CN110591159B - Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof - Google Patents
Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof Download PDFInfo
- Publication number
- CN110591159B CN110591159B CN201910964230.2A CN201910964230A CN110591159B CN 110591159 B CN110591159 B CN 110591159B CN 201910964230 A CN201910964230 A CN 201910964230A CN 110591159 B CN110591159 B CN 110591159B
- Authority
- CN
- China
- Prior art keywords
- silane compound
- silver particles
- nano silver
- modified
- antifouling paint
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
Abstract
The invention provides a modified nano silver particle and a preparation method thereof. The modified nano silver particles are of raspberry-shaped structures and comprise nano silver particles serving as inner cores and tannin shell layers coated outside the nano silver particles, and nano silicon dioxide particles are loaded on the surfaces of the tannin shell layers. The invention also provides a silane compound and a preparation method thereof. The silane compound is obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane under the initiation of an initiator. The invention also provides an antifouling paint and a preparation method thereof. The antifouling paint comprises at least one of the modified nano silver particles and the silane compound. The modified nano silver particles can control the release controllability of silver ions, improve the compatibility of the silver particles and a coating, improve the antifouling effect of the antifouling paint, and reduce the pollution and damage to the marine environment.
Description
Technical Field
The invention relates to the field of nano materials and coating materials, in particular to the field of modified nano silver materials and antifouling coating materials.
Background
With the development of the marine industry, the problem of marine fouling of buildings, ship bodies, pipelines, oil platforms, marine sensors and the like is increasingly obvious. Marine fouling is mainly caused by marine organism pollution caused by the undesirable accumulation of marine animals, plants and microorganisms, such as barnacles, algae, fungi, shellfish and the like on the surface of underwater facilities, so that the dirt on the surface of a building is continuously accumulated to cause pipeline blockage, the sailing resistance and fuel consumption of a ship are increased, the aggravation of corrosion is promoted, and the like, and huge economic loss and serious problems are brought to the marine industry.
The most effective and convenient method of preventing marine fouling is through coatings that release toxic molecules at a controlled rate to reduce or inhibit the growth of adhering organisms such as bacteria, algae and molluscs. However, the method has the high possibility of influencing the marine environmental pollution and the growth and survival of other marine organisms, so that the development of the low-toxicity effective environment-friendly antifouling agent is extremely important.
The nano silver has low toxicity and excellent antibacterial and antifouling activity, but the release controllability of silver ions and the compatibility with the coating cannot be well controlled and improved at the present stage, so that the pollution damage to the marine environment can be caused when the nano silver is applied to the antifouling coating, and the application of the nano silver in the antifouling coating is limited.
Disclosure of Invention
In view of the problems in the background art, the present invention aims to provide a modified nano silver particle, a preparation method thereof and an antifouling paint, which can control the release controllability of silver ions, improve the compatibility of the silver particle and a coating, improve the antifouling effect of the antifouling paint, and reduce pollution and damage to the marine environment.
In order to achieve the above object, in one aspect of the present invention, the present invention provides a modified nano silver particle, which has a raspberry-like structure and includes a nano silver particle as an inner core and a tannic acid shell layer coated outside the nano silver particle, wherein nano silica particles are supported on a surface of the tannic acid shell layer.
In another aspect of the present invention, the present invention provides a method for preparing modified silver nanoparticles, which is used for preparing the modified silver nanoparticles, and comprises the following steps: step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain nano silver particles; step 20, dispersing the nano silver particles obtained in the step 10 in ethanol, adding an ethanol solution of tannic acid for reaction to obtain tannic acid modified nano silver particles with a core-shell structure; and step 30, dispersing the nano silver particles with the core-shell structure modified by the tannic acid obtained in the step 20 in ethanol, adding water, and then adding an ethanol solution of ethyl orthosilicate for reaction to obtain the modified nano silver particles.
In still another aspect of the present invention, there is provided a silane compound obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, γ -methacryloxypropyltrimethoxysilane, and (3-aminopropyl) triethoxysilane under initiation of an initiator.
In still another aspect of the present invention, there is provided a method for preparing a silane compound, comprising the steps of: step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound; and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.
In still another aspect of the present invention, the present invention provides an antifouling paint comprising at least one of the above modified silver nanoparticles and the above silane-based compound.
In still another aspect of the present invention, there is provided a method for preparing the above antifouling paint, comprising the steps of: step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles; step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound; and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.
The invention at least comprises the following beneficial effects:
in the modified nano silver particles, the nano silver particles are coated by the tannic acid to form a nano-scale core-shell structure, the tannic acid is grafted on the surfaces of the nano silver particles to modify the surfaces of the nano silver particles, so that the next step of silicon dioxide loading is facilitated, and in addition, the tannic acid has certain protein resistance and antifouling performance, and the antifouling effect of the silver particles can be further improved due to the conjugation effect; and the nano silicon dioxide particles are loaded on the surface of the tannin shell layer, so that the rate of silver ions released by the silver particles in the air or in the case of a small amount of water can be reduced. Meanwhile, the silicon dioxide is loaded on the surface of the tannin shell layer in a particle form to form a raspberry-shaped structure, and the silicon dioxide has good thermal stability and physical and chemical stability and has high specific surface area when being loaded on the surface of the tannin shell layer in a particle form, so that the synergistic effect of the nano silver particles can be increased; the finally obtained modified nano silver particles with raspberry-shaped structures can better exert the antifouling effect, reduce the occurrence of agglomeration and reduce the release speed of silver ions.
After the modified nano silver particles are coated with the nano silver particles through the tannic acid and loaded through the silicon dioxide particles, the antifouling effect is more obvious, the modified nano silver particles are suitable for an antifouling paint, can have better compatibility with the paint, and improve the antifouling performance of the antifouling paint; the modified nano silver particles have better silver ion release controllability, so that the antifouling coating containing the modified nano silver particles has the advantages of safety, low toxicity and environmental friendliness. The silane compound can form a network structure after self-crosslinking after being cured, and can improve the mechanical strength of an antifouling coating when being added into an antifouling coating; the silane compound has certain low surface energy and protein resistance, and can effectively inhibit the adsorption of microorganisms in marine environment. When the antifouling paint simultaneously comprises the modified nano silver particles and the silane compound, the modified nano silver particles and the silane compound are not simply compounded by nano particles and a coating, but are mutually connected through covalent bonds and van der Waals force, so that the antifouling paint has a better combination effect, and is particularly suitable for the severe condition requirement and the environment-friendly requirement of marine antifouling.
Drawings
FIG. 1 is a TEM transmission of each product during the preparation of example 1; wherein, (a) is a TEM transmission image of the silver nanoparticles prepared in step 10, (b) is a TEM transmission image of the tannin-modified silver nanoparticles having a core-shell structure prepared in step 20, and (c) is a TEM transmission image of the modified silver nanoparticles prepared in step 30.
FIG. 2 is a chart of UV-VIS absorption spectra of each product during the preparation of example 1;
FIG. 3 is a graph of the infrared spectra of the polymers of each product and the final product of the preparation of example 5;
FIG. 4 is a graph showing the effect of the antifouling property test on the antifouling coatings prepared in examples 10 to 15.
Detailed Description
The modified nano-silver particles of the first aspect of the invention are raspberry-like structures, and comprise nano-silver particles as an inner core and a tannic acid shell layer coated outside the nano-silver particles, wherein nano-silica particles are loaded on the surface of the tannic acid shell layer.
In the modified nano silver particles, the nano silver particles are coated by the tannic acid to form a nano-scale core-shell structure, the tannic acid is grafted on the surfaces of the nano silver particles to modify the surfaces of the nano silver particles, so that the next step of silicon dioxide loading is facilitated, and in addition, the tannic acid has certain protein resistance and antifouling performance, and the antifouling effect of the silver particles can be further improved due to the conjugation effect; and the nano silicon dioxide particles are loaded on the surface of the tannin shell layer, so that the rate of silver ions released by the silver particles in the air or in the case of a small amount of water can be reduced. Meanwhile, the silicon dioxide is loaded on the surface of the tannin shell layer in a particle form to form a raspberry-shaped structure, and the silicon dioxide has good thermal stability and physical and chemical stability and has high specific surface area when being loaded on the surface of the tannin shell layer in a particle form, so that the synergistic effect of the nano silver particles can be increased; the finally obtained modified nano silver particles with raspberry-shaped structures can better exert the antifouling effect, reduce the occurrence of agglomeration and reduce the release speed of silver ions.
In the modified silver nanoparticles according to the first aspect of the present invention, the modified silver nanoparticles are obtained by reacting silver nanoparticles with tannic acid and ethyl orthosilicate; the silver nanoparticles are prepared by reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol; wherein the mass ratio of the silver nitrate to the polyvinylpyrrolidone, the glycol, the tannic acid and the ethyl orthosilicate is 0.1-2: 0.05-10: 10-500: 0.1-2: 0.005-0.20; preferably 0.5 to 2: 0.1-10: 50-250: 0.5-1.5: 0.015-0.06.
In the modified nano silver particles, the mass ratio of silver nitrate, polyvinylpyrrolidone, tannic acid and ethyl orthosilicate is reasonably controlled, so that the modified nano silver particles can be efficiently prepared, and the antifouling property of the prepared modified nano silver particles is improved.
The preparation method of the modified nano silver particles of the second aspect of the invention comprises the following steps:
step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain nano silver particles;
step 20, dispersing the nano silver particles obtained in the step 10 in ethanol, adding an ethanol solution of tannic acid for reaction to obtain tannic acid modified nano silver particles with a core-shell structure;
and step 30, dispersing the nano silver particles with the core-shell structure modified by the tannic acid obtained in the step 20 in ethanol, adding water, and then adding an ethanol solution of ethyl orthosilicate for reaction to obtain the modified nano silver particles.
In the preparation method of the modified nano silver particles, silver nitrate, polyvinylpyrrolidone and glycol are added into a reaction system together for reaction; the polyvinylpyrrolidone can be used for stabilizing and dispersing the nano silver particles, so that the agglomeration phenomenon of the nano silver particles is reduced, and the further modification of the ethylene glycol can be facilitated; the glycol can be used for modifying the surface of the nano silver particles so as to facilitate the tannin grafting on the surface of the nano silver particles; the tannin is grafted on the surface of the nano silver particles, so that the antifouling effect of the nano silver particles can be improved, and preparation can be made for the next step of grafting silicon dioxide.
In the second aspect of the present invention, in the step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in the ethylene glycol is 100-; preferably, in the step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in the ethylene glycol is 100-150 ℃, and the reaction time is 6-24 h.
In the second aspect of the present invention, in the step 10, an organic solvent is added to a reaction product of silver nitrate and polyvinylpyrrolidone, and the modified silver nanoparticles are obtained by centrifugation and ultrasonic washing. Wherein the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of acetone or isopropanol.
In the method for preparing modified silver nanoparticles according to the second aspect of the present invention, in step 20, the reaction between the silver nanoparticles and the tannic acid is performed in a reaction system having a pH of 8 to 10, at a reaction temperature of 23 to 25 ℃ for 6 to 48 hours; preferably, in step 20, the reaction between the silver nanoparticles and the tannic acid is performed in a reaction system with a pH of 9, the reaction temperature is 23 to 25 ℃, and the reaction time is 12 to 24 hours.
In the preparation method of the modified silver nanoparticles of the second aspect of the present invention, in step 30, the reaction between the silver nanoparticles with core-shell structure modified by tannic acid and the ethyl orthosilicate is performed in a reaction system with pH of 8-10, the reaction temperature is 23-25 ℃, and the reaction time is 6-48 h; preferably, in step 30, the reaction between the tannic acid modified silver nanoparticles having a core-shell structure and the tetraethoxysilane is performed in a reaction system at a pH of 9, the reaction temperature is 23 to 25 ℃, and the reaction time is 12 to 24 hours.
The silane compound of the third aspect of the present invention is obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, γ -methacryloxypropyltrimethoxysilane, and (3-aminopropyl) triethoxysilane under initiation of an initiator.
The silane compound of the third aspect of the present invention is named GHMK by the initials of its reactants glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, gamma-methacryloxypropyltrimethoxysilane MPS and (3-aminopropyl) triethoxysilane KH-550.
The silane compound is synthesized by using glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane, the cost of monomers for synthesizing products is low, and the synthesized silane compound GHMK can be self-crosslinked to form a polysilane compound PGHMK with a network structure after being cured and has higher mechanical strength.
In the silane-based compound according to the third aspect of the present invention, the molar ratio of the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ -methacryloxypropyltrimethoxysilane, and the (3-aminopropyl) triethoxysilane is 1 to 9: 1-9: 1-6: 1-3; preferably 1 to 6: 1-3: 2-4: 1-2.
In the silane compound, the reaction efficiency and the reaction completeness can be improved by reasonably controlling the molar ratio of glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane; and the silane compound prepared by the molar ratio is added into the antifouling paint, so that the antifouling paint has a good film forming effect, no bubbles are generated after film forming, the film forming thickness is moderate, and the adhesive force is good.
In the silane-based compound according to the third aspect of the invention, the initiator is azobisisobutyronitrile; the mass percentage of the azodiisobutyronitrile in the reaction system is 0.01-10 wt%; preferably, the mass ratio of the azobisisobutyronitrile in the reaction system is 0.1 to 5 wt%.
The method for preparing a silane compound of the fourth aspect of the present invention comprises the steps of:
step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound;
and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.
The preparation method of the silane compound has the advantages of simple synthesis method and low VOC in the synthesis process.
In the method for preparing silane compounds according to the fourth aspect of the present invention, the intermediate compound obtained in step 40 is named GHM by the initials of glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, gamma-methacryloxypropyltrimethoxysilane MPS.
In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 40, the reaction of glycidyl methacrylate, hydroxyethyl methacrylate and γ -methacryloxypropyltrimethoxysilane is performed in a polar organic solvent; preferably, the polar organic solvent is selected from methanol or isopropanol.
In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 40, the reaction temperature of the glycidyl methacrylate, the hydroxyethyl methacrylate and the gamma-methacryloxypropyltrimethoxysilane is 60 to 120 ℃, and the reaction time is 0.5 to 12 hours; preferably, in step 40, the reaction temperature of the glycidyl methacrylate, the hydroxyethyl methacrylate and the gamma-methacryloxypropyltrimethoxysilane is 60-90 ℃ and the reaction time is 1-6 h.
In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 50, the reaction temperature of the intermediate compound with (3-aminopropyl) triethoxysilane is 40-60 ℃, and the reaction time is 0.5-10 h; preferably, in step 50, the reaction temperature of the intermediate compound and (3-aminopropyl) triethoxysilane is 45-55 ℃ and the reaction time is 2-5 h.
In the method for preparing a silane compound according to the fourth aspect of the present invention, in step 50, a reaction product of an intermediate compound and (3-aminopropyl) triethoxysilane is cooled to room temperature, excess reaction liquid is spun off, a concentrated liquid obtained by the spin-evaporation is dropped into an organic solvent, and a white transparent liquid is obtained by washing a plurality of times, and the concentrated liquid is obtained by the spin-evaporation of the white transparent liquid, and the silane compound is obtained. Wherein the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of n-hexane or acetone.
The antifouling paint of the fifth aspect of the present invention includes at least one of the modified nano silver particles and the silane-based compound.
After the modified nano silver particles are coated with the nano silver particles through the tannic acid and loaded through the silicon dioxide particles, the antifouling effect is more obvious, the modified nano silver particles are suitable for an antifouling paint, can have better compatibility with the paint, and improve the antifouling performance of the antifouling paint; the modified nano silver particles have better silver ion release controllability, so that the antifouling coating containing the modified nano silver particles has the advantages of safety, low toxicity and environmental friendliness. The silane compound can form a network structure after self-crosslinking after being cured, and can improve the mechanical strength of an antifouling coating when being added into an antifouling coating; the silane compound has certain low surface energy and protein resistance, and can effectively inhibit the adsorption of microorganisms in marine environment. When the antifouling paint simultaneously comprises the modified nano silver particles and the silane compound, the modified nano silver particles and the silane compound are not simply compounded by nano particles and a coating, but are mutually connected through covalent bonds and van der Waals force, so that the antifouling paint has a better combination effect, and is particularly suitable for the severe condition requirement and the environment-friendly requirement of marine antifouling.
In the antifouling paint according to the fifth aspect of the present invention, the mass ratio of the modified silver nanoparticles to the silane-based compound is 0.001 to 0.05: 0.5 to 5; preferably 0.004 to 0.032: 1-4.5.
The method for producing an antifouling paint of the sixth aspect of the present invention comprises the steps of:
step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles;
step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound;
and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.
The preparation method of the antifouling paint is a low VOC process and has the advantage of environmental friendliness; and the prepared antifouling coating has excellent antifouling performance.
In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 60, the liquid dispersant is selected from any one of ethanol and methanol.
In the method of producing an antifouling paint according to the sixth aspect of the invention, in step 60, the mass concentration of the modified silver nanoparticles in the dispersion of the modified silver nanoparticles is 0.02mg/m L.
In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 70, the organic solvent is preferably methanol.
In the method of producing an antifouling paint according to the sixth aspect of the present invention, in step 80, the dispersion of modified silver nanoparticles and the solution of the silane compound are stirred at a temperature of 25 to 100 ℃ for 2 to 48 hours; preferably, in step 70, the dispersion of modified silver nanoparticles and the solution of the silane compound are stirred at a temperature of 30 to 60 ℃ for 2 to 24 hours.
The invention also provides an antifouling coating, which is formed by applying the antifouling coating on at least part of the surface of a substrate and then curing; preferably, the curing is carried out at a temperature of 40-150 ℃ and the duration of the curing is 12-72 h; more preferably, the curing is carried out at a temperature of 60-120 ℃ and the duration of the curing is 24-48 h.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Example 1
The preparation method of the modified nano silver particles comprises the following steps:
step 10, weighing 0.50g of silver nitrate and 1.50g of polyvinylpyrrolidone into a 500m L single-neck flask, adding 400m L of ethylene glycol, heating to 130 ℃, stirring for 30-60min, stopping stirring, continuously heating for 46h, then cooling to room temperature, adding 500m L of acetone, and obtaining nano silver particles after centrifugation and ethanol washing, wherein the result is shown in figure 1 (a);
step 20, dispersing the nano silver particles obtained in the step 10 in 10m L ethanol to obtain ethanol dispersion liquid of the nano silver particles, adding 80m L ethanol and 20m L distilled water, and adjusting the pH of the dispersion liquid to 9 by using ammonia water, dissolving 0.125g of tannic acid in 10m L ethanol, dropwise adding the tannic acid into the ethanol dispersion liquid of the nano silver particles, reacting for 24 hours at room temperature, and obtaining the nano silver particles modified by the tannic acid and having a core-shell structure after centrifugation and ultrasonic washing, wherein the result is shown in a figure 1 (b);
and 30, dispersing the tannic acid modified nano silver particles with the core-shell structure obtained in the step 20 in 200m L ethanol, adding 50m L of distilled water, adjusting the pH to 9 with ammonia water, dissolving 55 mu L of tetraethoxysilane in 10m L of ethanol, dropwise adding the mixture into the dispersion of the tannic acid modified nano silver particles with the core-shell structure, reacting at room temperature for 24 hours, centrifuging, and washing with ethanol to obtain the modified nano silver particles, wherein the result is shown in figure 1 (c).
As can be seen from fig. 1(a), the surface of the nano silver particles has a thin organic layer; as can be seen from fig. 1(b), the thickness of the organic layer on the surface of the nano silver particles increases after the Tannin (TA) is grafted, forming a tannin shell layer; as can be seen from fig. 1(c), after adding tetraethoxysilane, the surface of the tannin shell layer is loaded with silica particles, and the modified nano silver particles are integrally formed into a raspberry-like structure.
Meanwhile, the products obtained in the steps 10, 20 and 30 are analyzed by an ultraviolet-visible absorption spectrometry, as can be seen from an ultraviolet-visible absorption spectrogram in fig. 2, the maximum absorption wavelength of the nano silver particles (named as Ag in fig. 2) prepared in the step 10 is 432nm, and the tannic acid is modified in the step 20The maximum absorption wavelength of the nano silver particles (named as Ag @ TA in figure 2) with the core-shell structure modified by the tannic acid is 453nm, and the modified nano silver particles (named as Ag @ TA-SiO in figure 2) are obtained after the modification of the tetraethoxysilane in the step 302) Has a maximum absorption wavelength of 467 nm.
Examples 2 to 4
Examples 2-4 were prepared substantially as in example 1, except that the contents of silver nitrate, polyvinylpyrrolidone, ethylene glycol, tannic acid, and ethyl orthosilicate in examples 2-4 were as shown in Table 1.
Example 5
The preparation method of the silane compound GHMK is as follows:
step 40, taking 0.018mol of glycidyl methacrylate, 0.009mol of hydroxyethyl methacrylate and 0.003mol of gamma-methacryloxypropyltrimethoxysilane into a three-neck flask, adding 120m of L methanol, adding azobisisobutyronitrile, removing oxygen, and reacting at 80 ℃ for 8 hours under the condition of nitrogen to obtain an intermediate compound GHM;
and step 50, reducing the temperature of the intermediate compound GHM obtained in the step 40 to 50 ℃, then adding 0.006mol of (3-aminopropyl) triethoxysilane into the intermediate compound GHM, keeping the temperature at 50 ℃, continuously stirring and reacting for 6 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation to remove redundant reaction liquid, dropping concentrated liquid obtained after the rotary evaporation into n-hexane, washing for multiple times to obtain white transparent liquid, and performing rotary evaporation to obtain concentrated liquid, namely the silane compound GHMK.
Infrared spectroscopic analysis was performed on the intermediate compound GHM obtained in step 40, the silane compound GHMK product obtained in step 50, and the cured polymer PGHMK product obtained in step 50, and the analysis results are shown in fig. 3.
Examples 6 to 8
Examples 6 to 8 were prepared in substantially the same manner as in example 5 except that the contents of glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane, (3-aminopropyl) triethoxysilane in examples 6 to 8 were as shown in Table 1.
Example 9
The preparation method of the antifouling paint comprises the following steps:
step 60, dispersing 0.01g of the modified nano-silver particles prepared in step 30 in example 1 in ethanol to obtain ethanol dispersion of the modified nano-silver particles;
step 70, dissolving 3.0g of the silane compound GHMK prepared in the step 50 in the example 5 in methanol to obtain a methanol solution of the silane compound GHMK;
and step 80, stirring the ethanol dispersion liquid of the modified nano silver particles obtained in the step 60 and the methanol solution of the silane compound GHMK obtained in the step 70 at 40-50 ℃ for 12-24 hours, and performing rotary evaporation to obtain a concentrated liquid, namely the antifouling paint.
Applying the prepared antifouling paint on a clean substrate by adopting a spin coating method; and then curing for 6 hours in an oven at the temperature of 80-120 ℃ to obtain the antifouling coating applied on the substrate.
Examples 10 to 15
The preparation methods of examples 10 to 15 are substantially the same as those of example 9, except that the contents of the modified nano silver particles and the silane compounds in examples 10 to 12 are shown in Table 1.
For convenience of explanation, symbols are used in table 1 below to represent substances:
A1: silver nitrate
A2: polyvinylpyrrolidone
A3: ethylene glycol
A4: tannic acid
A5: tetraethoxysilane
B1: glycidyl methacrylate
B2: hydroxyethyl methacrylate
B3: gamma-methacryloxypropyltrimethoxysilane
B4: (3-aminopropyl) triethoxysilane
C1: modified nano silver particles
C2: silane compound
The following describes the test procedure and test results for the antifouling coating.
1) Test procedure
Clean glass sheets are used as the coating substrate of the antifouling paint.
The antifouling paints prepared in examples 10 to 15 were applied on clean substrates by spin coating to form paint layers, which were then cured in an oven at 80 to 120 ℃ for 6 hours to obtain clean glass sheets with different antifouling coatings as experimental groups 1 to 7. Meanwhile, a clean glass plate without any antifouling paint was used as a control.
Placing glass sheets of experimental group 1-7 and control group into Nitzschia closterium (3 × 10)5cell/m L), after culturing for 8 days in a simulated marine environment, removing nitzschia closterium which does not adhere to the surfaces of the glass flake and the antifouling coating, dyeing with a dyeing agent, washing with PBS, and observing under a fluorescence microscope.
2) Test results
The observation results are shown in FIG. 4, in which FIG. 4(a) is the test results of the control group, and FIGS. 4(b) - (h) are the test results of the experimental groups 1-7 in this order. It can be seen that the antifouling paint applied on the surface of the glass sheet has obvious antifouling effect after being cured to form the antifouling coating. The antifouling effect of the experimental group 1 without the modified silver nanoparticles is better than that of the control group, but the antifouling effect is far less than that of the experimental groups 2-7 with the modified silver nanoparticles. As can be seen from the comparison between fig. 4(c) - (h) and fig. 4(b), although only a very small amount of modified nano silver particles are added, the antifouling performance of the antifouling coating is remarkably enhanced, which indicates that the addition of the modified nano silver particles has a synergistic composite effect on the PGHMK; and, with the increase of the content of the modified nano silver particles, the antifouling effect becomes better.
Claims (11)
1. The silane compound is characterized by being obtained by reacting glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyltrimethoxysilane and (3-aminopropyl) triethoxysilane under the initiation of an initiator.
2. The silane compound according to claim 1, wherein the molar ratio of the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ -methacryloxypropyltrimethoxysilane, and the (3-aminopropyl) triethoxysilane is 1 to 9: 1-9: 1-6: 1-3.
3. The silane compound according to claim 2, wherein the molar ratio of the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ -methacryloxypropyltrimethoxysilane, and the (3-aminopropyl) triethoxysilane is 1 to 6: 1-3: 2-4: 1-2.
4. The silane compound according to claim 1, wherein the initiator is azobisisobutyronitrile; the mass percentage of the azodiisobutyronitrile in the reaction system is 0.01-10 wt%.
5. A silane compound according to claim 4, wherein the mass ratio of azobisisobutyronitrile in the reaction system is 0.1 to 5 wt%.
6. A method for producing a silane compound, which is used for producing the silane compound according to any one of claims 1 to 5, comprising the steps of:
step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyl trimethoxysilane under the initiation of an initiator to obtain an intermediate compound;
and step 50, reacting the intermediate compound obtained in the step 40 with (3-aminopropyl) triethoxysilane to obtain the silane compound.
7. An antifouling paint comprising the silane compound according to claim 1.
8. The antifouling paint according to claim 7, further comprising modified silver nanoparticles having a raspberry-like structure, wherein the modified silver nanoparticles comprise silver nanoparticles as an inner core and a tannic acid shell coated on the silver nanoparticles, and wherein the tannic acid shell is loaded with nano silica particles on the surface.
9. The antifouling paint according to claim 8, wherein the mass ratio of the modified silver nanoparticles to the silane compound is 0.001-0.05: 0.5-5.
10. The antifouling paint according to claim 9, wherein the mass ratio of the modified silver nanoparticles to the silane compound is 0.004 to 0.032: 1-4.5.
11. A method for producing an antifouling paint according to any one of claims 8 to 10, comprising the steps of:
step 60, dispersing the modified nano silver particles in a liquid dispersing agent to obtain a dispersion liquid of the modified nano silver particles;
step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound;
and step 80, mixing and stirring the dispersion liquid of the modified nano silver particles obtained in the step 60 and the solution of the silane compound obtained in the step 70, and performing rotary evaporation to obtain a concentrated transparent liquid, namely the antifouling paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910964230.2A CN110591159B (en) | 2019-10-11 | 2019-10-11 | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910964230.2A CN110591159B (en) | 2019-10-11 | 2019-10-11 | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110591159A CN110591159A (en) | 2019-12-20 |
| CN110591159B true CN110591159B (en) | 2020-07-10 |
Family
ID=68866552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910964230.2A Active CN110591159B (en) | 2019-10-11 | 2019-10-11 | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110591159B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111202091A (en) * | 2020-01-08 | 2020-05-29 | 华南理工大学 | Nano-silver loaded mesoporous silica antibacterial material and preparation method and application thereof |
| CN113773709A (en) * | 2021-09-03 | 2021-12-10 | 北京科技大学 | Self-warning and self-repairing dual-functional coating based on natural polyphenol filler and preparation |
| CN116239905B (en) * | 2022-06-21 | 2024-01-26 | 青岛科技大学 | Preparation method of marine anti-corrosion and anti-fouling multi-effect coating material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863154B (en) * | 2012-10-18 | 2014-07-16 | 齐鲁工业大学 | Method for preparing super-hydrophobicity surfaces |
| CN104497573B (en) * | 2014-12-02 | 2017-01-11 | 中国科学院化学研究所 | Silicone rubber composition |
| CN104607654B (en) * | 2015-02-10 | 2016-06-22 | 济南大学 | A kind of self-assembled material based on silver nano-grain and preparation method thereof |
| US20160243049A1 (en) * | 2015-02-19 | 2016-08-25 | Washington University | Nanoraspberries for photothermal cancer therapy |
| CN106964785A (en) * | 2017-04-20 | 2017-07-21 | 中国科学院深圳先进技术研究院 | A kind of preparation method of nano-Ag particles |
| WO2019088922A1 (en) * | 2017-10-30 | 2019-05-09 | Agency For Science, Technology And Research | Hollow silica spheres with raspberry-like structure and method for preparation thereof |
| CN108543505B (en) * | 2018-04-24 | 2020-04-28 | 中广核俊尔新材料有限公司 | Composite particle with multiple core-shell structures and preparation method thereof |
| CN109135487B (en) * | 2018-07-19 | 2020-11-06 | 重庆大学 | Organic silicon modified acrylic resin super-hydrophilic antifogging coating and preparation method thereof |
-
2019
- 2019-10-11 CN CN201910964230.2A patent/CN110591159B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110591159A (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110591159B (en) | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof | |
| EP3065884B1 (en) | Anticorrosion layer and process for production thereof | |
| KR20110003535A (en) | Ultrahydrophobic powder, structure with ultrahydrophobic surface, and processes for producing these | |
| KR101624372B1 (en) | Resin-coated metallic pigment, water-based paint containing same, painted item to which same has been applied, and manufacturing method for same | |
| WO2007119023A2 (en) | Use of a nanostructured material, as protective coating of metal surfaces | |
| JP2003502473A (en) | Self-polishing marine antifouling coating composition comprising silicon-containing copolymer and fiber | |
| WO2011068596A2 (en) | Polymer encapsulated aluminum particulates | |
| Deng et al. | Fabrication and synergistic antibacterial and antifouling effect of an organic/inorganic hybrid coating embedded with nanocomposite Ag@ TA-SiO2 particles | |
| CN110621747A (en) | Composite resin containing silver nanoparticles | |
| CN111944369A (en) | Antibacterial anticorrosive paint for building exterior wall and preparation method thereof | |
| WO2020022431A1 (en) | Antifouling paint composition, antifouling coating, substrate with antifouling coating, production method thereof, and repair method | |
| CN109366653B (en) | Long-acting mildew-proof wear-resistant processing method for bamboo wood | |
| CN115433497A (en) | Antifouling and antibacterial water-based wood paint and preparation method thereof | |
| CN113512160B (en) | Method for preparing antifouling surface by grafting organic-inorganic hybrid particle to lubricating oil | |
| DE19935230C2 (en) | Biofilm inhibitor | |
| CN113880996A (en) | Multifunctional marine antifouling coating resin and preparation method thereof | |
| CN108485452B (en) | Water-based paint suitable for wooden products and preparation method thereof | |
| CN114806312A (en) | Preparation method of polybenzazole modified graphene oxide/fluoroboric acrylate composite antifouling coating | |
| CN110698901B (en) | Capsaicin anti-fouling agent embedded and treated by acrylic resin and preparation method and application thereof | |
| CN113166579B (en) | Organic-inorganic nano composite antifouling coating for environment-friendly antifouling paint and preparation method thereof | |
| Pan et al. | Anti-bioadhesive polyurethane coatings enhanced by salicylic acid-carboxy-betaine modified nano-silica: Stepwise antifouling mechanism | |
| CN114702879B (en) | Anti-corrosion antifouling coating and preparation method thereof | |
| CN104892662A (en) | Preparation method of long chain terminal hydroxyl-containing silane coupling agent and application thereof | |
| CN115584175B (en) | Silica sol-hydroxy acrylic resin composite-dispersion and preparation method thereof | |
| CN113897117B (en) | Industrial coating capable of resisting marine organism fouling 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |