CN112694833A - Composite low-surface-energy antifouling paint containing basalt fiber powder and scale powder and preparation method thereof - Google Patents
Composite low-surface-energy antifouling paint containing basalt fiber powder and scale powder and preparation method thereof Download PDFInfo
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- CN112694833A CN112694833A CN202011569347.XA CN202011569347A CN112694833A CN 112694833 A CN112694833 A CN 112694833A CN 202011569347 A CN202011569347 A CN 202011569347A CN 112694833 A CN112694833 A CN 112694833A
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- 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
- C09D5/1675—Polyorganosiloxane-containing compositions
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- 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
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- 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
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Abstract
The invention provides a low surface energy antifouling paint, which comprises an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1; the antifouling component comprises a diluent and the following raw materials in parts by weight: 2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin; the functional basalt scales are silane-modified basalt scales. The method comprises the steps of mixing and ball-milling basalt fiber powder, basalt flakes, cuprous oxide and copper powder according to a certain proportion, and adding powder with a special micro-nano structure after ball milling into polysiloxane resin to prepare the antifouling paint. The antifouling paint has the characteristics of excellent antifouling performance, good mechanical performance, environmental protection and economy. Experimental results show that the antifouling coating prepared by the method has greatly reduced attachment rates of microorganisms, plants and animals.
Description
Technical Field
The invention relates to the technical field of coating materials, in particular to a low-surface-energy antifouling paint and a preparation method thereof.
Background
The ocean covers about 70% of the earth's surface, and is of great value for marine exploration or marine transportation, while mechanical equipment such as ships, submarines, deep sea detectors are important parts of marine transportation, military strategy or marine exploration. However, the seawater contains a large amount of microorganisms, plants and animals, which can adhere to the parts of the equipment immersed in the seawater, and have adverse effects on the parts, so that the performance of the equipment is reduced and even damaged, and the phenomenon is the biofouling phenomenon. To ameliorate this phenomenon, the development of marine fouling coatings has begun to be widely utilized.
The marine antifouling coating can prevent the marine equipment from being attached by fouling organisms, so that the damage speed of the equipment is reduced, but the antifouling agent which is widely used in the market at present has a protection effect on microorganisms, and can cause certain damage to the environment, so that marine pollution is caused, and the natural environment and the marine health are damaged.
In order to meet the environmental protection theme of the modern times, the pursuit of environment-friendly protective coatings is the current development trend and requirement, so that an important future development direction of antifouling coatings is low toxicity and no toxicity. Therefore, the development of the composite low-surface-energy antifouling paint can be quite suitable for the current theme of the environmental protection era.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low surface energy antifouling paint, which has excellent antifouling performance and is environment-friendly.
The invention provides a low surface energy antifouling paint, which comprises an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1;
the antifouling component comprises a diluent and the following raw materials in parts by weight:
2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin;
the functional basalt scales are silane-modified basalt scales.
Preferably, the preparation method of the functionalized basalt scales specifically comprises the following steps:
mixing silane, water and alcohol for hydrolytic polymerization, and then mixing and stirring the mixture with the basalt scales to obtain functional basalt scales; the pH of the polymerization is 4; the weight ratio of the silane to the water to the alcohol is 10:2: 88; the polymerization temperature is 50-70 ℃; the polymerization time is 4-6 h; the stirring time is 1-2 h.
Preferably, the silane is selected from one or more of glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and isooctyltriethoxysilane.
Preferably, the basalt fiber powder is powder remained in the basalt fiber drawing process.
Preferably, the length of the basalt fiber is 40 micrometers; the diameter of the basalt scale is 5 micrometers, and the diameter of the basalt scale is 9-11 micrometers.
Preferably, the diameter of the copper powder is 19-21 microns; the diameter of the cuprous oxide powder is 4-6 microns.
Preferably, the diluent is a mixture of an alcohol solvent and an active diluent, and the alcohol solvent is one or more of ethanol, isopropanol and butanol; the reactive diluent is one or more of C12-C14 alkyl glycidyl ether; wherein the alcohol accounts for 5-15% of the diluent by mass, and the active diluent accounts for 5-15% of the diluent by mass.
Preferably, the curing component comprises a curing agent; the curing agent is one or more of monoamino silane KH550 or bisamino silane KH 972.
The invention provides a preparation method of the low surface energy antifouling paint, which comprises the following steps:
A) mixing the functional basalt flakes and basalt fiber powder, and performing ball milling to obtain a basalt mixed material;
B) mixing and ball-milling the basalt mixed material, the copper powder and the cuprous oxide to obtain a composite antifouling agent;
C) uniformly dispersing the composite antifouling agent, polysiloxane resin and a diluent at a high speed according to a ratio to obtain an antifouling component;
D) and respectively packaging the antifouling component and the curing component consisting of the curing agent to obtain the low-surface-energy antifouling paint.
Preferably, the ball milling time in the step A) is 2-3 h; and B), the ball milling time is 8-10 h.
Compared with the prior art, the invention provides a low-surface-energy antifouling paint which comprises an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1; the antifouling component comprises a diluent and the following raw materials in parts by weight: 2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin; the functional basalt scales are silane-modified basalt scales. The method comprises the steps of mixing and ball-milling basalt fiber powder, basalt flakes, cuprous oxide and copper powder according to a certain proportion, and adding powder with a special micro-nano structure after ball milling into polysiloxane resin to prepare the antifouling paint. The antifouling paint has the characteristics of excellent antifouling performance, good mechanical performance, environmental protection and economy. The experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared by the method is more than 128 degrees, and after six months, the fungus adhesion amount, the algae adhesion amount and the protein adhesion amount of the low-surface-energy antifouling coating are not higher than 3.5%, 5.2% and 11.3%, respectively.
Drawings
FIG. 1 is a surface map of a low surface energy anti-fouling coating after six months of testing in example 5 of the present invention;
FIG. 2 is a surface map of a low surface energy anti-fouling coating after six months of testing in example 3 of the invention.
Detailed Description
The invention provides a low-surface-energy antifouling paint and a preparation method thereof, and a person skilled in the art can use the contents for reference and appropriately improve the process parameters to realize the antifouling paint. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a low surface energy antifouling paint, which comprises an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1;
the antifouling component comprises a diluent and the following raw materials in parts by weight:
2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin;
the functional basalt scales are silane-modified basalt scales.
The invention provides a low surface energy antifouling paint which comprises an antifouling component.
The antifouling component comprises 2-4 parts by weight of basalt fiber powder; specifically, it may include 2 parts by weight, 3 parts by weight or 4 parts by weight.
The basalt fiber powder is powder remained in the basalt fiber drawing process. The length of the basalt fiber is 40 micrometers; the diameter was 5 microns.
The antifouling component comprises 2-5 parts by weight of functionalized basalt flakes; specifically, it may include 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.
The functional basalt scales are silane-modified basalt scales.
The preparation method of the functionalized basalt flakes preferably comprises the following steps:
and mixing silane, water and alcohol for hydrolysis polymerization, and then mixing and stirring the mixture with the basalt scales to obtain the functional basalt scales. Filtering and drying after stirring to obtain functionalized basalt flakes; the drying temperature is preferably 80-90 ℃. The present invention is not limited to the specific stirring method and the specific filtration method, and those skilled in the art will be familiar with them.
The pH value of the hydrolytic polymerization is 4; the pH regulation of the invention can be one or a mixture of more of acetic acid, sulfuric acid, nitric acid, acrylic acid and methacrylic acid. The weight ratio of silane, water and alcohol is preferably 10:2: 88; the polymerization temperature is preferably 50-70 ℃; more preferably 55-65 ℃; most preferably 60 ℃; the polymerization time is preferably 4-6 h; more preferably 5 h. The stirring time is 1-2 h.
The silane is selected from one or more of glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and isooctyltriethoxysilane. The present invention is not limited in its source, and may be commercially available.
The diameter of the functionalized basalt scales is preferably 9-11 micrometers; more preferably 9.6 to 10.4 μm.
The antifouling component comprises 1 part by weight of copper powder. The diameter of the copper powder is preferably 19-21 micrometers; more preferably 19.5 to 20.5 μm.
The antifouling component of the invention comprises 1 weight part of cuprous oxide. The diameter of the cuprous oxide powder is preferably 4-6 microns; more preferably 4.5 to 5.5 μm.
The antifouling component comprises 10-65 parts by weight of polysiloxane resin; preferably 15 to 60 parts by weight.
The invention uses polysiloxane resin as film forming material.
The antifouling component of the invention comprises a diluent preferably in an amount of 10 to 25 parts by weight.
The invention adopts polysiloxane resin as a film forming material, and the content of the polysiloxane resin is 10-65%; the content of the basalt antifouling component with complex phase composition and special structure is 35-60%, the diluent used in the invention is a mixture of an alcohol solvent and an active diluent, and the alcohol solvent is one or more of ethanol, isopropanol and butanol; the reactive diluent is one or more of C12-C14 alkyl glycidyl ether. Wherein the alcohol accounts for 5-15% of the diluent by mass, and the active diluent accounts for 5-15% of the diluent by mass. The antifouling component of the invention also comprises other additives, such as zinc oxide, titanium oxide and ferric oxide, the contents of which are respectively 10-20%, 15-25% and 0-20% of the resin content.
The invention provides a low surface energy antifouling paint which comprises a curing component.
According to the invention, the weight ratio of the antifouling component to the curing component is 4-8: 1; preferably 4:1, 5:1, 4:1, 6:1, 7:1 or 8: 1.
The curing component of the present invention comprises a curing agent; the curing agent is one or more of monoamino silane KH550 or bisamino silane KH 972.
The method comprises the steps of mixing and ball-milling basalt fiber powder, basalt flakes, cuprous oxide and copper powder according to a certain proportion, adding powder with a special micro-nano structure after ball milling as an antifouling agent into polysiloxane resin to prepare the antifouling coating so as to achieve the purpose of low surface energy. The invention prevents the attachment of organisms on the surface by a physical and chemical synergistic effect method, belongs to an environment-friendly anti-fouling method, and plays a good role in protecting the marine environment.
The invention provides a preparation method of the low surface energy antifouling paint, which comprises the following steps:
A) mixing the functional basalt flakes and basalt fiber powder, and performing ball milling to obtain a basalt mixed material;
B) mixing and ball-milling the basalt mixed material, the copper powder and the cuprous oxide to obtain a composite antifouling agent;
C) uniformly dispersing the composite antifouling agent, polysiloxane resin and a diluent at a high speed according to a ratio to obtain an antifouling component;
D) and respectively packaging the antifouling component and the curing component consisting of the curing agent to obtain the low-surface-energy antifouling paint.
The preparation method of the low surface energy antifouling paint comprises the steps of mixing the functionalized basalt flakes and the basalt fiber powder, and performing ball milling to obtain the basalt mixed material. The ball milling time is 2-3 h.
The above-mentioned method for preparing the functionalized basalt flakes has been clearly described, and is not repeated herein.
The basalt fiber powder is powder remained in the basalt fiber drawing process. The length of the basalt fiber is 40 micrometers; the diameter was 5 microns. The drawing process is not limited by the present invention and is well known to those skilled in the art.
The weight ratio of the functionalized basalt flakes to the basalt fiber powder is preferably (2-5): (2-4).
And mixing and ball-milling the basalt mixed material, the copper powder and the cuprous oxide to obtain the composite antifouling agent.
The invention preferably comprises the following components in a mass ratio of 5-8: 1: and 1, mixing the basalt mixed material, copper powder and cuprous oxide, and putting the mixture into a ball milling tank for ball milling for 8-10 hours to obtain the composite antifouling agent with the micro-nano structure.
And uniformly dispersing the composite antifouling agent, polysiloxane resin and a diluent at a high speed according to a proportion to obtain an antifouling component.
Uniformly dispersing the obtained composite antifouling agent, polysiloxane resin and diluent in proportion at a high speed to obtain a mixture serving as a component A; the component B is a curing agent and is packaged independently. A: the weight ratio of B is 4-8: 1. namely subpackaging the mixture antifouling paint and the curing agent.
The weight ratio of the composite antifouling agent to the polysiloxane resin and the diluent is preferably (1-2) to (2-5): (3-12); more preferably, the weight ratio of the composite antifouling agent to the polysiloxane resin and the diluent is (1-2): (2-5): (5-12); specifically, the ratio may be 1:3:9, 1:3:11, 2:2:9, 2:2:11, 2:3:9, or 2:3: 11.
The invention provides a low surface energy antifouling paint, which comprises an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1; the antifouling component comprises a diluent and the following raw materials in parts by weight: 2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin; the functional basalt scales are silane-modified basalt scales. The method comprises the steps of mixing and ball-milling basalt fiber powder, basalt flakes, cuprous oxide and copper powder according to a certain proportion, and adding powder with a special micro-nano structure after ball milling into polysiloxane resin to prepare the antifouling paint. The antifouling paint has the characteristics of excellent antifouling performance, good mechanical performance, environmental protection and economy. The experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared by the method is more than 128 degrees, and after six months, the fungus adhesion amount, the algae adhesion amount and the protein adhesion amount of the low-surface-energy antifouling coating are not higher than 3.5%, 5.2% and 11.3%, respectively.
In order to further illustrate the present invention, the following will describe a low surface energy antifouling paint and a preparation method thereof in detail with reference to examples.
Example 1
A solution of 10 parts of methyltrimethoxysilane, 2 parts of water and 88 parts of alcohol was prepared, and the polymerization was carried out by hydrolysis in an environment of constant temperature of 60 ℃ at a pH of 4 for 5 hours. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 5:1:1, and then ball-milling for 8 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, the obtained composite antifouling agent, polysiloxane resin and diluent are uniformly dispersed at a high speed according to the mass ratio of 1:3:9 to obtain a mixture, the mixture is used as a component A, and the component B is a curing agent monoamino silane KH550 which are respectively and independently packaged. A: the weight ratio of B is 4: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion resistance and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 128.2 degrees; after six months, the amount of fungus attached to the low surface energy antifouling coating was 3.5%, the amount of algae attached was 4.2%, and the amount of protein attached was 11.3%.
Example 2
A solution comprising 10 parts of ethyltriethoxysilane, 2 parts of water and 88 parts of an alcohol was prepared, and the mixture was polymerized by hydrolysis at a constant temperature of 60 ℃ for 5 hours at a pH of 4. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 6:1:1, and then ball-milling for 9 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, the obtained composite antifouling agent, polysiloxane resin and diluent are uniformly dispersed at a high speed according to the mass ratio of 1:3:11 to obtain a mixture, the mixture is used as a component A, and the component B is a curing agent monoamino silane KH550 which are respectively and independently packaged. A: the weight ratio of B is 5: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion resistance and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 129 degrees; after six months, the amount of fungus attached to the low surface energy antifouling coating was 3%, the amount of algae attached was 4.2%, and the amount of protein attached was 10.9%.
Example 3
A solution of 10 parts of methyltrimethoxysilane, 2 parts of water and 88 parts of alcohol was prepared, and the polymerization was carried out by hydrolysis in an environment of constant temperature of 60 ℃ at a pH of 4 for 5 hours. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 7:1:1, and then ball-milling for 8 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, the obtained composite antifouling agent, polysiloxane resin and diluent are uniformly dispersed at a high speed according to the mass ratio of 2:2:9 to obtain a mixture, the mixture is used as a component A, and the component B is a curing agent bisaminosilane KH972, and the components are respectively and independently packaged. A: the weight ratio of B is 6: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion property and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 131.5 degrees; after six months, the amount of fungus attached to the low surface energy antifouling coating was 2.8%, the amount of algae attached was 4%, and the amount of protein attached was 9.5%. FIG. 2 is a surface map of a low surface energy anti-fouling coating after six months of testing in example 3 of the invention.
Example 4
A solution comprising 10 parts of isooctyltriethoxysilane, 2 parts of water and 88 parts of an alcohol was prepared, and the polymerization was carried out by hydrolysis at a pH of 4 at a constant temperature of 60 ℃ for 5 hours. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 7:1:1, and then ball-milling for 8 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, the obtained composite antifouling agent, polysiloxane resin and diluent are uniformly dispersed at a high speed according to the mass ratio of 2:2:11 to obtain a mixture, the component A is a mixture of diamino silane KH972 and monoamino silane KH550, and the mixture is packaged independently. A: the weight ratio of B is 7: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion resistance and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 128.5 degrees; after six months, the amount of fungus attached to the low surface energy antifouling coating was 3.3%, the amount of algae attached was 5.2%, and the amount of protein attached was 11.2%.
Experimental example 5
A solution of 10 parts of methacryloxypropyltrimethoxysilane, 2 parts of water and 88 parts of alcohol was prepared, and the polymerization was carried out by hydrolysis in an environment of constant temperature of 60 ℃ at a pH of 4 for 5 hours. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 8:1:1, and then ball-milling for 9 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, the obtained composite antifouling agent, polysiloxane resin and diluent are uniformly dispersed at a high speed according to the mass ratio of 2:3:9 to obtain a mixture, the mixture is a component A, and the component B is a mixture of bisaminosilane KH972 and monoaminosilane KH550, and the components are respectively and independently packaged. A: the weight ratio of B is 8: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion resistance and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 134 degrees; six months later, the amount of fungus attached to the low surface energy antifouling coating was 2.7%, the amount of algae attached was 3%, and the amount of protein attached was 8.7%. FIG. 1 is a surface map of a low surface energy anti-fouling coating after six months of testing in example 5 of the invention.
Experimental example 6
A solution of 10 parts of methacryloxypropyltrimethoxysilane, 2 parts of water and 88 parts of alcohol was prepared, and the polymerization was carried out by hydrolysis in an environment of constant temperature of 60 ℃ at a pH of 4 for 5 hours. Adding and stirring the basalt flakes for 2 hours, filtering, drying at 90 ℃ to obtain functionalized basalt flakes, mixing the functionalized basalt flakes and powder remained in the basalt fiber drawing process in a mass ratio of 1:1, and ball-milling in a ball mill for 3 hours to obtain the basalt mixed material. Mixing the basalt mixed material, copper powder and cuprous oxide according to the mass ratio of 5:1:1, and then ball-milling for 10 hours in a ball mill to obtain the composite antifouling agent with the micro-nano structure. And finally, uniformly dispersing the obtained composite antifouling agent, polysiloxane resin and diluent at a high speed according to the mass ratio of 2:3:11 to obtain a mixture, wherein the mixture is a component A, and the component B is a curing agent bisaminosilane KH972, and the components are respectively and independently packaged. A: the weight ratio of B is 8: 1.
the composite low-surface-energy antifouling coating obtained in the experimental example is subjected to surface contact angle, thermal stability, mechanical property, antibacterial adhesion property, algae adhesion property and protein adhesion resistance tests, and the experimental result shows that the contact angle of the low-surface-energy antifouling coating prepared in the embodiment is 130.9 degrees; after six months, the amount of fungus attached to the low surface energy antifouling coating was 3%, the amount of algae attached was 3.9%, and the amount of protein attached was 10%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A low surface energy antifouling paint is characterized by comprising an antifouling component and a curing component; the weight ratio of the antifouling component to the curing component is 4-8: 1;
the antifouling component comprises a diluent and the following raw materials in parts by weight:
2-4 parts of basalt fiber powder; 2-5 parts of functionalized basalt flakes; 1 part of copper powder; 1 part of cuprous oxide; 10-65 parts of polysiloxane resin;
the functional basalt scales are silane-modified basalt scales.
2. The low surface energy antifouling paint as claimed in claim 1, wherein the preparation method of the functionalized basalt flakes specifically comprises:
mixing silane, water and alcohol for hydrolytic polymerization, and then mixing and stirring the mixture with the basalt scales to obtain functional basalt scales; the pH of the polymerization is 4; the weight ratio of the silane to the water to the alcohol is 10:2: 88; the polymerization temperature is 50-70 ℃; the polymerization time is 4-6 h; the stirring time is 1-2 h.
3. The low surface energy antifouling paint according to claim 2, wherein the silane is selected from one or more of glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, and isooctyltriethoxysilane.
4. The low surface energy antifouling paint as claimed in claim 1, wherein the basalt fiber powder is a powder remaining during the drawing of basalt fiber.
5. The low surface energy antifouling paint of claim 1, wherein the basalt fiber has a length of 40 micrometers; the diameter of the basalt scale is 5 micrometers, and the diameter of the basalt scale is 9-11 micrometers.
6. The low surface energy antifouling paint according to claim 1, wherein the copper powder has a diameter of 19 to 21 μm; the diameter of the cuprous oxide powder is 4-6 microns.
7. The low surface energy antifouling paint as claimed in claim 1, wherein the diluent is a mixture of alcohol solvent and active diluent, the alcohol solvent is one or more of ethanol, isopropanol and butanol; the reactive diluent is one or more of C12-C14 alkyl glycidyl ether; wherein the alcohol accounts for 5-15% of the diluent by mass, and the active diluent accounts for 5-15% of the diluent by mass.
8. A low surface energy antifouling paint according to claim 1, wherein the curing component comprises a curing agent; the curing agent is one or more of monoamino silane KH550 or bisamino silane KH 972.
9. A method for preparing a low surface energy antifouling paint according to any one of claims 1 to 8, comprising:
A) mixing the functional basalt flakes and basalt fiber powder, and performing ball milling to obtain a basalt mixed material;
B) mixing and ball-milling the basalt mixed material, the copper powder and the cuprous oxide to obtain a composite antifouling agent;
C) uniformly dispersing the composite antifouling agent, polysiloxane resin and a diluent at a high speed according to a ratio to obtain an antifouling component;
D) and respectively packaging the antifouling component and the curing component consisting of the curing agent to obtain the low-surface-energy antifouling paint.
10. The preparation method of claim 9, wherein the ball milling time in step a) is 2-3 h; and B), the ball milling time is 8-10 h.
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