CN114854243B - Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating - Google Patents
Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating Download PDFInfo
- Publication number
- CN114854243B CN114854243B CN202210560902.5A CN202210560902A CN114854243B CN 114854243 B CN114854243 B CN 114854243B CN 202210560902 A CN202210560902 A CN 202210560902A CN 114854243 B CN114854243 B CN 114854243B
- Authority
- CN
- China
- Prior art keywords
- repellent
- oil
- water
- silicon dioxide
- silane coupling
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D21H21/16—Sizing or water-repelling agents
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention relates to the field of water-repellent and oil-repellent coatings, and discloses a preparation method and application of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating. The preparation method of the modified silicon dioxide comprises the following steps: (1) Uniformly mixing hexadecyl trimethyl ammonium bromide, urea and water to obtain a water phase; uniformly mixing tetraethoxysilane and an oil phase solvent to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide; (2) And (3) grafting a silane coupling agent onto the surface of the porous nano silicon dioxide obtained in the step (1) to obtain the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating. According to the invention, the nano silicon dioxide is prepared by adopting a special method, so that the surface of the nano silicon dioxide particles has a porous structure, the roughness of the surface of the coating is improved, and the coating is endowed with better water and oil repellency.
Description
Technical Field
The invention relates to the field of water-repellent and oil-repellent coatings, in particular to a preparation method and application of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating.
Background
The super-hydrophobic surface shows a static water Contact Angle (CA) of more than 150 degrees and a very low contact hysteresis angle of water, and has higher potential application value in the aspects of self-cleaning, oil-water separation, ice resistance, antibiosis, corrosion resistance and the like. It is reported that when the surface is rich in-CF 3 When the groups are present, a fluorinated compound can reduce the surface tension to 6.7mJ/m 2 This is considered to be the lowest surface free energy of all solids. In recent years, development of superhydrophobic oleophobic surfaces with different precursors, such as Fluorinated Alkylsilanes (FAS), has been widely studied.
Long fluorocarbon chain (C) n F 2n+1 N is more than or equal to 8), the oil-proof finishing agent can reduce the surface tension of the fabric to 10-15 mN/m, has excellent oil-proof effect, and the fabric finished by the oil-proof finishing agent has good hand feeling and excellent air permeability and moisture permeability. However, long fluorocarbon chains are non-degradable, and perfluorooctyl sulfonyl compounds (PFOS) and perfluorooctyl compounds (PFOA) are easily released, which are harmful to human health and the environment, and zero emission is currently required. Accordingly, research and development of PFOS/PFOA replacement finishing agents or replacement finishing methods have been attracting attention. Using short fluorocarbon chains or polymers (e.g. perfluorobutyl C) 4 F. Perfluorohexane C 6 F) The replacement of long fluorocarbon chain compounds is one of the main research directions. However, in contrast to PFOS/PFOA-containing products, C 4 F and C 6 F has poor oil repellency; and C 6 F has a better oil repellency than C 4 F, but there have been reports that C with better performance 6 Class F alternatives remain unsafe because of C 6 F and C 8 F is as difficult to decompose and has a toxicity ratio to certain aquatic organisms of C 8 F is also 3-5 times larger. Research and development of environmental protection, no pollution and excellent water and oil repellencyThe waterproof and oilproof finishing agent is forced to be in urgent eyebrows.
The silicon dioxide has no pollution to the environment, and by utilizing the silicon dioxide to construct a rough structure on the microscopic scale on the surface of the material, the surface can not be fully infiltrated when the liquid drops are contacted with the surface, air is reserved in the microscopic structure to form air cells, and the liquid drops can easily slide off the surface due to the existence of the air cells, so that the water and oil repellency of the surface of the material is improved. Patent CN201410693047.0 discloses a transparent superhydrophobic coating material, the raw materials of which comprise fumed silica nanoparticle dispersion liquid composed of fumed silica nanoparticles and a solvent and a hydrophobic treatment agent; the water repellent agent is an alkyl silane coupling agent, a fluorine-containing methacrylate polymer, a fluorine-containing acrylate polymer, an organosilicon compound or a fluorine-containing organosilicon compound. According to the patent, the fumed silica nano particles are coated on the surface of the substrate through a wiping method, and a porous microstructure can be formed on the surface of the substrate after the solvent is quickly volatilized, but the fumed silica nano particles do not have a surface structure with high roughness, so that the improvement effect on the water and oil repellency of the surface of the substrate is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating. In the preparation process of the modified silicon dioxide, the nano silicon dioxide is prepared by adopting a special method, so that the surface of the nano silicon dioxide particles has a porous structure, and the modified silicon dioxide is endowed with better water and oil repellency.
The specific technical scheme of the invention is as follows:
first, the invention provides a preparation method of modified silicon dioxide for an environment-friendly water-repellent and oil-repellent coating, which comprises the following steps:
(1) Uniformly mixing hexadecyl trimethyl ammonium bromide, urea and water to obtain a water phase; uniformly mixing tetraethoxysilane and an oil phase solvent to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide;
(2) Grafting a silane coupling agent to the porous nano-silica surface obtained in the step (1), wherein the silane coupling agent comprises SiCH 3 The silane coupling agent and the silane coupling agent containing perfluorobutyl are used for obtaining the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating.
In the step (1), the invention adopts a special method to prepare the nano silicon dioxide, so that the surface of the nano silicon dioxide particles has a porous structure, thereby endowing the nano silicon dioxide particles with higher surface roughness, and the specific mechanism is as follows: after the water phase and the oil phase in the step (1) are mixed, water-in-oil emulsion can be formed, the formation of porous nano silicon dioxide mainly occurs on a water-in-oil interface, tetraethoxysilane (TEOS) molecules are driven to be close to the tail of cetyltrimethylammonium bromide (CTAB) in the oil phase due to the concentration difference inside reverse micelles, and when the TEOS is close to the boundary, hydrolysis reaction is immediately carried out to generate silicate molecules. CTAB acts as a template and negatively charged silicate molecules penetrate into the reverse micelles and aggregate in free radial and limited tangential directions. Finally, the self-assembled silicate is condensed to make SiO 2 The material crystallizes in the reverse micelles, forming porous nano-silica particles. In this way, it is possible to obtain dendritic, coral-shaped, flower-shaped and raspberry-shaped nanosilica, the surface of which is distributed with a large number of pores.
In step (2), compared with perfluorooctyl (C) 8 F) Or perfluorohexyl (C) 6 F) In the case of perfluorobutyl (C) 4 F) Has short fluorocarbon chain, is easy to degrade, has no harm to human body and environment, but has relatively poor oil repellency. In order to ensure the safety and environmental protection and simultaneously endow the coating with better oil repellency, the invention contains-SiCH 3 The silane coupling agent and the silane coupling agent containing the perfluorobutyl are matched and used, and the orientation and the arrangement of the perfluorobutyl can be limited by utilizing the chemical incompatibility between the methyl and the perfluorobutyl and the mutual rejection of different groups on the special surface of the porous silicon dioxide, thereby being beneficial to-CF 3 The chain length of methyl groups is short and does not mask the perfluoro groups of the outermost layer. In this way, methyl groups and perfluorobutyl groups can produce a "1+1 > 2" synergismWith the same effect, the coating is endowed with lower surface energy, so that the coating has better oil repellency. In addition, contain-SiCH 3 The silane coupling agent and the silane coupling agent containing the perfluorobutyl are easy to degrade, have no harm to human health, and are safe and environment-friendly.
When the modified silica is used for the water-repellent and oil-repellent coating, the porous micro-nano structure of the coating can be endowed by utilizing the pores among the modified silica particles, and meanwhile, the roughness of the micro-nano structure can be further improved by utilizing a large number of pores on the surface of each modified silica particle. By utilizing the micro-nano structure, the buffer of a liquid/solid interface can be reduced by establishing balanced air, and the adhesive force of oil and water on the surface of a substrate can be reduced, so that the water and oil repellency of the surface of the substrate can be improved. The silane coupling agent grafted on the surface of the silicon dioxide particles can reduce the surface tension of the substrate while forming the micro-nano structure, and the silane coupling agent is synergistic with the micro-nano structure to endow the substrate with better water and oil repellency.
Preferably, in step (2), the catalyst comprises-SiCH 3 The mass ratio of the silane coupling agent containing the perfluorobutyl to the silane coupling agent containing the perfluorobutyl is 1:1-2.
When containing-SiCH 3 When the ratio of the silane coupling agent to the perfluorobutyl-containing silane coupling agent is too large or too small, the oil-repellent effect of the modified silica is unsatisfactory, and specifically: when the amount ratio is too small, the effect of the methyl group in restricting the orientation and arrangement of the perfluorobutyl group is weak, and it is difficult to effectively improve the oil-repellent effect of the perfluorobutyl group, so that the oil-repellent effect of the modified silica is poor; when the ratio is too large, the outermost-CF layer is formed 3 Too little will affect the oil repellency of the modified silica as well.
Preferably, in the step (1), the mass ratio of the hexadecyl trimethyl ammonium bromide, the urea and the water is 0.5-2:0.6-2.4:40-60.
Preferably, in the step (1), the oil phase solvent is cyclohexane and 1-amyl alcohol; the mass ratio of the tetraethoxysilane to the cyclohexane to the 1-amyl alcohol is 4-5:10-40:1-4.
Preferably, in the step (1), the mass ratio of the water phase to the oil phase is 1-2:1.
Preferably, in the step (1), the hydrolysis and condensation are performed at a temperature of 60 to 80 ℃ for a time of 12 to 16 hours.
Preferably, the specific process of step (2) comprises the following steps: dispersing the porous nano silicon dioxide obtained in the step (1) into an organic solvent, adding a silane coupling agent into the organic solvent, adjusting the pH to 9-10 according to the mass ratio of the porous nano silicon dioxide to the silane coupling agent to the organic solvent of 1:1-2:80-100, reacting for 5-6 hours at 60-70 ℃, and separating out a product to obtain the modified silicon dioxide for the environment-friendly water-repellent oil-repellent coating.
Second, the present invention provides a modified silica produced by the production method.
Third, the invention provides application of the modified silica in a water-repellent and oil-repellent coating.
Preferably, the preparation method of the water-repellent and oil-repellent coating comprises the following steps: spraying the adhesive on the surface of the substrate, and drying to form an adhesive layer; dispersing the modified silicon dioxide into a solvent to prepare suspension, spraying the surface of the adhesive layer, and drying to form the water-repellent and oil-repellent coating.
The water-repellent and oil-repellent coating is suitable for different base materials such as cotton, paper, glass, terylene, aluminum sheets, iron sheets and the like. When the modified silicon dioxide is sprayed on the surface of the adhesive layer, the modified silicon dioxide can spontaneously enter the adhesive layer to form firm combination with the substrate by utilizing good interfacial compatibility between the modified silicon dioxide and the adhesive layer, so that a water-repellent and oil-repellent surface with a micro-nano structure is formed.
Preferably, the mass ratio of the modified silicon dioxide to the solvent is 1:80-100.
Compared with the prior art, the invention has the following advantages:
(1) The nano silicon dioxide is prepared by adopting a special method, so that the surface of the nano silicon dioxide particles has a porous structure, the roughness of the surface of the coating is improved, and the coating is endowed with better water and oil repellency;
(2) Will contain-SiCH 3 The silane coupling agent and the silane coupling agent containing the perfluorobutyl are matched for use, so that the safety and environmental protection are ensured, and meanwhile, the synergistic effect between the methyl and the perfluorobutyl can be utilized, and the coating is endowed with good water and oil repellency.
Drawings
FIG. 1 is an SEM image of flower-like porous silica nanoparticles prepared in example 1;
FIG. 2 is a photograph of a comparative example 3 in which diiodomethane, water and disperse red dye were added dropwise to the surface of the different substrates;
FIG. 3 is a super-hydrophobic dynamic schematic;
fig. 4 is a contact angle and a hysteresis angle of the substrate after the water-repellent and oil-repellent treatment in example 1 and comparative examples 2 to 5 with respect to oil.
Detailed Description
The invention is further described below with reference to examples.
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
Example 1
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
The prepared flower-like porous nano silicon dioxide structure is shown in figure 1. The test shows that the particle size of the flower-shaped porous nano silicon dioxide is 200-300 nm, and the pore width is 25nm.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 0.5g of nonafluorohexyl triethoxysilane and 0.5g of methyltriethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Example 2
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 0.67g of nonafluorohexyl triethoxysilane and 0.33g of methyltriethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Example 3
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 0.33g of nonafluorohexyl triethoxysilane and 0.67g of methyltriethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Example 4
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 0.8g of nonafluorohexyl triethoxysilane and 0.2g of methyltriethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Comparative example 1
(1) Grafted silane coupling agent:
1g of commercially available spherical nano silicon dioxide with the particle size of 200-300 nm is added into 100g of ethanol, ultrasonic dispersion is carried out, a silicon dioxide dispersion liquid is obtained, 0.5g of nonafluorohexyl triethoxysilane and 0.5g of methyl triethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Comparative example 2
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 1g of methyltriethoxysilane is added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Diiodomethane, water and disperse red dye were dropped onto the surface of the water-and oil-repellent treated substrate, and the results are shown in fig. 2, in which none of the three droplets wetted the substrate surface.
Comparative example 3
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silicon dioxide is added into 100g of ethanol, ultrasonic dispersion is carried out, silicon dioxide dispersion liquid is obtained, 1g of octadecyltriethoxysilane is added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Comparative example 4
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silicon dioxide is added into 100g of ethanol, ultrasonic dispersion is carried out, silicon dioxide dispersion liquid is obtained, 1g of nonafluorohexyl triethoxysilane is added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Comparative example 5
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silica is added into 100g of ethanol, ultrasonic dispersion is carried out, a silica dispersion liquid is obtained, 0.5g of nonafluorohexyl triethoxysilane and 0.5g of octadecyl triethoxysilane are added into the mixture, the pH is regulated to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Comparative example 6
(1) Preparing porous nano silicon dioxide:
0.5g CTAB and 0.6g urea were dissolved in 40g water and magnetically stirred for 1 hour to obtain an aqueous phase. 3ml of TEOS, 20ml of cyclohexane and 2ml of 1-pentanol were mixed and stirred for 30min to obtain an oil phase. After mixing the aqueous and oil phases, stirring was carried out at 80℃for 16h. And finally, centrifugally purifying and drying at 65 ℃ to obtain the flower-shaped porous nano silicon dioxide.
(2) Grafted silane coupling agent:
1g of flower-like porous nano silicon dioxide is added into 100g of ethanol, ultrasonic dispersion is carried out, silicon dioxide dispersion liquid is obtained, 1g of heptadecafluorodecyl triethoxysilane is added into the mixture, the pH is adjusted to 9, and the mixture is reacted for 6 hours at 70 ℃. Washing with pure water and ethanol, precipitating, centrifuging, and oven drying to obtain modified silica.
(3) Preparing a water-repellent and oil-repellent coating:
spraying commercial adhesive (commercial adhesive Super 77, available from Shanghai Sumitomo 3M Co., ltd.) onto the surfaces of different substrates (paper, cotton fabric, polyester, aluminum sheet and glass), and drying at room temperature for 30s to form an adhesive layer; dispersing 1g of modified silicon dioxide into 100g of ethanol to prepare suspension, spraying the surface of the adhesive layer, drying for 30min, and repeating the spraying and drying steps for 5 times to form the water-repellent and oil-repellent coating. And rubbing the substrates against each other to remove the modified silica which is not firmly bonded to the substrates by the adhesive, thereby obtaining the water-repellent and oil-repellent treated substrates.
Test case
The coatings of examples 1 to 4 and comparative examples 1 to 6 were examined for water and oil repellency by the following method: the static contact angles of water and diiodomethane on the surface of the substrate (cotton fabric) after the water and oil repellent treatment, i.e. the water contact angle and the oil contact angle, were measured respectively using a DSA100 (kruss, germany) contact angle measuring device, the measuring system of which measures the object surface contact angle based on the interface shape analysis method. The results are shown in Table 1.
Fig. 3 is a superhydrophobic dynamic schematic of a substrate surface after water and oil repellent treatment. Fig. 4 is a contact angle and a hysteresis angle of the substrate after the water-repellent and oil-repellent treatment in example 1 and comparative examples 2 to 5 with respect to oil.
Table 1 comparison of the properties of examples 1 to 4 and comparative examples 1 to 6
From Table 1 and FIG. 4 it can be seen that:
(1) From the perspective of water repellency, the water contact angles of examples 1-4 and comparative examples 1-6 were all greater than 145 °, indicating good hydrophobicity.
(2) In terms of oil repellency, when nonafluorohexyltriethoxysilane and methyltriethoxysilane were used in combination (example 1), the oil repellency was superior to that of other degradable silane coupling agents (comparative examples 2 to 5), and was comparable to that of heptadecafluorodecyltriethoxysilane (comparative example 6), which was difficult to degrade and was more contaminated. And, in the case that the total amount of the silane coupling agent is the same, the two are compounded to have a better oil repellent effect than the case of using a single methyltriethoxysilane (comparative example 2) or nonafluorohexyltriethoxysilane (comparative example 4), illustrating that nonafluorohexyltriethoxysilane and methyltriethoxysilane can produce a synergistic effect of "1+1 > 2", since the orientation and alignment of perfluorobutyl groups can be restricted by chemical incompatibility between methyl groups and perfluorobutyl groups and mutual repellency of different groups at the specific surface of porous silica, contributing to-CF 3 Stacking at the outermost layer. However, when methyltriethoxysilane is changed to octadecyltriethoxysilane (comparative example 5), the oil repellent effect of nonafluorohexyltriethoxysilane is rather impaired because, for octadecyl side chains, on the surface of flower-like silica, although perfluorobutyl is promoted to crystallize due to its special crystallization property, the surface having a lower surface tension, octadecyl side chains occupy the outermost layer preferentially, and perfluoro groups are masked.
(3) In examples 1 and 3, the mass ratio of methyltriethoxysilane to nonafluorohexyltriethoxysilane was 1:1 and 1:0.5, respectively, and the oil repellency of example 1 was significantly better than that of example 3; in examples 2 and 4, the mass ratio of methyltriethoxysilane to nonafluorohexyltriethoxysilane was 1:2 and 1:4, respectively, the oil repellent effect of example 2 is significantly better than that of example 4. The fact that the oil-repellent effect of the modified silica is not ideal when the ratio of the methyl triethoxysilane to the nonafluorohexyl triethoxysilane is too large or too small is shown, because the effect of the methyl on limiting the orientation and arrangement of the perfluorobutyl is weak when the ratio of the methyl to the nonafluorohexyl triethoxysilane is too small, the oil-repellent effect of the perfluorobutyl is difficult to effectively improve, and the oil-repellent effect of the modified silica is poor; when (when)When the ratio of the amount is too large, the outermost-CF layer is formed 3 Too small a content may affect the oil repellency of the modified silica as well.
(4) Compared with the spherical nano silicon dioxide (comparative example 1) on the market, the porous nano silicon dioxide (example 1) prepared by the invention can endow the coating with better water and oil repellency. The preparation method can enable the surfaces of the nano silicon dioxide particles to have a porous structure, so that the roughness of the surfaces of the coatings is improved, and the coatings are endowed with better water and oil repellency.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (9)
1. The preparation method of the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating is characterized by comprising the following steps of:
(1) Uniformly mixing hexadecyl trimethyl ammonium bromide, urea and water to obtain a water phase; uniformly mixing tetraethoxysilane and an oil phase solvent to obtain an oil phase; mixing the water phase and the oil phase, performing hydrolytic condensation, and separating out a product to obtain porous nano silicon dioxide;
(2) Grafting a silane coupling agent to the porous nano-silica surface obtained in the step (1), wherein the silane coupling agent comprises SiCH 3 Silane coupling agent containing-SiCH and silane coupling agent containing perfluorobutyl 3 Silane coupling agent and perfluorobutyl-containing agent the mass ratio of the silane coupling agent is 1: 1-2, obtaining the modified silicon dioxide for the environment-friendly water-repellent and oil-repellent coating.
2. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the cetyltrimethylammonium bromide, the urea and the water is 0.5 to 2:0.6 to 2.4:40 to 60.
3. The method of claim 1, wherein in step (1), the oil phase solvent is cyclohexane and 1-pentanol; the mass ratio of tetraethoxysilane, cyclohexane and 1-amyl alcohol is 4-5: 10 to 40:1 to 4.
4. The method according to claim 1, 2 or 3, wherein in the step (1), the mass ratio of the aqueous phase to the oil phase is 1 to 2:1.
5. the process according to claim 1, 2 or 3, wherein in the step (1), the hydrolytic condensation is carried out at a temperature of 60 to 80℃for a period of 12 to 16 hours.
6. The preparation method according to claim 1, wherein the specific process of step (2) comprises the steps of: dispersing the porous nano silicon dioxide obtained in the step (1) into an organic solvent, adding a silane coupling agent into the organic solvent, the mass ratio of the porous nano silicon dioxide to the silane coupling agent to the organic solvent is 1: 1-2: 80-100, regulating pH to 9-10, reacting at 60-70 ℃ for 5-6 h, separating out the product, and obtaining the environment-friendly modified silicon dioxide for the water-repellent and oil-repellent coating.
7. A modified silica produced by the production process according to any one of claims 1 to 6.
8. Use of the modified silica of claim 7 in water and oil repellent coatings.
9. The use according to claim 8, wherein the method for preparing the water-repellent and oil-repellent coating comprises the steps of: spraying the adhesive on the surface of the substrate, and drying to form an adhesive layer; dispersing the modified silicon dioxide into a solvent to prepare suspension, spraying the surface of the adhesive layer, and drying to form the water-repellent and oil-repellent coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210560902.5A CN114854243B (en) | 2022-05-20 | 2022-05-20 | Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210560902.5A CN114854243B (en) | 2022-05-20 | 2022-05-20 | Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114854243A CN114854243A (en) | 2022-08-05 |
| CN114854243B true CN114854243B (en) | 2023-05-30 |
Family
ID=82639049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210560902.5A Active CN114854243B (en) | 2022-05-20 | 2022-05-20 | Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854243B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948515A (en) * | 2023-07-26 | 2023-10-27 | 苏州弘道新材料有限公司 | Anti-fouling coating liquid composition, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6333454B1 (en) * | 2017-08-18 | 2018-05-30 | 株式会社フェクト | Method for forming water / oil repellent coating and water / oil repellent coating |
| JP2019014793A (en) * | 2017-07-05 | 2019-01-31 | 凸版印刷株式会社 | Water- and oil-repellent base material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8163393B2 (en) * | 2007-03-19 | 2012-04-24 | Dai Nippon Printing Co., Ltd. | Anti-dazzling optical laminate |
| KR20110003535A (en) * | 2008-08-11 | 2011-01-12 | 디아이씨 가부시끼가이샤 | Ultrahydrophobic powder, structure with ultrahydrophobic surface, and processes for producing these |
| CN103201331B (en) * | 2010-11-10 | 2014-12-17 | 3M创新有限公司 | Hydrophobic fluorinated coatings |
| EP2638116B1 (en) * | 2010-11-10 | 2015-08-12 | 3M Innovative Properties Company | Optical device surface treatment process and smudge-resistant article produced thereby |
| CN110028412B (en) * | 2019-04-23 | 2021-11-30 | 南京信息工程大学 | Perfluoro-substituted micromolecule end group diol and preparation method and application thereof |
| CN113136120B (en) * | 2020-01-20 | 2023-03-24 | 中国科学院化学研究所 | Transparent, water-impact-resistant and super-lyophobic coating as well as preparation method and application thereof |
| CN113249971B (en) * | 2021-05-06 | 2022-06-14 | 义乌市中力工贸有限公司 | Core-shell type short-chain fluorine-containing acrylate fabric water-repellent and oil-repellent finishing agent and preparation method and application thereof |
-
2022
- 2022-05-20 CN CN202210560902.5A patent/CN114854243B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019014793A (en) * | 2017-07-05 | 2019-01-31 | 凸版印刷株式会社 | Water- and oil-repellent base material |
| JP6333454B1 (en) * | 2017-08-18 | 2018-05-30 | 株式会社フェクト | Method for forming water / oil repellent coating and water / oil repellent coating |
Non-Patent Citations (4)
| Title |
|---|
| 朱杰 ; 郑奎 ; 王丽阁 ; 王恩泽 ; .超疏水涂膜的制备及其性能.西南科技大学学报.2018,(第02期),第15-21页. * |
| 王静 ; 孔庆刚 ; 张龙 ; 钱海燕 ; .含氟低表面能修饰的超双疏涂层制备及其性能.表面技术.2018,(第11期),第76-82页. * |
| 许莉丽 ; 李晓光 ; 倪星元 ; 沈军 ; .微结构与表面修饰对二氧化硅多孔薄膜疏水性能的影响.无机化学学报.2013,(第03期),第32-37页. * |
| 马林娟 ; 凌波 ; 魏栖梧 ; 周磊 ; .二氧化硅改性后超疏水性质的粒径效应研究.南昌航空大学学报(自然科学版).2020,(第01期),第63-68页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114854243A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6463523B2 (en) | Surface-modified nanoparticle composition | |
| CN101469250B (en) | Removable antifogging coating, product, coating composition and method | |
| EP2317006A1 (en) | Ultrahydrophobic powder, structure with ultrahydrophobic surface, and processes for producing these | |
| KR100548658B1 (en) | Fluoroalkyl-functional organosiloxane-containing compositions based on alcohols and preparation methods thereof | |
| Yin et al. | Functional and versatile colorful superhydrophobic nanocellulose-based membrane with high durability, high-efficiency oil/water separation and oil spill cleanup | |
| CN102504612B (en) | Novel modified nano silicon dioxide and composite coating prepared from same | |
| CN104694001B (en) | A kind of preparation method of super-hydrophobic superparamagnetic silicone resin composite material coating | |
| DE10330020A1 (en) | Highly filled silane preparation | |
| CN112717710B (en) | Air super-oleophobic and super-hydrophilic film and preparation method and application thereof | |
| JP4503086B2 (en) | Superhydrophobic powder, structure having superhydrophobic surface using the same, and production method thereof | |
| DE102006014875A1 (en) | Particle, useful in e.g. a surface coating and a molded body, comprises a polymerization product of a polyadditionable, polycondensable or polymerizable siloxane and/or silane; and solid particulates | |
| CN113004749A (en) | Super-hydrophobic coating and preparation method and application thereof | |
| CN114854243B (en) | Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating | |
| EP3289026A1 (en) | Aqueous stain resistant coating composition | |
| Xu et al. | Preparation of vinyl silica-based organic/inorganic nanocomposites and superhydrophobic polyester surfaces from it | |
| CN111607283A (en) | Modified halloysite, composite coating based on modified halloysite and preparation method of composite coating | |
| CN104193289A (en) | Hydrophobic protective paint and preparation method thereof | |
| CN107074564B (en) | Hydrophobic silica and method for producing same | |
| KR101125163B1 (en) | Method for Preparing Superhydrophobic Polyethylene terephthalate Fabric Using Nano Silica Particle and Water-repellent Agent | |
| Chung et al. | Water-borne composite coatings using nanoparticles modified with dopamine derivatives | |
| Phan et al. | Durable tetra-scale superhydrophobic coatings with virus-like nanoparticles for oil–water separations | |
| CN115354497B (en) | Hydrophilic oleophylic-underwater oleophobic-underwater oleophylic paint in air as well as preparation method and application thereof | |
| CN113292876B (en) | Super-hydrophobic coating and preparation method and application thereof | |
| CN110117901A (en) | A kind of afterfinish method of fabric | |
| JP4503091B2 (en) | Superhydrophobic powder, structure having superhydrophobic surface using the same, and production 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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No. 19, Dangui Road, Yinan Industrial Zone, Fotang Town, Yiwu City, Jinhua City, Zhejiang Province 322000 Applicant after: YIWU ZHONGLI INDUSTRY & TRADE Co.,Ltd. Applicant after: ZHEJIANG SCI-TECH University Address before: 322000 No.5 Changqing Road, Liuqing Industrial Zone, Yiwu City, Jinhua City, Zhejiang Province Applicant before: YIWU ZHONGLI INDUSTRY & TRADE Co.,Ltd. Applicant before: ZHEJIANG SCI-TECH University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |