CN112812663A - Method for preparing flower-like zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint - Google Patents
Method for preparing flower-like zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint Download PDFInfo
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- CN112812663A CN112812663A CN202011630391.7A CN202011630391A CN112812663A CN 112812663 A CN112812663 A CN 112812663A CN 202011630391 A CN202011630391 A CN 202011630391A CN 112812663 A CN112812663 A CN 112812663A
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- zinc oxide
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- wall paint
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003973 paint Substances 0.000 title claims abstract description 53
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 17
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229940043825 zinc carbonate Drugs 0.000 claims description 2
- 229940098697 zinc laurate Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 2
- 238000005034 decoration Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention relates to a method for preparing flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint, which comprises the steps of preparing a precursor solution of zinc oxide-based composite photocatalytic particles, and sequentially and mechanically stirring and uniformly mixing the precursor solution and the components of the water-based interior wall paint to obtain a mixed coating; and (3) carrying out microwave reaction synthesis on the mixed coating to obtain the flower-shaped photocatalytic particle antibacterial water-based interior wall paint. The composite photocatalytic nano-particles are dispersed in the water-based interior wall paint in the form of precursor mixed liquid, so that the photocatalytic particles are better in stability and better in dispersibility and have more excellent antibacterial performance; the attached photocatalytic nanoparticles are uniformly dispersed and coated on the flower-shaped zinc oxide photocatalytic particles, so that the specific surface area is larger, more active sites are provided, and the antibacterial inactivation is better; the zinc oxide is commonly used for indoor decoration, is green and environment-friendly and has high safety. The flower-shaped photocatalytic particles have larger specific surface area, more quantity of photocatalytic nanoparticles can be supported and attached on the surface, and the degradability and the bactericidal property under visible light are higher.
Description
Technical Field
The invention belongs to the technical field of photocatalytic environment-friendly coatings, and particularly relates to a method for preparing a flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint.
Background
As interior wall decoration materials widely used in aqueous interior wall paints are in contact with human bodies for a long time in living and working, the contents of VOC, APEO and PFOS harmful substances and the contents of free formaldehyde, lead, chromium and other heavy metal ions in the aqueous interior wall paints have attracted much attention to the safety of long-term use thereof. Meanwhile, as the requirement of people on the indoor air quality is higher and higher, especially the continuous influence of air-borne diseases of various closed spaces, the people are forced to put forward higher requirements on the indoor antibacterial decorative material. The existing photocatalytic interior wall paint is basically prepared by simply mechanically stirring ready-made photocatalytic particles, resin emulsion and other additives, and the uniform dispersibility and agglomeration of the photocatalytic particles cannot be guaranteed. In addition, the addition of the single structure or single kind of photocatalytic particles can also cause the poor photocatalytic antibacterial effect of the water-based interior wall paint.
Disclosure of Invention
In conclusion, the invention aims to provide a method for preparing a flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint, so as to solve the problem that the prepared photocatalytic water-based interior wall paint is poor in antibacterial effect because photocatalytic particles with a single structure or a single kind are added in the water-based interior wall paint and are easy to agglomerate and have uneven dispersibility.
In order to achieve the purpose, the invention provides the following technical scheme:
the method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a zinc oxide-based composite photocatalytic particle precursor solution, specifically comprising
Step 1.1, weighing a zinc oxide zinc source, dissolving the zinc oxide zinc source in ultrapure water, adding an ammonia water solution to control a zinc-ammonia complex compound to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain a zinc-ammonia complex compound precipitate;
step 1.2, adding a solution with 6mg/mL of attached photocatalytic nanoparticles into the zinc-ammonia complex precipitate prepared in the step 1.1, configuring the solution into a precursor solution with 4.0-5.0mol/L by ammonia water and ultrapure water, and carrying out ultrasonic oscillation for 30min to fully disperse the precursor solution to obtain a precursor solution of the zinc oxide-based composite photocatalytic particles;
step 2, sequentially mechanically stirring and uniformly mixing the composite precursor solution obtained in the step 1 and the components of the water-based interior wall paint in a reaction kettle to obtain a mixed coating;
and 3, synthesizing the mixed coating through microwave reaction to obtain the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint.
Further, the zinc oxide-based composite photocatalytic particles comprise zinc oxide photocatalytic particles and attached photocatalytic nanoparticles.
Further, the zinc oxide source in step 1.2 is one or more of zinc stearate, zinc nitrate hexahydrate, zinc laurate, zinc acetate, zinc carbonate and zinc sulfate.
Further, the attached photocatalytic nanoparticles in step 1.2 are one or more of silver nanowires, graphene oxide, reduced graphene oxide, or graphene quantum dots.
Further, in the step 2, the zinc oxide-based composite photocatalytic particles and the water-based interior wall paint comprise, by mass, 13-15 wt% of the zinc oxide-based composite photocatalytic particles, 47-65 wt% of single-component water-based resin, 14-20 wt% of pigment and filler, 2-3 wt% of a dispersant, 2-3 wt% of a defoaming agent, 1-2 wt% of a thickening agent and 17-20 wt% of water.
Further, the method for mixing the composite precursor solution and the components of the water-based interior wall paint in the step 2 is that the single-component water-based resin is added into the composite precursor solution and fully stirred for 30min at the stirring speed of 850r/min, and then the mixture of the pigment, the dispersant, the defoamer and the thickener is added and fully stirred for 1h at the stirring speed of 1600 + 1900 r/min.
Further, in the step 3, the heating temperature of the microwave reaction is 70-100 ℃, and the reaction time is 1-4 min.
Further, the single-component water-based resin is one or more of water-based alkyd resin, water-based acrylic resin and water-based polyurethane resin.
Furthermore, the pigment and filler is one or more of calcium carbonate, calcined kaolin and titanium dioxide.
The flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint synthesized by microwave is observed under a scanning electron microscope, and the diameter of the obtained flower-shaped zinc oxide-based composite photocatalytic particles is concentrated between 2 and 4 mu m.
The invention has the beneficial effects that:
1. according to the invention, the zinc oxide-based composite photocatalytic nanoparticles are dispersed in the water-based interior wall paint in the form of precursor mixed liquid, so that the photocatalytic particles have better stability, and the zinc oxide-based composite photocatalytic particles have better dispersibility in the water-based interior wall paint and are not easy to agglomerate, so that the water-based interior wall paint prepared finally has more excellent photocatalytic antibacterial performance;
2. the flower-shaped zinc-based composite photocatalytic particles are synthesized in the water-based interior wall paint through a microwave rapid reaction, compared with the traditional photocatalytic particles, the attached photocatalytic nanoparticles are uniformly dispersed and coated on the flower-shaped zinc oxide photocatalytic particles, the specific surface area of the synthesized flower-shaped zinc oxide-based composite photocatalytic particles is larger, more active site numbers are provided, the antibacterial and bactericidal effects of the prepared composite water-based interior wall paint can be effectively improved, and finally, the photocatalytic antibacterial inactivation of escherichia coli and staphylococcus aureus in the composite water-based interior wall paint under the condition of visible light can be realized in a short time;
3. according to the invention, by adopting different adding sequences and adding processes of the zinc oxide-based composite photocatalytic particle precursor mixed liquid and various water-based interior wall paint raw materials, on one hand, the resin in the water-based interior wall paint has the advantages of good mechanical property, machining property, good film forming property, strong adhesive force, high drying speed and the like, and the defects of insufficient mechanical property of direct mixing of the photocatalytic particles and the water-based interior wall paint raw materials are solved. On the other hand, the flower-shaped zinc oxide-based composite photocatalytic particles are more tightly combined with the water-based interior wall paint, the photocatalytic particles are not easy to fall off and agglomerate in the construction and long-term use processes, and the problems that the photocatalytic particles with single structures or single components are not tightly combined with the water-based interior wall paint, and the photocatalytic particles are easy to fall off or agglomerate are solved;
4. zinc oxide is commonly used for producing astringent, nutritional supplement, feed additive, baby talcum powder and other products, is a nontoxic inorganic substance, and does not produce rejection reaction on human bodies, so that zinc oxide is used as an antibacterial functional additive of water-based interior wall paint for indoor decoration, is green and environment-friendly and has high safety.
5. Compared with other shapes of zinc oxide composite photocatalytic particles, such as particles, rods and the like, the flower-shaped zinc oxide composite photocatalytic particles have larger specific surface area, more photocatalytic nanoparticles can be supported and attached on the surface, and the supported space direction and active sites are richer, so that the degradability and the bactericidal property of the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint under visible light are higher under the same photocatalytic particle loading.
Drawings
FIG. 1 is a 3900-time microscopic structure diagram of the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint prepared in example 3 of the invention.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will become apparent to those skilled in the art after reading the present application and which fall within the limits of the appended claims.
Example 1
The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a zinc oxide-based composite photocatalytic particle precursor solution: weighing zinc oxide zinc source zinc stearate, dissolving the zinc oxide zinc source zinc stearate in ultrapure water, adding an ammonia water solution to control a zinc-ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying box to obtain the zinc-ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nanoparticle graphene and reduced graphene oxide into the prepared zinc-ammonia complex precipitate, configuring the solution into a precursor solution of 4mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed zinc oxide-based composite photocatalytic particle precursor solution. And 2, selecting 30 wt% of the composite precursor solution prepared in the step 1 and 51 wt% of waterborne polyurethane resin, fully stirring for 30min in a reaction kettle at a stirring speed of 750r/min, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h in the reaction kettle at a stirring speed of 1700r/min, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 1min at 70 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint reaches 92% of 10mg/L rhodamine B solution degraded in 50min under the condition of visible light, 100% of escherichia coli and staphylococcus aureus are killed in 1 hour under the condition of visible light, the VOC content is 0, the alkali resistance is not abnormal (24 hours), and the drying time is 30min (surface drying).
Example 2
The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a zinc oxide-based composite photocatalytic particle precursor solution: weighing zinc oxide zinc source zinc stearate, dissolving the zinc oxide zinc source zinc stearate in ultrapure water, adding an ammonia water solution to control a zinc-ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying box to obtain the zinc-ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nano-particle graphene and reduced graphene oxide into the prepared zinc-ammonia complex precipitate, configuring the solution into a precursor solution of 4.5mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed zinc oxide-based composite photocatalytic particle precursor solution. And 2, selecting 31 wt% of the composite precursor solution prepared in the step 1 and 50 wt% of waterborne polyurethane resin, fully stirring for 30min at a stirring speed of 800r/min in a reaction kettle, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h at a stirring speed of 1800r/min in the reaction kettle, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 2.5min at 85 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint reaches 94% of 10mg/L rhodamine B solution degraded within 40min under the condition of visible light, 100% of escherichia coli and staphylococcus aureus are killed within 50min under the condition of visible light, the VOC content is 0, the alkali resistance is not abnormal (24h), and the drying time is 30min (surface drying).
Example 3
The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint comprises the following steps:
step 1, preparing a zinc oxide-based composite photocatalytic particle precursor solution: weighing zinc oxide zinc source zinc stearate, dissolving the zinc oxide zinc source zinc stearate in ultrapure water, adding an ammonia water solution to control a zinc-ammonia complex to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying box to obtain the zinc-ammonia complex precipitate. And then adding a solution of 6mg/mL attached photocatalytic nano-particle graphene and reduced graphene oxide into the prepared zinc-ammonia complex precipitate, configuring the solution into a precursor solution of 5mol/L by ammonia water and ultrapure water, and performing ultrasonic oscillation for 30min to obtain the uniformly dispersed zinc oxide-based composite photocatalytic particle precursor solution. And 2, selecting 34 wt% of the composite precursor solution prepared in the step 1 and 47 wt% of waterborne polyurethane resin, fully stirring for 30min in a reaction kettle at a stirring speed of 850r/min, then adding a mixture of 14 wt% of pigment and filler, 2 wt% of dispersing agent, 2 wt% of defoaming agent and 1 wt% of thickening agent, and fully stirring for 1h in the reaction kettle at a stirring speed of 1900r/min, wherein the pigment and filler comprises 33 wt% of calcium carbonate, 11 wt% of calcined kaolin and 56 wt% of titanium dioxide. And 3, putting the mixed coating prepared in the step 2 into a microwave rapid reaction synthesizer to react for 4min at 100 ℃. The photocatalytic degradation performance of the finally prepared flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint reaches 98% of 10mg/L rhodamine B solution degraded within 30min under the visible light condition, 100% of escherichia coli and staphylococcus aureus are killed within 37min under the visible light condition, the VOC content is 0, the alkali resistance is not abnormal (24h), and the drying time is 30min (surface drying).
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint is characterized by comprising the following steps of:
step 1, preparing a zinc oxide-based composite photocatalytic particle precursor solution, specifically comprising
Step 1.1, weighing a zinc oxide zinc source, dissolving the zinc oxide zinc source in ultrapure water, adding an ammonia water solution to control a zinc-ammonia complex compound to separate out a precipitate, then performing suction filtration to separate the precipitate, fully cleaning the precipitate by using ultrapure water and absolute ethyl alcohol, and drying in a constant-temperature drying oven to obtain a zinc-ammonia complex compound precipitate;
step 1.2, adding a solution with 6mg/mL of attached photocatalytic nanoparticles into the zinc-ammonia complex precipitate prepared in the step 1.1, configuring the solution into a precursor solution with 4.0-5.0mol/L by ammonia water and ultrapure water, and carrying out ultrasonic oscillation for 30min to fully disperse the precursor solution to obtain a precursor solution of the zinc oxide-based composite photocatalytic particles;
step 2, sequentially mechanically stirring and uniformly mixing the composite precursor solution obtained in the step 1 and the components of the water-based interior wall paint in a reaction kettle to obtain a mixed coating;
and 3, synthesizing the mixed coating through microwave reaction to obtain the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint.
2. The method for preparing a flower-like zinc oxide-based composite photocatalytic antibacterial aqueous interior wall paint according to claim 1, wherein the zinc oxide-based composite photocatalytic particles comprise zinc oxide photocatalytic particles and attached photocatalytic nanoparticles.
3. The method for preparing the flower-like zinc oxide-based composite photocatalytic antibacterial aqueous interior wall paint according to claim 1, wherein the zinc oxide source of step 1.2 is one or more of zinc stearate, zinc nitrate hexahydrate, zinc laurate, zinc acetate, zinc carbonate and zinc sulfate.
4. The method for preparing the flower-like zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint according to claim 1, wherein the attached photocatalytic nanoparticles in the step 1.2 are one or more of nano silver wires, graphene oxide, reduced graphene oxide or graphene quantum dots.
5. The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 1, wherein the zinc oxide-based composite photocatalytic particles and the water-based interior wall paint in step 2 comprise, by mass, 13-15 wt% of the zinc oxide-based composite photocatalytic particles, 47-65 wt% of a single-component water-based resin, 14-20 wt% of a pigment and filler, 2-3 wt% of a dispersant, 2-3 wt% of an antifoaming agent, 1-2 wt% of a thickener and 17-20 wt% of water.
6. The method for preparing the flower-like zinc oxide-based composite photocatalytic antibacterial aqueous interior wall paint as claimed in claim 1, wherein the method for mixing the composite precursor solution and the components of the aqueous interior wall paint in the step 2 is to add single-component aqueous resin into the composite precursor solution, fully stir for 30min at the stirring speed of 550-1900 r/min, then add the mixture of pigment, filler, dispersant, defoamer and thickener, fully stir for 1h at the stirring speed of 1600-1900 r/min.
7. The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint as claimed in claim 1, wherein the heating temperature of the microwave reaction in the step 3 is 70-100 ℃, and the reaction time is 1-4 min.
8. The method for preparing the flower-like zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint according to claim 5, wherein the single-component water-based resin is one or more of water-based alkyd resin, water-based acrylic resin and water-based polyurethane resin.
9. The method for preparing the flower-shaped zinc oxide-based composite photocatalytic antibacterial water-based interior wall paint according to claim 5, wherein the pigment and filler is one or more of calcium carbonate, calcined kaolin and titanium dioxide.
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| US20080171804A1 (en) * | 2006-08-24 | 2008-07-17 | Venkataram Krishnan | Anionic latex as a carrier for bioactive ingredients and methods for making and using the same |
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| US20080171804A1 (en) * | 2006-08-24 | 2008-07-17 | Venkataram Krishnan | Anionic latex as a carrier for bioactive ingredients and methods for making and using the same |
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