-acting self-cleaning graphene ceramic water paint and a preparation method and application thereof; the graphene ceramic water paint provided by the application has the advantages that the cured coating has high contact angle, low rolling angle and high adhesion level, and has a long-acting self-cleaning function.
The technical scheme adopted for solving the technical problems is as follows:
the application provides a long-acting self-cleaning graphene ceramic water paint, which comprises the following raw materials in parts by weight:
modified silica sol: 134-195 parts
Modified graphene oxide: 96-122 parts
Coupling agent: 10-15 parts
Grafting agent: 5-8 parts
Dispersing agent: 3-5 parts.
Preferably, the modified silica sol comprises the following raw materials in parts by weight:
silica: 20-25 parts
Water glass: 8-10 parts
Ammonia water: 3-5 parts
Modifier A:3-5 parts
Water: 100-150 parts.
More preferably, the modifier A is cetyltrimethylammonium bromide.
Preferably, the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15-20 parts of a lubricant;
modifier B:1-2 parts
Ethanol: 30-40 parts
Water: 50-60 parts.
More preferably, the modifier B is 3-glycidyl ether-propyl trimethoxysilane.
Preferably, the coupling agent is an aluminum zirconate coupling agent.
Preferably, the grafting agent is a mixture of cuprous bromide and polyamine. Specifically, the polyamine is any one of triethylamine or diethylenetriamine.
Preferably, the dispersing agent is lauryl alcohol ether phosphate.
The second object of the application is to provide a preparation method of the long-acting self-cleaning graphene ceramic water paint, which comprises the following steps:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, ammonia water, a modifier A and water, and reacting for 10-12h at 60-70 ℃; after the reaction is finished, regulating the pH to 9-10 to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 5-7h at 70-80 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, and reacting for 4-5 hours at 50-60 ℃; adding grafting agent and dispersant, mixing thoroughly, and reacting at 50-60 ℃ for 0.5-1h; and cooling to room temperature to obtain the graphene ceramic water paint.
The third object of the application is to provide the graphene ceramic water paint which is applied to the outer wall of a building, the outer surface of an automobile and the surface of a monocrystalline silicon plate of a photovoltaic power station.
The graphene oxide has high surface energy and is easy to generate agglomeration phenomenon, so that the dispersibility of the graphene oxide in a solvent is greatly influenced, and the application is limited, so that the graphene oxide is required to be modified to solve the problems of easy agglomeration and the like, and the dispersibility of the graphene oxide in a coating is improved; according to the application, after the graphene oxide is modified by using the modifier B, the modified silica sol and the modified graphene oxide can be well coupled by using the coupling agent, so that the dispersibility of the graphene oxide and the silica in the coating is improved.
The beneficial effects of the application are as follows:
the graphene ceramic water paint prepared by the method has a long-acting self-cleaning function, and is particularly applied to a coating template, wherein a contact angle is 156-161 degrees before a water resistance test, a rolling angle is 4-6 degrees, and the contact angle and the rolling angle are basically unchanged after the water resistance test is carried out; the adhesion rating is 0; in the long-acting cleaning test, the cleaning is easy.
Detailed Description
The application will be further illustrated by the following examples, which are not intended to limit the scope of the application, in order to facilitate the understanding of those skilled in the art.
Example 1
The long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 134 parts of
Modified graphene oxide: 96 parts of
Coupling agent (aluminum zirconate coupling agent): 10 parts of
Grafting agent: 1 part of cuprous bromide and 3 parts of triethylamine
Dispersant (lauryl ether phosphate): 3 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 20 parts of
Water glass (modulus 1.5): 8 parts of
Saturated concentrated ammonia water: 3 parts of
Modifier a (cetyl trimethylammonium bromide): 3 parts of
Water: 100 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15 parts of
Modifier B (3-glycidyl ether-propyl trimethoxysilane): 1 part of
Ethanol: 30 parts of
Water: 50 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, saturated concentrated ammonia water, a modifier A and water, and then reacting for 12 hours at 60 ℃; after the reaction is finished, regulating the pH to 9 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 7h at 70 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, reacting for 4 hours at 50 ℃, adding the grafting agent and the dispersing agent, fully mixing, and reacting for 0.5 hour at 50 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Example 2
The long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 195 parts
Modified graphene oxide: 122 parts of
Coupling agent (aluminum zirconate coupling agent): 15 parts of
Grafting agent: 2 parts of cuprous bromide and 5 parts of diethylenetriamine
Dispersant (lauryl ether phosphate): 5 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 25 parts of
Water glass (modulus 2.0): 10 parts of
Saturated concentrated ammonia water: 5 parts of
Modifier a (cetyl trimethylammonium bromide): 5 parts of
Water: 150 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 20 parts of
Modifier B (3-glycidyl ether-propyl trimethoxysilane): 2 parts of
Ethanol: 40 parts of
Water: 60 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, saturated concentrated ammonia water, a modifier A and water, and then reacting for 10 hours at 70 ℃; after the reaction is finished, regulating the pH to 9 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 5 hours at 80 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, reacting for 4 hours at 60 ℃, adding the grafting agent and the dispersing agent, fully mixing, and reacting for 1 hour at 60 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Example 3
The long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 170 parts of
Modified graphene oxide: 108 parts of
Coupling agent (aluminum zirconate coupling agent): 12 parts of
Grafting agent: 1 part of cuprous bromide and 4 parts of diethylenetriamine
Dispersant (lauryl ether phosphate): 4 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 23 parts of
Water glass (modulus 1.8): 9 parts of
Saturated concentrated ammonia water: 4 parts of
Modifier a (cetyl trimethylammonium bromide): 4 parts of
Water: 130 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 17 parts of
Modifier B (3-glycidyl ether-propyl trimethoxysilane): 1 part of
Ethanol: 35 parts of
Water: 55 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; silica is prepared from,
Fully mixing water glass, saturated strong ammonia water, a modifier A and water, and reacting for 11 hours at 65 ℃; after the reaction is finished, regulating the pH to 9.5 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 6 hours at 75 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, reacting for 4.5 hours at 55 ℃, adding the grafting agent and the dispersing agent, fully mixing, and reacting for 0.8 hour at 55 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Example 4
The long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 195 parts
Modified graphene oxide: 122 parts of
Coupling agent (aluminum zirconate coupling agent): 10 parts of
Grafting agent: 1 part of cuprous bromide and 3 parts of triethylamine
Dispersant (lauryl ether phosphate): 5 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 25 parts of
Water glass (modulus 1.5): 10 parts of
Saturated concentrated ammonia water: 5 parts of
Modifier a (cetyl trimethylammonium bromide): 5 parts of
Water: 150 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 20 parts;
modifier B (3-glycidyl ether-propyl trimethoxysilane): 2 parts of
Ethanol: 40 parts of
Water: 60 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, saturated concentrated ammonia water, a modifier A and water, and then reacting for 10 hours at 60 ℃; after the reaction is finished, regulating the pH to 9 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; graphene oxide is treated by,
Fully mixing the modifier B, ethanol and water, and reacting for 5 hours at 70 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, reacting for 4 hours at 50 ℃, adding the grafting agent and the dispersing agent, fully mixing, and reacting for 1 hour at 50 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Example 5
The long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 134 parts of
Modified graphene oxide: 122 parts of
Coupling agent (aluminum zirconate coupling agent): 15 parts of
Grafting agent: 2 parts of cuprous bromide and 5 parts of triethylamine
Dispersant (lauryl ether phosphate): 3 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 20 parts of
Water glass (modulus 2.0): 8 parts of
Saturated concentrated ammonia water: 5 parts of
Modifier a (cetyl trimethylammonium bromide): 3 parts of
Water: 100 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15 parts of
Modifier B (3-glycidyl ether-propyl trimethoxysilane): 1 part of
Ethanol: 30 parts of
Water: 50 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, saturated concentrated ammonia water, a modifier A and water, and then reacting for 112h at 70 ℃; after the reaction is finished, regulating the pH to 10 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and then reacting for 7h at 80 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, reacting for 5 hours at 60 ℃, adding the grafting agent and the dispersing agent, fully mixing, and reacting for 0.5 hour at 60 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Comparative example 1, without grafting agent, specifically:
the long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 134 parts of
Modified graphene oxide: 96 parts of
Coupling agent (aluminum zirconate coupling agent): 10 parts of
Dispersant (lauryl ether phosphate): 3 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 20 parts of
Water glass (modulus 1.5): 8 parts of
Saturated concentrated ammonia water: 3 parts of
Modifier a (cetyl trimethylammonium bromide): 3 parts of
Water: 100 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15 parts of
Modifier B (3-glycidyl ether-propyl trimethoxysilane): 1 part of
Ethanol: 30 parts of
Water: 50 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, saturated concentrated ammonia water, a modifier A and water, and then reacting for 12 hours at 60 ℃; after the reaction is finished, regulating the pH to 9 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 7h at 70 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, and reacting for 4 hours at 50 ℃; adding a dispersing agent, fully mixing, and reacting for 0.5h at 50 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Comparative example 2, without coupling agent, specifically:
the long-acting self-cleaning graphene ceramic water paint comprises the following raw materials in parts by weight:
modified silica sol: 134 parts of
Modified graphene oxide: 96 parts of
Grafting agent: 1 part of cuprous bromide and 3 parts of triethylamine
Dispersant (lauryl ether phosphate): 3 parts.
Wherein: the modified silica sol comprises the following raw materials in parts by weight:
silica: 20 parts of
Water glass (modulus 1.5): 8 parts of
Saturated concentrated ammonia water: 3 parts of
Modifier a (cetyl trimethylammonium bromide): 3 parts of
Water: 100 parts;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15 parts;
modifier B (3-glycidyl ether-propyl trimethoxysilane): 1 part of
Ethanol: 30 parts of
Water: 50 parts.
The preparation method of the long-acting self-cleaning graphene ceramic water paint comprises the following steps of:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; silica is prepared from,
Fully mixing water glass, saturated strong ammonia water, a modifier A and water, and reacting for 12 hours at 60 ℃; after the reaction is finished, regulating the pH to 9 (using glacial acetic acid) to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 7h at 70 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol and the modified graphene oxide, adding a grafting agent and a dispersing agent, and reacting for 0.5h at 50 ℃; and cooling to room temperature to obtain the graphene ceramic water paint.
Wherein, the sheet diameter of the graphene oxide used in the application is 1-20 mu m, and CAS number: 7782-42-5 from: shanghai Inset technology Co., ltd. The particle size of the silica was 50nm.
The following performance tests were carried out on the water paints prepared in examples 1 to 5 and comparative examples 1 to 2:
(1) Template preprocessing
The tinplate is selected from 50mm multiplied by 130mm multiplied by 0.8mm, is polished by sand paper to remove rust, is washed for a plurality of times by deionized water and ethanol solution, and is dried for standby after cleaning.
(2) Coating preparation
The graphene ceramic water paint of the examples and the comparative examples is uniformly coated on the surface of the tin plate by adopting a roll coating method by using a bar, so that the coating film is ensured to be uniform and no shrinkage cavity is formed. The coated panel was left at room temperature for 15min, then placed in a forced air drying oven to cure at 80℃for 2h, and after curing the coating thickness was about 45 (+ -5) μm, to give a coated panel.
(3) Detection method
Contact angle and roll angle tests; performing contact angle and rolling angle tests on the coating template;
long-term cleanliness test: after the coating template is placed on a construction site for one month, the coating template is cleaned by using a 12000-turn car-washing water gun, and the cleaning result is recorded.
And (3) water resistance test: the water resistance test was performed with a water immersion coating, with reference to the GB/T30648.2-2015 standard. After 7 days of soaking, the sample plate is taken out, the water is absorbed, and the sample plate is dried for 24 hours at room temperature. The contact angle and the rolling angle of the coating before and after the water resistance test were measured.
Adhesion rating: the test was carried out according to GB/T9286.
The above detection results are summarized in the following table 1:
TABLE 1
From table 1 above, it can be seen that the graphene ceramic water paint prepared in examples 1-5 is applied to a coating template, and the detection result is: the contact angle is 156-161 degrees before the water resistance test, the rolling angle is 4-6 degrees, and the contact angle and the rolling angle are basically unchanged after the water resistance test; the adhesion rating is 0; in the long-acting cleaning test, the cleaning is easy.
In comparative example 1, after the grafting agent is absent, the modified silica sol and the modified graphene oxide coupled in the ceramic water paint are not easy to graft and polymerize on the template, so that the adhesion level is obviously reduced, the adhesion level is represented by level 4, the contact angle is 135 degrees before the water resistance test, the rolling angle is 16 degrees, and the coating is peeled off after the water resistance test is carried out; in the long-term cleanliness test, there is a portion of the cleaning.
In comparative example 1, in the absence of the coupling agent, the modified silica sol and the modified graphene oxide in the ceramic water paint are not coupled, so that the contact angle and the rolling angle of the coating are obviously reduced after curing, specifically, the contact angle is 106 degrees before the water resistance test, the rolling angle is 28 degrees, and the contact angle is 93 degrees after the water resistance test, and the rolling angle is 36 degrees; in the long-term cleaning test, the cleaning agent is basically not washed off.
The above embodiments are preferred embodiments of the present application, and besides, the present application may be implemented in other ways, and any obvious substitution is within the scope of the present application without departing from the concept of the present application.
Claims (4)
1. The long-acting self-cleaning graphene ceramic water paint is characterized by comprising the following raw materials in parts by weight:
modified silica sol: 134-195 parts
Modified graphene oxide: 96-122 parts
Coupling agent: 10-15 parts
Grafting agent: 5-8 parts
Dispersing agent: 3-5 parts;
the modified silica sol comprises the following raw materials in parts by weight:
silica: 20-25 parts
Water glass: 8-10 parts
Ammonia water: 3-5 parts
Modifier A:3-5 parts
Water: 100-150 parts;
modifier A is cetyl trimethyl ammonium bromide;
the modified graphene oxide comprises the following raw materials in parts by weight:
graphene oxide: 15-20 parts of a lubricant;
modifier B:1-2 parts
Ethanol: 30-40 parts
Water: 50-60 parts;
the modifier B is 3-glycidyl ether-propyl trimethoxy silane;
the coupling agent is an aluminum zirconate coupling agent;
the grafting agent is a mixture composed of cuprous bromide and polyamine;
the preparation process of the modified silica sol comprises the following steps:
preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, ammonia water, a modifier A and water, and reacting for 10-12h at 60-70 ℃; after the reaction is finished, regulating the pH to 9-10 to obtain modified silica sol;
the preparation process of the modified graphene oxide comprises the following steps:
preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 5-7h at 70-80 ℃; and obtaining the modified graphene oxide.
2. The long-acting self-cleaning graphene ceramic water paint according to claim 1, wherein the dispersant is lauryl alcohol ether phosphate.
3. The method for preparing the long-acting self-cleaning graphene ceramic water paint according to any one of claims 1 to 2, which is characterized by comprising the following steps:
s1, preparation of modified silica sol
Preparing corresponding raw materials according to the weight parts of the modified silica sol; fully mixing silicon dioxide, water glass, ammonia water, a modifier A and water, and reacting for 10-12h at 60-70 ℃; after the reaction is finished, regulating the pH to 9-10 to obtain modified silica sol;
s2, preparation of modified graphene oxide
Preparing corresponding raw materials according to the weight parts of the modified graphene oxide; fully mixing graphene oxide, a modifier B, ethanol and water, and reacting for 5-7h at 70-80 ℃; obtaining modified graphene oxide;
s3, preparation of ceramic water paint
Preparing corresponding raw materials according to the composition of the graphene ceramic water paint in parts by weight; fully mixing the modified silica sol, the modified graphene oxide and the coupling agent, and reacting for 4-5 hours at 50-60 ℃; adding grafting agent and dispersant, fully mixing, and reacting at 50-60 ℃ for 0.5-1h; and cooling to room temperature to obtain the graphene ceramic water paint.
4. The application of the long-acting self-cleaning graphene ceramic water paint is characterized in that the graphene ceramic water paint disclosed in any one of claims 1-2 or the graphene ceramic water paint prepared by the preparation method disclosed in claim 3 is applied to the surface of a building outer wall, the surface of an automobile and the surface of a monocrystalline silicon plate of a photovoltaic power station.
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