CN113529493A - Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof - Google Patents
Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof Download PDFInfo
- Publication number
- CN113529493A CN113529493A CN202110808388.8A CN202110808388A CN113529493A CN 113529493 A CN113529493 A CN 113529493A CN 202110808388 A CN202110808388 A CN 202110808388A CN 113529493 A CN113529493 A CN 113529493A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- wallpaper
- rgo
- reaction
- photocatalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/64—Inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The invention discloses a wallpaper for photocatalytic synergistic decomposition of formaldehyde and a preparation method thereof, wherein the wallpaper comprises amino modified diatomite and supported MnO2G to C of3N4-rGO catalyst and 3 steps for preparing the wallpaper for photocatalytic synergistic decomposition of formaldehyde, the supported MnO provided by the invention2G to C of3N4-rGO catalysisIn the agent, rGO can capture g-C3N4The electrons effectively separate photoproduction electron-hole pairs, thereby promoting the decomposition of formaldehyde and improving the decomposition performance of the formaldehyde, and the formaldehyde and MnO are generated at weak illumination and at night2The hydroxyl on the surface forms a hydrogen bond and is adsorbed in MnO2Surface of (1), then MnO2The active oxygen on the surface oxidizes the formaldehyde into formate, carbonate and CO in turn2MnO after consuming surface active oxygen for Formaldehyde Oxidation2Will form oxygen vacancies, then MnO2Can adsorb oxygen molecules in air and decompose into new active oxygen, and can also react with g-C under strong illumination3N4rGO forms a concerted catalysis, further improving catalytic performance.
Description
Technical Field
The invention relates to the technical field of wallpaper preparation, in particular to a wallpaper for photocatalytic synergistic decomposition of formaldehyde and a preparation method thereof.
Background
The wallpaper is a material for decorating indoor wall surfaces, is favored with unique style and decorative and beautification effect, becomes an important indoor wall surface decoration material like paint so far, the domestic wallpaper market is continuously expanded, has the development trend of replacing paint, and 90 percent of indoor decoration adopts the wallpaper at home and abroad, so the market at home and abroad is huge.
Along with the continuous improvement of living standard of people, the indoor living environment and quality are concerned more and more, formaldehyde is used as the most common harmful substance in the indoor environment, is usually released by home decoration materials, the release period can even reach more than 10 years, and because the indoor environment is usually closed, the environment with higher formaldehyde concentration is easier to form, so that the body is damaged.
The currently common formaldehyde removing method in the market is an active carbon formaldehyde absorption method, the active carbon has a microporous structure calculated by microns, has an adsorption capacity on formaldehyde, and has an effect of eliminating formaldehyde before the active carbon is saturated by absorption, but the active carbon does not have a function of decomposing formaldehyde, and the formaldehyde still can be released again along with the change of the environment, so that the active carbon formaldehyde absorption method is an unstable and incomplete method, and the active carbon is placed indoors in any way, really attractive, and is not favored by general people.
Patent document CN106320094B discloses PVC wallpaper capable of degrading formaldehyde through visible light catalysisThe method uses urea as a nitrogen source, uses tetrabutyl titanate as a titanium source, and adopts a sol-gel method to prepare nitrogen-doped titanium dioxide (N-TiO)2) The photocatalyst takes PVC wallpaper as a carrier, and photocatalyst N-TiO is attached to the surface of the wallpaper2The photocatalytic PVC wallpaper prepared by the invention can decompose formaldehyde gas under visible light, has high photocatalytic activity, but the indoor illumination condition is often insufficient, and the photocatalytic PVC wallpaper is an environment completely without illumination at night, which greatly influences the formaldehyde decomposition efficiency of a photocatalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the wallpaper for decomposing formaldehyde through photocatalysis and cooperation and the preparation method thereof, and solves the technical problem that the existing photocatalyst wallpaper is low in formaldehyde decomposition efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the wallpaper for decomposing formaldehyde through photocatalysis and synergism comprises the following preparation raw materials in parts by weight: 15-20 parts of amino modified diatomite and supported MnO2G to C of3N43-4 parts of rGO catalyst, 20-30 parts of adhesive, 0.4-0.5 part of sodium polyacrylate, 0.02-0.03 part of defoaming agent, 0.05-0.06 part of carboxymethyl cellulose, 0.6-0.8 part of seaweed gel, 0.04-0.05 part of dioctyl phthalate, 0.2-0.5 part of nano zinc oxide, 0.3-0.4 part of copper oxide and 40-50 parts of deionized water, wherein the defoaming agent is SN-154 or 1410, and the adhesive is VAE adhesive, 2011-adhesive or PVA adhesive.
Preferably, the preparation method of the amino modified diatomite comprises the following steps:
(1) calcining and cooling diatom ooze, then carrying out ultrasonic treatment by using sulfuric acid, and obtaining porous diatomite through standing, precipitating, filtering, washing and vacuum drying;
(2) adding porous diatomite and hexamethylene diisocyanate into an anhydrous toluene solvent, performing ultrasonic dispersion uniformly, performing heating and stirring reaction under the nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
(3) adding isocyanated diatomite into deionized water, carrying out hydrolysis reaction, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain the amino modified diatomite.
Preferably, in the step (1), the calcining temperature is 500-.
Preferably, in the step (2), the mass ratio of the porous diatomite to the hexamethylene diisocyanate is 100:80-120, the heating and stirring reaction temperature is 80-100 ℃, and the reaction time is 5-8 h.
Preferably, in the step (3), the mass ratio of the isocyanated diatomite to the deionized water is 1:1.09, the hydrolysis reaction temperature is 80-100 ℃, and the reaction time is 36-72 hours.
Preferably, the load MnO2G to C of3N4-a process for the preparation of rGO catalyst, comprising in particular the steps of: mixing potassium permanganate with g-C3N4Dispersing the-rGO in deionized water, adding D (+) -glucose, stirring uniformly, standing for 30-40min, and drying at the temperature of 100 ℃ and 110 ℃ for 24-30h to obtain the supported MnO2G to C of3N4-rGO catalyst.
Preferably, the potassium permanganate, g-C3N4The mass ratio of the-rGO, the deionized water and the D (+) -glucose is 10:180-200:500-600: 2-3.
Preferably, said g-C3N4-a process for the preparation of rGO comprising the steps of: calcining and cooling melamine in the air atmosphere to obtain layered porous g-C3N4Then the layered porous g-C is put3N4Adding GO and the water solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 20-30min, then carrying out hydrothermal reaction, and after the reaction is finished, naturally cooling, filtering, washing and vacuum drying the reaction product to obtain g-C3N4-rGO。
Preferably, the layered porous g-C3N4The mass ratio of GO to the absolute ethyl alcohol is 100:10-15:400-600, the temperature of the hydrothermal reaction is 180-190 ℃, and the reaction time is 2-3 h.
The invention also provides a preparation method of the wallpaper for photocatalytic synergistic decomposition of formaldehyde, which comprises the following steps: sequentially adding amino modified diatomite and supported MnO into deionized water2G to C of3N4The preparation method comprises the following steps of (1) stirring a rGO catalyst, sodium polyacrylate, a defoaming agent, carboxymethyl cellulose, seaweed gel, an adhesive, dioctyl phthalate, nano zinc oxide and copper oxide for 60-90min to obtain a coating, and then carrying out a coating process on the coating to obtain the wallpaper capable of decomposing formaldehyde in a photocatalytic and synergistic manner.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a wallpaper for photocatalytic synergistic decomposition of formaldehyde and a preparation method thereof3N4Further thermally decomposing to obtain layered porous g-C3N4Then compounding the graphene oxide with graphene to obtain g-C3N4-rGO, then at g-C3N4On the outer surface of the-rGO, MnO-loaded MnO was synthesized by a rapid redox reaction between potassium permanganate and D (+) -glucose2G to C of3N4-rGO followed by mixing the modified diatomaceous earth with the supported MnO2G to C of3N4Grinding and blending rGO, adding a dispersing agent, a water-retaining agent, a defoaming agent, an adhesive and a plasticizer to prepare a coating, and finally preparing the wallpaper capable of decomposing formaldehyde in a photocatalytic and synergetic manner by a coating process.
(2) The invention provides a wallpaper for photocatalytic synergistic decomposition of formaldehyde and a preparation method thereof, and provides MnO-loaded wallpaper2G to C of3N4In the rGO catalyst, the rGO can capture g-C3N4The electrons effectively separate photoproduction electron-hole pairs, thereby promoting the decomposition of formaldehyde and improving the decomposition performance of the formaldehyde, and the formaldehyde and MnO are generated at weak illumination and at night2The surface hydroxyl groups form hydrogen bondsAdsorbed in MnO2Surface of (1), then MnO2The active oxygen on the surface oxidizes the formaldehyde into formate, carbonate and CO in turn2MnO after consuming surface active oxygen for Formaldehyde Oxidation2Will form oxygen vacancies, then MnO2Can adsorb oxygen molecules in air and decompose into new active oxygen, and can also react with g-C under strong illumination3N4rGO forms a concerted catalysis, further improving catalytic performance.
(3) The invention provides a wallpaper for photocatalytic synergistic decomposition of formaldehyde and a preparation method thereof, wherein diatomite is subjected to acid treatment, the surface of the diatomite contains a large number of silicon hydroxyl groups, the diatomite can react with diisocyanate, and isocyanate groups are hydrolyzed to obtain amino groups, so that the amino groups are introduced into the diatomite, and the amino groups have a pair of lone pair electrons, so that the amino groups have extremely strong chemical adsorption performance on carbonyl carbon lacking electrons in formaldehyde, and under the synergistic action of physical adsorption and chemical adsorption, the wallpaper is endowed with excellent formaldehyde adsorption performance, the formaldehyde absorption rate of the wallpaper can be greater than the indoor formaldehyde release rate, so that the indoor formaldehyde concentration is always kept below a safety value, meanwhile, the modified diatomite has excellent adsorption degradation performance and humidity regulation performance, the household environment can be continuously improved in use, and the life quality is improved.
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are commercially available.
Example 1
A preparation method of a wallpaper for photocatalytic synergistic decomposition of formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 500 ℃ for 1h, cooling, performing ultrasonic treatment for 20min by using 20 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 80g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 6 hours at 80 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 100g of deionized water, carrying out hydrolysis reaction at 80 ℃ for 36h, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparation of Supported MnO2G to C of3N4-rGO catalyst:
50g of melamine is placed in a crucible, the temperature is raised to 480 ℃ at the heating rate of 1 ℃/min in the air atmosphere, then the mixture is calcined for 9h, and the layered porous g-C is obtained after cooling3N4；
50g of layered porous g-C3N4Adding 5g of GO into 200g of absolute ethyl alcohol, carrying out ultrasonic treatment for 20min to obtain a dispersion liquid, then adding the dispersion liquid into a polytetrafluoroethylene lining, carrying out reaction in a hydrothermal reaction kettle at 180 ℃ for 2h, and after the reaction is finished, naturally cooling, filtering, washing and vacuum drying a reaction product to obtain g-C3N4-rGO；
2g of potassium permanganate and 36g g-C3N4-rGO is dispersed in 100g deionized water, then 0.5g D (+) -glucose is added, the mixture is stirred evenly and then stands for 30min, and the mixture is dried for 24h at 100 ℃ to obtain the supported MnO2G to C of3N4-rGO catalyst;
(3) preparing the wallpaper for photocatalytic synergistic decomposition of formaldehyde:
150g of amino-modified diatomaceous earth and 30g of supported MnO2G to C of3N4Mixing and grinding the rGO catalyst in an agate bowl to obtain a mixture, then adding the obtained mixture, 4g of sodium polyacrylate, 0.2g of defoaming agent SN-154, 0.5g of water retention agent carboxymethyl cellulose, 6g of seaweed gel, 250g of VAE adhesive, 0.4g of plasticizer dioctyl phthalate, 2g of nano zinc oxide and 3g of copper oxide into 400mL of deionized water in sequence, stirring for 60min,and (3) obtaining a coating, adding the coating into a coating groove of a coating machine, performing a coating process on A4 paper, setting the parameters of the coating machine to be 50N of roller pressure, 28N of scraper pressure, 18 degrees of scraper angle and 8m/min of coating speed, and performing infrared heating for 30s after coating to obtain the wallpaper capable of decomposing formaldehyde in a photocatalytic and synergetic manner.
Example 2
A preparation method of a wallpaper for photocatalytic synergistic decomposition of formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 550 ℃ for 1.5h, cooling, performing ultrasonic treatment for 30min by using 25 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 90g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 6 hours at 85 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 100g of deionized water, carrying out hydrolysis reaction at 85 ℃ for 36h, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparation of Supported MnO2G to C of3N4-rGO catalyst:
50g of melamine is placed in a crucible, the temperature is raised to 480 ℃ at the heating rate of 1 ℃/min in the air atmosphere, then the mixture is calcined for 9h, and the layered porous g-C is obtained after cooling3N4；
50g of layered porous g-C3N4Adding 6g of GO into 200g of absolute ethyl alcohol, carrying out ultrasonic treatment for 20min to obtain dispersion liquid, then adding the dispersion liquid into a polytetrafluoroethylene lining, carrying out reaction in a hydrothermal reaction kettle at 185 ℃ for 2h, and after the reaction is finished, naturally cooling, filtering, washing and vacuum drying a reaction product to obtain g-C3N4-rGO；
2g of potassium permanganate and38g g-C3N4-rGO is dispersed in 100g of deionized water, then 0.4g of D (+) -glucose is added, the mixture is stirred uniformly and then stands for 35min, and the mixture is dried for 26h at 100 ℃ to obtain the supported MnO2G to C of3N4-rGO catalyst;
(3) preparing the wallpaper for photocatalytic synergistic decomposition of formaldehyde:
150g of amino-modified diatomaceous earth and 32g of supported MnO2G to C of3N4Mixing and grinding a rGO catalyst in an agate bowl to obtain a mixture, then sequentially adding the obtained mixture, 4.2g of sodium polyacrylate, 0.2g of defoaming agent SN-154, 0.5g of water retention agent carboxymethyl cellulose, 6.2g of seaweed gel, 250g of VAE adhesive, 0.42g of plasticizer dioctyl phthalate, 2.5g of nano zinc oxide and 3.2g of copper oxide into 420mL of deionized water, stirring for 60min to obtain a coating, adding the coating into a coating tank of a coating machine, and performing a coating process on A4 paper, wherein the parameters of the coating machine are set as roller pressure 50N, scraper pressure 28N, scraper angle 18 degrees, coating speed 8m/min, and infrared heating for 30s after coating to obtain the wallpaper for photocatalytic synergistic decomposition of formaldehyde.
Example 3
A preparation method of a wallpaper for photocatalytic synergistic decomposition of formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 580 ℃ for 1.5h, cooling, performing ultrasonic treatment for 30min by using 26 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 95g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 6 hours at 90 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 105g of deionized water, carrying out hydrolysis reaction for 42h at 90 ℃, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparation of Supported MnO2G to C of3N4-rGO catalyst:
50g of melamine is placed in a crucible, the temperature is raised to 480 ℃ at the heating rate of 1 ℃/min in the air atmosphere, then the mixture is calcined for 9h, and the layered porous g-C is obtained after cooling3N4；
50g of layered porous g-C3N4And 6.5g of GO is added into 200g of absolute ethyl alcohol, ultrasonic treatment is carried out for 20min to obtain dispersion liquid, then the dispersion liquid is added into a polytetrafluoroethylene lining, the reaction is carried out in a hydrothermal reaction kettle at 190 ℃ for 2h, after the reaction is finished, the reaction product is naturally cooled, filtered, washed and dried in vacuum to obtain g-C3N4-rGO；
2g of potassium permanganate and 39g g-C3N4-rGO is dispersed in 100g deionized water, then 0.5g D (+) -glucose is added, the mixture is stirred evenly and then stands for 40min, and the mixture is dried for 26h at 100 ℃, thus obtaining the supported MnO2G to C of3N4-rGO catalyst;
(3) preparing the wallpaper for photocatalytic synergistic decomposition of formaldehyde:
150g of amino-modified diatomaceous earth and 34g of supported MnO2G to C of3N4Mixing and grinding a rGO catalyst in an agate bowl to obtain a mixture, then sequentially adding the obtained mixture, 4.5g of sodium polyacrylate, 0.25g of defoaming agent SN-154, 0.5g of water retention agent carboxymethyl cellulose, 6.2g of seaweed gel, 250g of VAE adhesive, 0.45g of plasticizer dioctyl phthalate, 3g of nano zinc oxide and 3.4g of copper oxide into 420mL of deionized water, stirring for 60min to obtain a coating, adding the coating into a coating tank of a coating machine, and performing a coating process on A4 paper, wherein the parameters of the coating machine are set as roller pressure 50N, scraper pressure 28N, scraper angle 18 degrees, coating speed 8m/min, and infrared heating for 30s after coating to obtain the wallpaper for photocatalytic synergistic decomposition of formaldehyde.
Example 4
A preparation method of a wallpaper for photocatalytic synergistic decomposition of formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 600 ℃ for 2h, cooling, performing ultrasonic treatment for 40min by using 30 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 120g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 8 hours at 100 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 108g of deionized water, carrying out hydrolysis reaction at 95 ℃ for 48h, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparation of Supported MnO2G to C of3N4-rGO catalyst:
50g of melamine is placed in a crucible, the temperature is raised to 480 ℃ at the heating rate of 1 ℃/min in the air atmosphere, then the mixture is calcined for 9h, and the layered porous g-C is obtained after cooling3N4；
50g of layered porous g-C3N4Adding 7g of GO into 250g of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min to obtain dispersion liquid, then adding the dispersion liquid into a polytetrafluoroethylene lining, carrying out reaction in a hydrothermal reaction kettle at 190 ℃ for 2.5h, and after the reaction is finished, naturally cooling, filtering, washing and vacuum drying a reaction product to obtain g-C3N4-rGO；
2g of potassium permanganate and 40g g-C3N4-rGO is dispersed in 100g deionized water, then 0.5g D (+) -glucose is added, the mixture is stirred evenly and then stands for 40min, and the mixture is dried for 26h at 100 ℃, thus obtaining the supported MnO2G to C of3N4-rGO catalyst;
(3) preparing the wallpaper for photocatalytic synergistic decomposition of formaldehyde:
150g of amino-modified diatomaceous earth and 36g of supported MnO2G to C of3N4Mixing and grinding the-rGO catalyst in an agate bowl to obtain a mixture, and then sequentially mixing and grindingAdding the obtained mixture, 5g of sodium polyacrylate, 0.3g of defoaming agent SN-154, 0.6g of water retention agent carboxymethyl cellulose, 6.5g of seaweed gel, 250g of VAE adhesive, 0.5g of plasticizer dioctyl phthalate, 3g of nano zinc oxide and 4g of copper oxide into 500mL of deionized water, stirring for 60min to obtain a coating, adding the coating into a coating tank of a coating machine, and performing a coating process on A4 paper, wherein the parameters of the coating machine are set as roller pressure 50N, scraper pressure 28N, scraper angle 18 degrees, coating speed 8m/min, and infrared heating for 30s after coating to obtain the wallpaper capable of decomposing formaldehyde in a photocatalytic cooperation manner.
Comparative example 1
A preparation method of the wallpaper for removing formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 580 ℃ for 1.5h, cooling, performing ultrasonic treatment for 30min by using 26 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 95g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 6 hours at 90 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 105g of deionized water, carrying out hydrolysis reaction for 42h at 90 ℃, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparing the wallpaper for removing formaldehyde: adding 150g of amino modified diatomite, 4.5g of sodium polyacrylate, 0.25g of defoaming agent SN-154, 0.5g of water retention agent carboxymethyl cellulose, 6.2g of seaweed gel, 250g of VAE adhesive, 0.45g of plasticizer dioctyl phthalate, 3g of nano zinc oxide and 3.4g of copper oxide into 420mL of deionized water in sequence, stirring for 60min to obtain a coating, adding the coating into a coating tank of a coating machine, performing a coating process on A4 paper, setting the parameters of the coating machine to be 50N of roller pressure, 28N of scraper pressure, 18 degrees of scraper angle, 8m/min of coating speed, and performing infrared heating for 30s after coating to obtain the formaldehyde-removed wallpaper.
Comparative example 2
A preparation method of wallpaper for photocatalytic decomposition of formaldehyde comprises the following steps:
(1) preparing amino modified diatomite:
calcining the diatom ooze in a muffle furnace at 580 ℃ for 1.5h, cooling, performing ultrasonic treatment for 30min by using 26 wt% sulfuric acid, standing for precipitation, filtering, washing, and performing vacuum drying to obtain porous diatomite;
adding 100g of porous diatomite and 95g of hexamethylene diisocyanate into 500mL of anhydrous toluene solvent, ultrasonically dispersing uniformly, stirring for 6 hours at 90 ℃ in an oil bath kettle in a nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
adding 100g of isocyanated diatomite into 105g of deionized water, carrying out hydrolysis reaction for 42h at 90 ℃, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain amino modified diatomite;
(2) preparation of g-C3N4-rGO catalyst
50g of melamine is placed in a crucible, the temperature is raised to 480 ℃ at the heating rate of 1 ℃/min in the air atmosphere, then the mixture is calcined for 9h, and the layered porous g-C is obtained after cooling3N4；
50g of layered porous g-C3N4And 6.5g of GO is added into 200g of absolute ethyl alcohol, ultrasonic treatment is carried out for 20min to obtain dispersion liquid, then the dispersion liquid is added into a polytetrafluoroethylene lining, the reaction is carried out in a hydrothermal reaction kettle at 190 ℃ for 2h, after the reaction is finished, the reaction product is naturally cooled, filtered, washed and dried in vacuum to obtain g-C3N4-rGO；
(3) Preparing the wallpaper for photocatalytic decomposition of formaldehyde: 150g of amino-modified kieselguhr was mixed with 34g g-C3N4Mixing and grinding the rGO catalyst in an agate bowl to obtain a mixture, and then sequentially mixing the obtained mixture, 4.5g of sodium polyacrylate, 0.25g of defoaming agent SN-154 and 0.5g of water retentionAdding carboxymethyl cellulose serving as a raw material, 6.2g of seaweed gel, 250g of VAE adhesive, 0.45g of plasticizer dioctyl phthalate, 3g of nano zinc oxide and 3.4g of copper oxide into 420mL of deionized water, stirring for 60min to obtain a coating, adding the coating into a coating tank of a coating machine, and performing a coating process on A4 paper, wherein the parameters of the coating machine are set to be 50N of roller pressure, 28N of scraper pressure, 18 degrees of scraper angle and 8m/min of coating speed, and performing infrared heating for 30s after coating to obtain the wallpaper for photocatalytic decomposition of formaldehyde.
The wallpaper prepared in the example 3 and the comparative examples 1-2 is subjected to a formaldehyde adsorption experiment, and the specific experimental steps are as follows: the wallpaper prepared in the example 3 and the comparative examples 1-2 is pasted on three sides of a cubic glass box with the side length of 500mm, one side faces the sun and is not pasted with the wallpaper, the same formaldehyde release source and a formaldehyde tester are placed in the glass box under the condition that light exists, a TP1000 paperless recorder is used for recording the formaldehyde concentration, the recording interval is 1h, the test period is 5d, and the highest concentration and the lowest concentration are respectively recorded; the wallpaper prepared in example 3 and comparative examples 1-2 was applied to four sides of a square glass box with a side length of 500mm, the same formaldehyde emission source and formaldehyde meter were placed in the glass box, and the formaldehyde concentration was recorded using a TP1000 paperless recorder with a recording interval of 1h and a test period of 5d, with the test results shown in the following table:
as can be seen from the table, the wallpaper prepared in the example has good adsorption capacity to formaldehyde under both light and no light conditions, the adsorption capacity to formaldehyde is obviously reduced under both light and no light conditions without adding the photocatalyst in the comparative example 1, and the photocatalyst in the comparative example 2 does not load MnO2Which has a significant change in the adsorption capacity for formaldehyde in the presence and absence of light due to formaldehyde and MnO when the light is weak and at night2The hydroxyl on the surface forms a hydrogen bond and is adsorbed in MnO2Surface of (1), then MnO2Surface ofThe active oxygen of (A) oxidizes the formaldehyde into formate, carbonate and CO in turn2MnO after consuming surface active oxygen for Formaldehyde Oxidation2Will form oxygen vacancies, then MnO2Can adsorb oxygen molecules in the air and decompose the oxygen molecules into new active oxygen to continuously degrade formaldehyde in the air.
Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the present invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.
Claims (10)
1. The wallpaper for decomposing formaldehyde through photocatalysis and synergism is characterized by comprising the following preparation raw materials in parts by weight: 15-20 parts of amino modified diatomite and supported MnO2G to C of3N43-4 parts of rGO catalyst, 20-30 parts of adhesive, 0.4-0.5 part of sodium polyacrylate, 0.02-0.03 part of defoaming agent, 0.05-0.06 part of carboxymethyl cellulose, 0.6-0.8 part of seaweed gel, 0.04-0.05 part of dioctyl phthalate, 0.2-0.5 part of nano zinc oxide, 0.3-0.4 part of copper oxide and 40-50 parts of deionized water, wherein the defoaming agent is SN-154 or 1410, and the adhesive is VAE adhesive, 2011-adhesive or PVA adhesive.
2. The wallpaper for photocatalytic and synergistic formaldehyde decomposition according to claim 1, wherein the preparation method of the amino modified diatomite comprises the following steps:
(1) calcining and cooling diatom ooze, then carrying out ultrasonic treatment by using sulfuric acid, and obtaining porous diatomite after standing, precipitating, filtering, washing and vacuum drying treatment;
(2) adding porous diatomite and hexamethylene diisocyanate into an anhydrous toluene solvent, performing ultrasonic dispersion uniformly, then performing heating and stirring reaction under the nitrogen atmosphere, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying on a reaction product to obtain isocyanated diatomite;
(3) adding isocyanated diatomite into deionized water, carrying out hydrolysis reaction, and after the reaction is finished, filtering, washing and vacuum-drying a reaction product to obtain the amino modified diatomite.
3. The wallpaper for photocatalytic and synergetic decomposition of formaldehyde as claimed in claim 2, wherein in the step (1), the calcination temperature is 500-.
4. The wallpaper for photocatalytic and synergistic formaldehyde decomposition as claimed in claim 2, wherein in the step (2), the mass ratio of the porous diatomite to the hexamethylene diisocyanate is 100:80-120, the heating and stirring reaction temperature is 80-100 ℃, and the reaction time is 5-8 h.
5. The wallpaper for photocatalytic and synergistic formaldehyde decomposition as claimed in claim 2, wherein in the step (3), the mass ratio of the isocyanated diatomite to the deionized water is 1:1.09, the hydrolysis reaction temperature is 80-100 ℃, and the reaction time is 36-72 h.
6. The wallpaper for photocatalytic and synergistic decomposition of formaldehyde as claimed in claim 1, wherein the supported MnO is MnO2G to C of3N4-a process for the preparation of rGO catalyst, comprising in particular the steps of: mixing potassium permanganate with g-C3N4Dispersing the-rGO in deionized water, adding D (+) -glucose, stirring uniformly, standing for 30-40min, and drying at the temperature of 100 ℃ and 110 ℃ for 24-30h to obtain the supported MnO2G to C of3N4-rGO catalyst.
7. The wallpaper for photocatalytic and synergistic decomposition of formaldehyde according to claim 6, wherein the potassium permanganate is g-C3N4The mass ratio of the-rGO, the deionized water and the D (+) -glucose is 10:180-200:500-600: 2-3.
8. According to the rightThe wallpaper for photocatalytic and synergistic formaldehyde decomposition according to claim 6, wherein the g-C is3N4-a process for the preparation of rGO comprising the steps of: calcining and cooling melamine in the air atmosphere to obtain layered porous g-C3N4Then the layered porous g-C is put3N4Adding GO and the water solution into absolute ethyl alcohol, carrying out ultrasonic treatment for 20-30min, then carrying out hydrothermal reaction, and after the reaction is finished, naturally cooling, filtering, washing and vacuum drying the reaction product to obtain g-C3N4-rGO。
9. The wallpaper for photocatalytic and synergistic formaldehyde decomposition according to claim 8, wherein the layered porous g-C3N4The mass ratio of GO to absolute ethyl alcohol is 100:10-15:400-600, the temperature of the hydrothermal reaction is 180-190 ℃, and the reaction time is 2-3 h.
10. A method for preparing a wallpaper for photocatalytic and synergistic formaldehyde decomposition according to any one of claims 1-9, comprising the following steps: sequentially adding amino modified diatomite and supported MnO into deionized water2G to C of3N4The preparation method comprises the following steps of (1) stirring a rGO catalyst, sodium polyacrylate, a defoaming agent, carboxymethyl cellulose, seaweed gel, an adhesive, dioctyl phthalate, nano zinc oxide and copper oxide for 60-90min to obtain a coating, and then carrying out a coating process on the coating to obtain the wallpaper capable of decomposing formaldehyde in a photocatalytic and synergistic manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110808388.8A CN113529493B (en) | 2021-07-16 | 2021-07-16 | Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110808388.8A CN113529493B (en) | 2021-07-16 | 2021-07-16 | Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113529493A true CN113529493A (en) | 2021-10-22 |
| CN113529493B CN113529493B (en) | 2022-07-19 |
Family
ID=78099895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110808388.8A Active CN113529493B (en) | 2021-07-16 | 2021-07-16 | Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113529493B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186304A (en) * | 2007-09-03 | 2008-05-28 | 南京工业大学 | Formaldehyde in-situ absorption inserted layer assembling function composite material and preparation method thereof |
| CN105817255A (en) * | 2016-05-11 | 2016-08-03 | 武汉理工大学 | Manganese oxide-graphite phase carbon nitride composite photocatalytic material and preparation method thereof |
| CN108047808A (en) * | 2018-01-26 | 2018-05-18 | 北京欧美中科学技术研究院 | A kind of light catalyzed coating graphene additive and preparation method thereof |
| CN108912752A (en) * | 2018-06-27 | 2018-11-30 | 宁波智通环保科技有限公司 | A kind of diatom ooze coating and preparation method thereof that formaldehyde is catalytically decomposed |
| CN109020388A (en) * | 2018-08-31 | 2018-12-18 | 广东太氧谷环保科技有限公司 | A kind of diatom ooze material and preparation method thereof of non-photocatalyst-type purification air formaldehyde |
| CN109772412A (en) * | 2019-02-23 | 2019-05-21 | 辽宁大学 | MnOx/g-C3N4Composite catalyst and its application in photo-thermal Synergistic degradation gaseous-phase organic pollutant |
| CN111644191A (en) * | 2020-06-09 | 2020-09-11 | 嵊州市汇业新材料科技有限公司 | Nano WO3-g-C3N4-rGO heterojunction supported foam nickel photocatalytic material and preparation method thereof |
| CN111647288A (en) * | 2020-04-13 | 2020-09-11 | 赵梓权 | Environment-friendly coating and preparation method thereof |
-
2021
- 2021-07-16 CN CN202110808388.8A patent/CN113529493B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186304A (en) * | 2007-09-03 | 2008-05-28 | 南京工业大学 | Formaldehyde in-situ absorption inserted layer assembling function composite material and preparation method thereof |
| CN105817255A (en) * | 2016-05-11 | 2016-08-03 | 武汉理工大学 | Manganese oxide-graphite phase carbon nitride composite photocatalytic material and preparation method thereof |
| CN108047808A (en) * | 2018-01-26 | 2018-05-18 | 北京欧美中科学技术研究院 | A kind of light catalyzed coating graphene additive and preparation method thereof |
| CN108912752A (en) * | 2018-06-27 | 2018-11-30 | 宁波智通环保科技有限公司 | A kind of diatom ooze coating and preparation method thereof that formaldehyde is catalytically decomposed |
| CN109020388A (en) * | 2018-08-31 | 2018-12-18 | 广东太氧谷环保科技有限公司 | A kind of diatom ooze material and preparation method thereof of non-photocatalyst-type purification air formaldehyde |
| CN109772412A (en) * | 2019-02-23 | 2019-05-21 | 辽宁大学 | MnOx/g-C3N4Composite catalyst and its application in photo-thermal Synergistic degradation gaseous-phase organic pollutant |
| CN111647288A (en) * | 2020-04-13 | 2020-09-11 | 赵梓权 | Environment-friendly coating and preparation method thereof |
| CN111644191A (en) * | 2020-06-09 | 2020-09-11 | 嵊州市汇业新材料科技有限公司 | Nano WO3-g-C3N4-rGO heterojunction supported foam nickel photocatalytic material and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| JIANHUA XU等: "Constructing Sheet-On-Sheet Structured Graphitic Carbon Nitride/Reduced Graphene Oxide/Layered MnO2 Ternary Nanocomposite with Outstanding Catalytic Properties on Thermal Decomposition of Ammonium Perchlorate", 《NANOMATERIALS》 * |
| 余德池: "《装饰工》", 30 September 1999, 陕西科学技术出版社 * |
| 姚运先: "《室内环境污染控制》", 30 June 2007, 中国环境科学出版社 * |
| 杨伯涵: "《化工生产安全基础知识实用读本》", 31 March 2017, 苏州大学出版社 * |
| 王灿等: "纳米矿物材料净化甲醛污染的研究进展", 《材料导报》 * |
| 胡宏玖: "《非石棉垫片复合材料设计与性能》", 31 March 2006, 上海大学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113529493B (en) | 2022-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5756525B2 (en) | Manufacturing method and use of manganese dioxide nanorods | |
| CN109833868A (en) | A kind of preparation method of manganese based composite metal oxidate ozone decomposition catalyst | |
| CN109331853B (en) | Nitrogen oxide nanoparticle photocatalyst and application thereof | |
| CN108620113B (en) | Preparation method of nitrogen-doped carbon-cerium composite nanosheet | |
| CN111036201A (en) | Supported monatomic Pt catalyst and preparation method and application thereof | |
| CN108660481A (en) | A kind of novel N doping biological carbon Quito hole elctro-catalyst preparation method | |
| CN112111211B (en) | Environment-friendly coating | |
| CN113262808A (en) | Water-soluble graphite-phase carbon nitride nanosheet catalyst for efficiently removing formaldehyde at room temperature and preparation method thereof | |
| CN101723333A (en) | Method for preparing mesoporous metallic oxides with different appearances | |
| CN113529493B (en) | Wallpaper for photocatalytic synergistic decomposition of formaldehyde and preparation method thereof | |
| CN113201975B (en) | Preparation method and application of modified diatomite formaldehyde adsorption humidifying wallpaper | |
| CN110935441B (en) | Titanium-based composite catalytic net for efficiently degrading formaldehyde and preparation method thereof | |
| CN109021750B (en) | Diatom ooze coating for interior decoration | |
| CN111250077A (en) | Composite metal oxide catalyst and application thereof | |
| CN109078644B (en) | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof | |
| CN109233455B (en) | Diatom ooze coating with purification effect | |
| CN108855170B (en) | A kind of preparation method and nanocomposite of the graphene-based bismuth system nanocomposite of carnation sample | |
| CN103539121A (en) | Porous carbonate and porous oxide preparation methods | |
| CN114653356A (en) | Preparation method of lanthanum-doped cerium dioxide catalyst material and formaldehyde-removing compound | |
| CN110860296A (en) | Method for preparing crystal face-controllable nano cerium-based composite oxide based on cellulose | |
| CN110918101B (en) | Ultralow-content Pt composite catalyst for catalytic decomposition of formaldehyde gas at room temperature and preparation method thereof | |
| CN114950530A (en) | Preparation method of nitrogen-doped eggshell nano enzyme with peroxidase-like activity | |
| CN112138684B (en) | Visible-light-driven photocatalyst, and preparation method and application thereof | |
| CN113713803A (en) | Catalytic active component, preparation method thereof, catalyst and application thereof | |
| CN108940265B (en) | Catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220627 Address after: No. 9, Yangda Road, Shanyang Town, Jinshan District, Shanghai Applicant after: SHANGHAI WEIZE DECORATION MATERIALS Co.,Ltd. Address before: 430000 room 10, floor 5, building B18, phase II of financial background service center base construction project, No. 77, Guanggu Avenue, Donghu New Technology Development Zone, Wuhan, Hubei Province Applicant before: Wuhan Ziqiang Ecological Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |