CN111138950A - Photoresponse self-cleaning coating and preparation method thereof - Google Patents
Photoresponse self-cleaning coating and preparation method thereof Download PDFInfo
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- CN111138950A CN111138950A CN202010047849.XA CN202010047849A CN111138950A CN 111138950 A CN111138950 A CN 111138950A CN 202010047849 A CN202010047849 A CN 202010047849A CN 111138950 A CN111138950 A CN 111138950A
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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
- 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
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Abstract
The invention provides a photoresponse self-cleaning coating which is characterized by comprising a component A and a component B in a weight ratio of 1: 3-5, wherein the component A comprises the following raw materials in parts by weight: modified g-C3N420-40 parts of water, 200-300 parts of water and 200-300 parts of water-based epoxy resin; the component B comprises the following raw materials in parts by weight: 20-40 parts of water-based curing agent and 50-100 parts of water; the modification g-C3N4Is obtained by doping and modifying a carbon-containing nitrogen-rich precursor by using metal. The preparation method of the invention is that the g-C is modified by metal3N4Compared with the traditional TiO, the photoresponse self-cleaning coating prepared by mixing the coating with the waterborne epoxy resin2The paint is completely nontoxic and pollution-free, and is more suitable for indoor use; the invention adopts g-C modified by metal3N4As the filler, g-C modified by metal modification3N4Is more active than the unmodified photocatalysis activityAnd (5) greatly improving.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a photoresponse self-cleaning coating and a preparation method thereof.
Background
The water-based epoxy paint is widely used in the aspects of environmental protection, particularly indoor and outdoor and decorative materials, but the paint color is faded and is difficult to clean due to organic precipitation caused by air pollution or improper use which is inevitable in the use process, and finally the paint cannot be used.
The common photoresponse self-cleaning coating on the market at present is prepared by mixing titanium dioxide (TiO)2) And various oxide sulfides such as zinc oxide (ZnO), cadmium sulfide (CdS) and the like are used as photocatalysts and added into the coating. However, zinc oxide, cadmium sulfide and other metal oxides and sulfides are unstable in use, and thus some metal ions are dissolved out, and certain biotoxicity is achieved, so that the zinc oxide, cadmium sulfide and other metal oxides and sulfides are rarely used for civil use. The titanium dioxide has a large limitation because the titanium dioxide can have a catalytic effect only under the irradiation of ultraviolet light.
Graphite-like phase carbon nitride (g-C)3N4) The graphene/triazine ring composite material is a planar two-dimensional lamellar structure similar to graphene, and a triazine ring and a 3-s-triazine ring are used as basic structural units to extend infinitely to form a net structure. Compared with TiO, the material is used as a novel nonmetal photocatalytic material2The material is nontoxic and pollution-free, is more suitable for indoor air pollution treatment and organic matter degradation, but the g-C3N4The range of the optical response is limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a photoresponse self-cleaning coating and a preparation method thereof3N4The composite coating is mixed with epoxy resin, so that the composite coating has a photoresponse self-cleaning function, and is more suitable for indoor self-cleaning and other functions when being compounded with water-based epoxy resin.
The purpose of the invention is realized by the following technical scheme:
a photoresponse self-cleaning coating is prepared from a component A and a component B in a weight ratio of 1: 3-5, wherein the component A comprises the following raw materials in parts by weightConsists of the following components: modified g-C3N420-40 parts of water, 200-300 parts of water and 200-300 parts of water-based epoxy resin; the component B comprises the following raw materials in parts by weight: 20-40 parts of water-based curing agent and 50-100 parts of water;
the modification g-C3N4Is obtained by doping and modifying a carbon-containing nitrogen-rich precursor by using metal.
The modification g-C3N4The preparation method comprises the following steps:
(1) and (2) putting 0.5 wt% of metal salt solution into the carbon-containing nitrogen-rich precursor, uniformly stirring, heating and evaporating water to obtain a solid A, wherein the ratio of the volume of the metal salt solution to the mass of the carbon-containing nitrogen-rich precursor is (1-2): (2-4);
(2) the solid A is heated at 5-20 ℃ for min-1Heating to 530-600 ℃ at a heating speed, preserving heat for 3-6 h, and cooling to obtain modified g-C3N4And (3) powder.
Further, the metal solution in the step (1) is MgCl2Or CaCl2。
Further, the carbon-containing nitrogen-rich precursor in the step (1) is one or more of melamine, dicyandiamide, cyanamide and urea.
A preparation method of a photoresponse self-cleaning coating comprises the following steps:
(1) uniformly mixing 200-300 parts of water and 200-300 parts of waterborne epoxy resin, and then adding 20-40 parts of modified g-C3N4Performing ball milling dispersion on the powder to obtain a photoresponse self-cleaning coating mother solution;
(2) uniformly mixing 20-40 parts of aqueous curing agent and 50-100 parts of water, and mixing the mixture with the mother liquor in a ratio of 1: and (3) uniformly mixing the components in the volume ratio to obtain the photoresponse self-cleaning coating.
Further, the water-based epoxy resin in the step (1) is one or more of Ar555 epoxy resin, H228A epoxy resin, E44 epoxy emulsion, E51 epoxy emulsion and E20 epoxy emulsion.
Further, the water-based curing agent in the step (2) is one or more of Aq419, H228B, W651 and W650.
The invention has the advantages and effects that:
(1) the preparation method of the invention is that the g-C is modified by metal3N4Compared with the traditional TiO, the photoresponse self-cleaning coating prepared by mixing the coating with the waterborne epoxy resin2And the paint is completely nontoxic and pollution-free, and is more suitable for indoor use.
(2) The invention adopts g-C modified by metal3N4As the filler, g-C modified by metal modification3N4The photocatalytic activity is greatly improved compared with that of the unmodified photocatalyst.
Drawings
FIG. 1 shows g-C after metal modification3N4Schematic representation.
FIG. 2 shows g-C3N4The mechanism diagram of photocatalysis.
FIG. 3 is TiO2Unmodified g-C3N4Modified g-C3N4Experimental comparison graph for degrading rhodamine B.
Detailed description of the invention
The present invention will be described in detail with reference to examples.
The invention proposes the modification of g-C with metals3N4Preparation method of water-based epoxy resin coating, wherein the used filler is g-C modified by metal3N4The material has the advantages of no toxicity, no pollution, low use requirement, obvious photocatalytic effect and the like. After the metal modification is used, the visible light response range of the material is further improved. Greatly improves the capability of the composite coating in cleaning organic dirt.
The modification g-C3N4A method of preparing a powder comprising the steps of:
(1) preparing 10-20 mL (0.5 wt%) of metal salt solution, and adding 10-20 g of carbon-containing nitrogen-rich precursor (g-C)3N4) And uniformly stirring, heating and evaporating water to obtain a solid A.
(2) The solid A is heated at 5-20 ℃ for min-1Heating to 530-600 ℃ at a heating speed, preserving heat for 3-6 h, and cooling to obtain modified g-C3N4And (3) powder.
Example 1
(1) Metal modified g-C3N4：
1) Preparation of 10ml (0.5% by weight) of CaCl2Putting the solution into a 20g melamine sample, uniformly stirring, and heating at 60 ℃ to evaporate water;
2) weighing 10g of the treated sample at room temperature, adding the sample into a crucible, placing the crucible into a muffle furnace, and raising the temperature at a speed of 5 ℃ for min-1Heating to 530 ℃, preserving heat for 3h at the temperature, and naturally cooling to room temperature to obtain calcium metal doped modified g-C3N4Powder;
(2) preparing the composite coating:
1) taking 200 parts of water-based epoxy resin and 200 parts of water;
2) 20 portions of calcium metal are taken to be doped and modified g-C3N4Adding the mixture into the resin system, and dispersing for 2 hours by using a ball mill;
3) uniformly mixing 20 parts of water-based curing agent and 50 parts of water; mixing the mother liquor of the water-based epoxy composite coating and the diluted water-based curing agent according to the ratio of 3: 1, coating the mixture on a substrate in a mixed manner, controlling the thickness to be 30-200um, and curing at room temperature;
the waterborne epoxy resin is Ar555 epoxy resin, and the waterborne curing agent is Aq 419.
Example 2
(1) Metal modified g-C3N4：
1) Preparation of 15ml (0.5% by weight) of CaCl2Putting the solution into a 30g melamine sample, uniformly stirring, and heating at 60 ℃ to evaporate water;
2) weighing 20g of the treated sample at room temperature, adding the sample into a crucible, placing the crucible into a muffle furnace, and raising the temperature at a speed of 10 ℃ min-1Heating to 550 ℃, preserving heat for 4h at the temperature, and naturally cooling to room temperature to obtain calcium metal doped modified g-C3N4Powder;
(2) preparing the composite coating:
1) taking 250 parts of water-based epoxy resin and 250 parts of water;
2) taking 30 parts of calcium metal to dope and modify g-C3N4Adding the mixture into the resin system, and dispersing for 2 hours by using a ball mill;
3) uniformly mixing 30 parts of water-based curing agent and 80 parts of water; mixing the mother liquor of the water-based epoxy composite coating with the diluted water-based curing agent according to the ratio of 4: 1, coating the mixture on a substrate in a mixed manner, controlling the thickness to be 30-200um, and curing at room temperature;
the waterborne epoxy resin is Ar555 epoxy resin, and the waterborne curing agent is Aq 419.
Example 3
(1) Metal modified g-C3N4：
1) Preparation of 20ml (0.5 wt%) CaCl2Putting the solution into 40g of melamine sample, uniformly stirring, and heating at 60 ℃ to evaporate water;
2) weighing 30g of the treated sample at room temperature, adding the sample into a crucible, placing the crucible into a muffle furnace, and raising the temperature at a speed of 20 ℃ for min-1Heating to 600 ℃, preserving heat for 6h at the temperature, and naturally cooling to room temperature to obtain calcium metal doped modified g-C3N4Powder;
(2) preparing the composite coating:
1) taking 200 parts of water-based epoxy resin and 300 parts of water;
2) 40 parts of calcium metal is taken to be doped and modified g-C3N4Adding the mixture into the resin system, and dispersing for 2 hours by using a ball mill;
3) uniformly mixing 40 parts of water-based curing agent with 100 parts of water; mixing the mother liquor of the water-based epoxy composite coating with the diluted water-based curing agent according to the ratio of 5: 1, coating the mixture on a substrate in a mixed manner, controlling the thickness to be 30-200um, and curing at room temperature;
the waterborne epoxy resin is Ar555 epoxy resin, and the waterborne curing agent is Aq 419.
Comparative example 1TiO2Self-cleaning coating
(1) 200 parts of water-based epoxy resin and 200 parts of water are uniformly mixed, and 20 parts of TiO is added2Dispersing the powder for 2 hours by using a ball mill;
(3) uniformly mixing 20 parts of water-based curing agent and 50 parts of water; mixing the mother liquor of the water-based epoxy composite coating and the diluted water-based curing agent according to the ratio of 3: 1, coating the mixture on a substrate in a mixed manner, controlling the thickness to be 30-200um, and curing at room temperature;
the waterborne epoxy resin is Ar555 epoxy resin, and the waterborne curing agent is Aq 419.
Comparative example 2 unmodified g-C3N4Coating material
Except using unmodified g-C3N4Other components and preparation methods were the same as in example 1.
(1) Adding 10ml of water into 20g of melamine, uniformly stirring, and heating at 60 ℃ to evaporate water; then 10g of the treated melamine was taken and added to a crucible and placed in a muffle furnace at a temperature rise rate of 5 ℃ for min-1Heating to 530 deg.C, keeping the temperature for 3h, and naturally cooling to room temperature to obtain powder.
(2) Uniformly mixing 200 parts of waterborne epoxy resin and 200 parts of water, adding 20 parts of powder, and dispersing for 2 hours by using a ball mill;
(3) uniformly mixing 20 parts of water-based curing agent and 50 parts of water; mixing the mother liquor of the water-based epoxy composite coating and the diluted water-based curing agent according to the ratio of 3: 1, coating the mixture on a substrate in a mixed manner, controlling the thickness to be 30-200um, and curing at room temperature;
the waterborne epoxy resin is Ar555 epoxy resin, and the waterborne curing agent is Aq 419.
FIG. 3 is a graph showing a photo-responsive self-cleaning coating prepared in example 1, and TiO of comparative example 12Self-cleaning coating and unmodified g-C of comparative example 23N4The coating film of the coating material degrades rhodamine B analysis chart under ultraviolet irradiation, and the modified g-C can be seen from FIG. 33N4The coating film of the coating has better capability of degrading rhodamine B under the irradiation of ultraviolet rays than other two groups.
Claims (7)
1. The photoresponse self-cleaning coating is characterized by comprising a component A and a component B in a weight ratio of 1: 3-5, wherein the component A comprises the following raw materials in parts by weight: modified g-C3N420-40 parts of water, 200-300 parts of water and 200-300 parts of water-based epoxy resin; the component B comprises the following raw materials in parts by weight: water (W)20-40 parts of a curing agent and 50-100 parts of water;
the modification g-C3N4Is obtained by doping and modifying a carbon-containing nitrogen-rich precursor by using metal.
2. The photo-responsive self-cleaning coating of claim 1, wherein the modified g-C3N4The preparation method comprises the following steps:
(1) and (2) putting 0.5 wt% of metal salt solution into the carbon-containing nitrogen-rich precursor, uniformly stirring, heating and evaporating water to obtain a solid A, wherein the ratio of the volume of the metal salt solution to the mass of the carbon-containing nitrogen-rich precursor is (1-2): (2-4);
(2) the solid A is heated at 5-20 ℃ for min-1Heating to 530-600 ℃ at a heating speed, preserving heat for 3-6 h, and cooling to obtain modified g-C3N4And (3) powder.
3. The photo-responsive self-cleaning coating of claim 1, wherein the metal solution in step (1) is MgCl2Or CaCl2。
4. The photo-responsive self-cleaning coating material of claim 1, wherein the carbon-nitrogen-rich precursor in step (1) is one or more of melamine, dicyandiamide, cyanamide and urea.
5. The photo-responsive self-cleaning coating of claim 1, wherein the water-based epoxy resin is one or more of Ar555 epoxy resin, H228A epoxy resin, E44 epoxy emulsion, E51 epoxy emulsion and E20 epoxy emulsion.
6. The photo-responsive self-cleaning coating material of claim 1, wherein the aqueous curing agent is one or more of Aq419, H228B, W651 and W650.
7. A preparation method of a photoresponse self-cleaning coating comprises the following steps:
(1) uniformly mixing 200-300 parts of water and 100-200 parts of waterborne epoxy resin, and then adding 20-40 parts of modified g-C3N4Performing ball milling dispersion on the powder to obtain a photoresponse self-cleaning coating mother solution;
(2) uniformly mixing 20-40 parts of aqueous curing agent and 50-100 parts of water, and mixing the mixture with the mother liquor in a ratio of 1: and (3) uniformly mixing the components in the volume ratio to obtain the photoresponse self-cleaning coating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115029028A (en) * | 2022-06-16 | 2022-09-09 | 大连理工大学 | Application of novel photocatalytic antifouling agent |
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2020
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Application publication date: 20200512 |