Inorganic composite environment-friendly coating for photocatalytic purification of air and preparation method of inorganic composite environment-friendly coating

Abstract

The invention discloses an inorganic composite environment-friendly coating for photocatalytic air purification and a preparation method of the inorganic composite environment-friendly coating. The coating comprises the following raw material components in parts by mass: 30-60 parts of emulsion; 5 to 20 parts of a porous substance-dye molecularly-TiO2 photocatalytic composite material; 10 to 30 parts of an inorganic filler; 1-5 parts of an auxiliary agent; 10 to 40 parts of water; wherein the porous substance-dye molecularly-TiO2 photocatalytic composite material is a composite material formed by loading dye molecules onto the surface of titanium dioxide on the surface or in pore channels of a porous substance. A more sufficient photocatalytic substrate is provided by utilizing a porous substance, and the photocatalytic capability is promoted by utilizing the light absorption capability of dye molecules, so that the air purification effect is enhanced, and the purification efficiency is improved.

Description

Technical Field

[0001] The present application relates to the field of coating technology, and in particular to an inorganic composite environmentally friendly coating for photocatalytic air purification and a preparation method thereof. Background Art

[0002] Traditional coatings release harmful gases such as formaldehyde during the drying and curing process, which seriously affects the indoor air quality and poses potential harm to the health of residents. Related technical research has added photocatalysts to the coating formula to use light sources to excite the photocatalysts in the coating to produce highly active hydroxyl free radicals with strong oxidizing ability, thereby degrading organic pollutants and decomposing harmful substances such as formaldehyde in the air.

[0003] However, the photocatalytic effect of photocatalytic environmentally friendly coatings is directly affected by the light source conditions. The photocatalytic environmentally friendly coatings currently on the market have strict requirements on light sources and need to pay attention to sufficient light source supply. The purification efficiency of harmful gases is not high. Summary of the invention

[0004] The present application provides an inorganic composite environmentally friendly coating for photocatalytic air purification and a preparation method thereof, so as to solve the technical problem that the current photocatalytic coating has low purification efficiency for harmful gases.

[0005] In order to solve the above technical problems, in the first aspect, the present application provides an inorganic composite environmentally friendly coating for photocatalytic air purification, comprising the following raw material components in parts by mass:

[0006] 30 to 60 parts of emulsion;

[0007] 5 to 20 parts of porous material-dye molecule-TiO2 photocatalytic composite material;

[0008] 10 to 30 parts of inorganic filler;

[0009] 1 to 5 parts of additives;

[0010] 10 to 40 parts of water;

[0011] The porous material-dye molecule-TiO2 photocatalytic composite material is a composite material formed by loading dye molecules onto the surface of titanium dioxide on the surface or in the pores of the porous material.

[0012] In some embodiments, the method for preparing the porous material-dye molecule-TiO2 photocatalytic composite material comprises the following steps:

[0013] Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 20 minutes to 40 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7 to 9, and stirring for 2 hours to 4 hours to obtain a titanium dioxide dispersion;

[0014] The dye molecules are dissolved in dimethyl sulfoxide, and then added to the titanium dioxide dispersion, stirred for 6 to 12 hours, filtered and impurities removed to obtain dye molecule-TiO2 composite particles;

[0015] The porous material is evenly dispersed in ethanol, and then the dye molecule-TiO2 composite particles are added. After stirring at 500rpm-1000rpm for 2h-4h, methyl cellulose is added and stirring is continued for 30min-60min. The porous material is filtered, impurities are removed, and dried. After heat treatment at 300℃-500℃, it is cooled to room temperature to obtain a porous material-dye molecule-TiO2 photocatalytic composite material.

[0016] In some embodiments, the particle size of the titanium dioxide particles is 10 nm to 50 nm.

[0017] In some of the embodiments, the mass ratio of the titanium dioxide particles, the dye molecules and the porous material is 5:1:10.

[0018] In some embodiments, the porous material includes, but is not limited to, one or more of diatomaceous earth, activated carbon, zeolite, porous ceramics, montmorillonite, bentonite, porous silica, and porous alumina.

[0019] In some embodiments, the dye molecules include, but are not limited to, one or more of phthalocyanine dye molecules, porphyrin dye molecules, rhodamine dye molecules, and pyridine dye molecules.

[0020] In some of the embodiments, the phthalocyanine dye molecules include one or two of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine;

[0021] Or, the porphyrin dye molecules include one or more of hematoporphyrin, porphyrin iron, porphyrin copper, dihydrochlorin e6 and dihydrochlorin e4;

[0022] Or, the rhodamine dye molecules include one or two of rhodamine B, rhodamine 6G, rhodamine X and rhodamine green;

[0023] Alternatively, the pyridine dye molecules include one or both of zinc pyridine and cobalt pyridine.

[0024] In some embodiments, the emulsion includes any one of acrylic emulsion, styrene acrylic emulsion, polyvinyl acetate emulsion and polyvinyl alcohol emulsion;

[0025] The inorganic filler includes one or more of silicon dioxide, talc, mica, kaolin, calcium carbonate, barium sulfate, wollastonite, titanium dioxide, graphite and carbon black.

[0026] In some embodiments, the auxiliary agent includes one or more of a dispersant, a defoamer, a leveling agent, a thickener, a preservative, a wetting agent, an antistatic agent, a mildewproof agent, a cross-linking agent and a flame retardant.

[0027] In a second aspect, the present application also provides a method for preparing the above-mentioned inorganic composite environmentally friendly coating for photocatalytic air purification, comprising the following steps:

[0028] Add emulsion, inorganic filler, additive and water into a stirrer, stir at 500rpm-1000rpm for 15min-30min; then add porous substance-dye molecule-TiO2 photocatalytic composite material, stir at 1500rpm-3000rpm for 1h-2h, and obtain composite environmentally friendly coating for photocatalytic air purification.

[0029] Compared with the prior art, this application has at least the following beneficial effects:

[0030] The present application composites a porous material, a dye molecule and TiO2 into a photocatalytic composite material, so that in photocatalysis, the porous material has a high specific surface area, can provide a large number of adsorption sites, effectively adsorb organic pollutants, particulate matter, harmful gases, etc. in the air, and provide more sufficient substrates for subsequent photocatalytic reactions; the dye molecule has a strong ability to absorb visible light, can extend the light response range of TiO to the visible light region, reduce the light source requirements and enhance the light absorption efficiency, after the dye molecule absorbs light energy, it transfers the energy to TiO through an energy transfer mechanism, so that it produces more active oxygen species, so as to improve the photocatalytic efficiency, and the pore structure of the porous material can increase light scattering, further enhancing the photocatalytic effect; the dye molecule absorbs visible light to generate an excited state, and the excited dye molecule transfers electrons to the conduction band of titanium dioxide to become an oxidized state, thereby effectively separating photogenerated electron-hole pairs through the photosensitization of the dye molecule, and the pore structure of the porous material promotes the separation of photogenerated electrons and hole pairs, and the separated electrons and holes participate in the photocatalytic reaction, thereby enhancing the air purification effect and improving the purification efficiency. DETAILED DESCRIPTION

[0031] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0032] As used herein, the term "prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0033] When amount, concentration or other value or parameter is expressed as range, preferred range or a series of upper preferred value and lower preferred value limit range, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when disclosing range "1 to 5", described range should be interpreted as including range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the range is intended to include its end value and all integers and fractions within the range.

[0034] In addition, the indefinite articles "a" and "an" before the elements or components of the present invention have no restrictions on the quantity requirements (i.e. the number of occurrences) of the elements or components. Therefore, "a" or "an" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number is obviously intended to be in the singular form.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0036] Composite material preparation example 1

[0037] The preparation method of the activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material comprises the following steps:

[0038] The raw materials were weighed with a mass ratio of 10 nm titanium dioxide particles, copper phthalocyanine and activated carbon of 5:1:10;

[0039] Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 20 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7-9, and stirring for 4 hours to obtain a titanium dioxide dispersion;

[0040] Dissolve copper phthalocyanine in dimethyl sulfoxide, add it to the titanium dioxide dispersion, stir for 6 hours, filter and remove impurities to obtain copper phthalocyanine-TiO2 composite particles;

[0041] The activated carbon was evenly dispersed in ethanol, and then the dye molecule-TiO2 composite particles were added. After stirring at 500 rpm for 4 hours, methyl cellulose was added and stirring was continued for 60 minutes. The mixture was filtered, impurities were removed, and dried. After heat treatment at 300°C, it was cooled to room temperature to obtain an activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material.

[0042] Composite material preparation example 2

[0043] The method for preparing a porous silica-porphyrin copper-TiO2 photocatalytic composite material comprises the following steps:

[0044] The raw materials were weighed at a mass ratio of 25 nm titanium dioxide particles, porphyrin copper and porous silica of 5:1:10;

[0045] Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 40 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7-9, and stirring for 2 hours to obtain a titanium dioxide dispersion;

[0046] The copper porphyrin was dissolved in dimethyl sulfoxide, and then added to the titanium dioxide dispersion, stirred for 12 hours, filtered and impurities were removed to obtain the copper porphyrin-TiO2 composite particles;

[0047] The porous silica was evenly dispersed in ethanol, and then porphyrin copper-TiO2 composite particles were added. After stirring at 1000 rpm for 2 hours, methyl cellulose was added and stirring was continued for 30 minutes. The mixture was filtered, impurities were removed, and dried. After heat treatment at 500°C, it was cooled to room temperature to obtain a porous silica-porphyrin copper-TiO2 photocatalytic composite material.

[0048] Composite material preparation example 3

[0049] The preparation method of diatomite-rhodamine green-TiO2 photocatalytic composite material comprises the following steps:

[0050] The raw materials were weighed with a mass ratio of 35 nm titanium dioxide particles, rhodamine green and diatomaceous earth of 5:1:10;

[0051] Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 30 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7-9, and stirring for 3 hours to obtain a titanium dioxide dispersion;

[0052] The dye molecules are dissolved in dimethyl sulfoxide, and then added to the titanium dioxide dispersion, stirred for 8 hours, filtered and impurities removed to obtain dye molecule-TiO2 composite particles;

[0053] The porous material was evenly dispersed in ethanol, and then the dye molecule-TiO2 composite particles were added. After stirring at 700 rpm for 3.5 hours, methyl cellulose was added and stirring was continued for 35 minutes. The mixture was filtered, impurities were removed, and dried. After heat treatment at 400°C, it was cooled to room temperature to obtain a diatomaceous earth-rhodamine green-TiO2 photocatalytic composite material.

[0054] Composite material preparation example 4

[0055] The preparation method of bentonite-cobalt pyridine-TiO2 photocatalytic composite material comprises the following steps:

[0056] The raw materials were weighed with a mass ratio of 50 nm titanium dioxide particles, cobalt pyridine and bentonite of 5:1:10;

[0057] Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 35 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7-9, and stirring for 2.8 hours to obtain a titanium dioxide dispersion;

[0058] Dissolve cobalt pyridine in dimethyl sulfoxide, add it to the titanium dioxide dispersion, stir for 10 hours, filter and remove impurities to obtain dye molecule-TiO2 composite particles;

[0059] The porous material was evenly dispersed in ethanol, and then the dye molecule-TiO2 composite particles were added. After stirring at 900 rpm for 2.5 hours, methyl cellulose was added and stirring was continued for 45 minutes. The mixture was filtered, impurities were removed, and dried. After heat treatment at 400°C, it was cooled to room temperature to obtain a bentonite-cobalt pyridine-TiO2 photocatalytic composite material.

[0060] Example 1

[0061] The composite environmentally friendly paint for photocatalytic air purification includes the following raw material components by mass:

[0062] 30 parts of acrylic emulsion;

[0063] 5 parts of the activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material of Preparation Example 1;

[0064] 10 parts of calcium carbonate;

[0065] 1 part of fatty alcohol polyoxyethylene ether;

[0066] 10 parts water;

[0067] The preparation method of the composite environmentally friendly coating for photocatalytic air purification comprises the following steps:

[0068] The emulsion, inorganic filler, additive and water were added into a stirrer and stirred at 500 rpm for 30 min. Then, the activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material was added and stirred at 3000 rpm for 1 h to obtain a composite environmentally friendly coating for photocatalytic air purification.

[0069] Example 2

[0070] The composite environmentally friendly paint for photocatalytic air purification includes the following raw material components by mass:

[0071] Acrylic emulsion 60 parts;

[0072] 20 parts of porous silica-porphyrin copper-TiO2 photocatalytic composite material;

[0073] Calcium carbonate 30 parts;

[0074] 5 parts of fatty alcohol polyoxyethylene ether;

[0075] 40 parts water;

[0076] The preparation method of the composite environmentally friendly coating for photocatalytic air purification comprises the following steps:

[0077] The emulsion, inorganic filler, additive and water were added into a stirrer and stirred at 1000 rpm for 15 min. The porous silica-porphyrin copper-TiO2 photocatalytic composite material was then added and stirred at 1500 rpm for 2 h to obtain a composite environmentally friendly coating for photocatalytic air purification.

[0078] Example 3

[0079] The composite environmentally friendly paint for photocatalytic air purification includes the following raw material components by mass:

[0080] 40 parts of acrylic emulsion;

[0081] 10 parts of diatomite-rhodamine green-TiO2 photocatalytic composite material;

[0082] 15 parts of calcium carbonate;

[0083] 3 parts of fatty alcohol polyoxyethylene ether;

[0084] 20 parts water;

[0085] The preparation method of the composite environmentally friendly coating for photocatalytic air purification comprises the following steps:

[0086] The emulsion, inorganic filler, additive and water were added into the stirrer and stirred at 600 rpm for 25 min. Then, the diatomaceous earth-rhodamine green-TiO2 photocatalytic composite material was added and stirred at 2000 rpm for 1.5 h to obtain a composite environmentally friendly coating for photocatalytic air purification.

[0087] Example 4

[0088] The composite environmentally friendly paint for photocatalytic air purification includes the following raw material components by mass:

[0089] 40 parts of acrylic emulsion;

[0090] 15 parts of bentonite-cobalt pyridine-TiO2 photocatalytic composite material;

[0091] Calcium carbonate 25 parts;

[0092] 3 parts of fatty alcohol polyoxyethylene ether;

[0093] 30 parts water;

[0094] The preparation method of the composite environmentally friendly coating for photocatalytic air purification comprises the following steps:

[0095] The emulsion, inorganic filler, additive and water were added into a stirrer and stirred at 900 rpm for 25 min. Then, the bentonite-cobalt pyridine-TiO2 photocatalytic composite material was added and stirred at 2500 rpm for 1.5 h to obtain a composite environmentally friendly coating for photocatalytic air purification.

[0096] Comparative Example 1

[0097] Compared with Example 1, the titanium dioxide particles of Preparation Example 1 are used to replace the activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material, and the rest is the same as Example 1.

[0098] Comparative Example 2

[0099] Compared with Example 1, the copper phthalocyanine-TiO2 composite particles of Preparation Example 1 are used to replace the activated carbon-copper phthalocyanine-TiO2 photocatalytic composite material, and the rest is the same as Example 1.

[0100] Comparative Example 3

[0101] Compared with Example 1, activated carbon-TiO2 composite particles are used instead of activated carbon-copper phthalocyanine-TiO2 photocatalytic composite materials, and the rest is the same as Example 1. The preparation method of activated carbon-TiO2 composite particles includes: dispersing titanium dioxide particles in anhydrous ethanol, ultrasonically treating for 20 minutes until the titanium dioxide particles are uniformly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7-9, stirring for 4 hours, and obtaining a titanium dioxide dispersion; uniformly dispersing activated carbon in the titanium dioxide dispersion, stirring at 500 rpm for 4 hours, adding methyl cellulose and continuing to stir for 60 minutes, filtering, removing impurities, drying, and then heat-treating at 300°C and cooling to room temperature to obtain activated carbon-TiO2 composite particles.

[0102] In accordance with GBT 18204.26-2000 Requirements for the determination of organic gases in the air of public places, the photocatalytic purification efficiency of the coatings of Examples 1 to 4 and Comparative Examples 1 to 3 was tested for organic gas; in accordance with JC / T1074-2008 Purification Performance of Indoor Air Purification Functional Coating Materials, the formaldehyde purification efficiency of the above coatings was tested.

[0103]

[0104]

[0105] As can be seen from the above table, compared with Comparative Examples 1 to 3, the organic gas decomposition efficiency of the composite environmentally friendly coatings prepared in Examples 1 to 4 of the present application under 4h photocatalysis reaches more than 92.2%, and the formaldehyde purification efficiency is greater than 99%, which is significantly better than Comparative Examples 1 to 3. It can be seen that the present application uses a porous material-dye molecule-TiO2 photocatalytic composite material as a photocatalyst, which makes the coating have better purification effect and purification efficiency.

[0106] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0107] The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present application in detail. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the scope of protection of the present application. It is particularly pointed out that for those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. An inorganic composite environmentally friendly coating for photocatalytic air purification, characterized in that: The invention comprises the following raw material components by weight: 30 to 60 parts of emulsion; 5 to 20 parts of porous material-dye molecule-TiO2 photocatalytic composite material; 10 to 30 parts of inorganic filler; 1 to 5 parts of additives; 10 to 40 parts of water; The porous material-dye molecule-TiO2 photocatalytic composite material is a composite material formed by loading dye molecules onto the surface of titanium dioxide on the surface or in the pores of the porous material.

2. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 1, characterized in that: The method for preparing the porous material-dye molecule-TiO2 photocatalytic composite material comprises the following steps: Dispersing titanium dioxide particles in anhydrous ethanol, and ultrasonically treating for 20 minutes to 40 minutes until the titanium dioxide particles are evenly dispersed; then adding 3-aminopropyltriethoxysilane, adjusting the pH to 7 to 9, and stirring for 2 hours to 4 hours to obtain a titanium dioxide dispersion; The dye molecules are dissolved in dimethyl sulfoxide, and then added to the titanium dioxide dispersion, stirred for 6 to 12 hours, filtered and impurities removed to obtain dye molecule-TiO2 composite particles; The porous material is evenly dispersed in ethanol, and then the dye molecule-TiO2 composite particles are added. After stirring at 500rpm-1000rpm for 2h-4h, methyl cellulose is added and stirring is continued for 30min-60min. The porous material is filtered, impurities are removed, and dried. After heat treatment at 300℃-500℃, it is cooled to room temperature to obtain a porous material-dye molecule-TiO2 photocatalytic composite material.

3. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 2, characterized in that: The particle size of the titanium dioxide particles is 10nm to 50nm.

4. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 2, characterized in that: The mass ratio of the titanium dioxide particles, the dye molecules and the porous material is 5:1:

10.

5. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 1, characterized in that: The porous substance includes, but is not limited to, one or more of diatomaceous earth, activated carbon, zeolite, porous ceramics, montmorillonite, bentonite, porous silica and porous alumina.

6. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 1, characterized in that: The dye molecules include, but are not limited to, one or more of phthalocyanine dye molecules, porphyrin dye molecules, rhodamine dye molecules and pyridine dye molecules.

7. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 6, characterized in that: The phthalocyanine dye molecules include one or two of copper phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine; Or, the porphyrin dye molecules include one or more of hematoporphyrin, porphyrin iron, porphyrin copper, dihydrochlorin e6 and dihydrochlorin e4; Or, the rhodamine dye molecules include one or two of rhodamine B, rhodamine 6G, rhodamine X and rhodamine green; Alternatively, the pyridine dye molecules include one or both of zinc pyridine and cobalt pyridine.

8. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 1, characterized in that: The emulsion includes any one of acrylic emulsion, styrene acrylic emulsion, polyvinyl acetate emulsion and polyvinyl alcohol emulsion; The inorganic filler includes one or more of silicon dioxide, talc, mica, kaolin, calcium carbonate, barium sulfate, wollastonite, titanium dioxide, graphite and carbon black.

9. The inorganic composite environmentally friendly paint for photocatalytic air purification according to claim 1, characterized in that: The auxiliary agent includes one or more of a dispersant, a defoamer, a leveling agent, a thickener, a preservative, a wetting agent, an antistatic agent, a mildewproof agent, a crosslinking agent and a flame retardant.

10. A method for preparing an inorganic composite environmentally friendly coating for photocatalytic air purification according to any one of claims 1 to 9, characterized in that: The following steps are involved: Add emulsion, inorganic filler, additive and water into a stirrer, stir at 500rpm-1000rpm for 15min-30min; then add porous substance-dye molecule-TiO2 photocatalytic composite material, stir at 1500rpm-3000rpm for 1h-2h, and obtain composite environmentally friendly coating for photocatalytic air purification.

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