CN113956756B - Quaternary ammonium salt antibacterial anticorrosive paint, preparation method, coating preparation method and application - Google Patents
Quaternary ammonium salt antibacterial anticorrosive paint, preparation method, coating preparation method and application Download PDFInfo
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- CN113956756B CN113956756B CN202111274816.XA CN202111274816A CN113956756B CN 113956756 B CN113956756 B CN 113956756B CN 202111274816 A CN202111274816 A CN 202111274816A CN 113956756 B CN113956756 B CN 113956756B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention discloses a quaternary ammonium salt antibacterial anticorrosive paint, a preparation method, a coating preparation method and application, in the preparation method of the quaternary ammonium salt antibacterial anticorrosive paint, epoxy resin and titanium dioxide are respectively subjected to quaternary ammonium salt modification, and are mixed with butyl acetate and n-butyl alcohol, and the mixture is mixed with a curing agent before the coating is prepared by spraying to obtain the quaternary ammonium salt antibacterial anticorrosive paint; the quaternary ammonium salt antibacterial anticorrosive coating applied to the space cabin is obtained after the coating is sprayed and cured, the antibacterial rate of the coating is more than 99%, the mildew-proof grade is superior to the grade-1 standard, and the coating has good vacuum volatility, does not generate toxic gas and organic gaseous pollutants during combustion, is green and environment-friendly, and has wide application prospect in the field of space stations.
Description
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to a quaternary ammonium salt antibacterial anticorrosive coating for a space station, a preparation method and a coating preparation method.
Background
The manned space station creates a good environment for long-term residence of astronauts, and also provides favorable conditions for breeding of microorganisms. Pathogenic microorganisms can cause astronauts to become sick; fungi and mold can corrode and degrade various materials of the space station, leading to space station equipment failure, risk of platform failure and reduced sealing, and the like. The astronaut is in the space radiation environment for a long time, the autoimmunity can be reduced, the performance of space station materials can be degraded, the activity of microorganisms can be enhanced, and the harm to human bodies and space stations can be gradually increased. Therefore, there is a need to develop an antibacterial and anticorrosive coating for space stations, which can radically prevent the growth of microorganisms in the cabin of the space station. And the high index requirements of space station strict cabin coating binding force, surface density, flame retardance, environmental protection and the like provide higher requirements and challenges for the research and development of the antibacterial and mildewproof coating.
The high molecular quaternary ammonium salt has the advantages of difficult precipitation and volatilization, good heat resistance, good stability, low toxicity, low stimulation, high efficiency and the like, and is widely valued by scholars at home and abroad. However, due to the enhancement of drug resistance, single polymer quaternary ammonium salt cannot meet the broad-spectrum antibacterial requirement, and the development of a high-efficiency spectrum quaternary ammonium salt antibacterial coating is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects and provides a quaternary ammonium salt antibacterial anticorrosive paint, a preparation method, a coating preparation method and application, in the preparation method of the quaternary ammonium salt antibacterial anticorrosive paint, epoxy resin and titanium dioxide are respectively subjected to quaternary ammonium salt modification, and are mixed with butyl acetate and n-butyl alcohol, and the mixture is mixed with a curing agent before the coating is prepared by spraying to obtain the quaternary ammonium salt antibacterial anticorrosive paint; the quaternary ammonium salt antibacterial anticorrosive coating applied to the space cabin is obtained after the coating is sprayed and cured.
In order to achieve the above purpose, the invention provides the following technical scheme:
the quaternary ammonium salt antibacterial anticorrosive paint comprises a component A and a component B, wherein the component A and the component B respectively comprise the following components in parts by mass:
a component A:
b, component B:
0.5-1 part of polyamide resin curing agent;
1-2 parts of butyl acetate;
and 0.1-0.2 part of n-butyl alcohol.
The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint comprises the following steps:
step (1): the preparation of the component A specifically comprises the following steps:
(11) preparing quaternary ammonium salt modified epoxy resin;
(12) preparing quaternary ammonium salt modified titanium oxide;
(13) mixing quaternary ammonium salt modified epoxy resin, quaternary ammonium salt modified titanium oxide, butyl acetate and n-butyl alcohol to obtain a component A in the quaternary ammonium salt antibacterial anticorrosive paint; the mass parts of the quaternary ammonium salt modified epoxy resin are 1-1.5, the mass parts of the quaternary ammonium salt modified titanium oxide are 1-1.5, the mass parts of butyl acetate are 4-5, and the mass parts of n-butyl alcohol are 0.4-0.8;
step (2): preparing the component B, specifically, uniformly dispersing a polyamide resin curing agent in butyl acetate and n-butyl alcohol; the polyamide resin curing agent comprises, by mass, 0.5-1 part of a polyamide resin curing agent, 1-2 parts of butyl acetate and 0.1-0.2 part of n-butyl alcohol;
and (3): mixing the component A and the component B.
Further, in the step (11), the epoxy resin is modified by triethylamine hydrochloride to prepare the quaternary ammonium salt modified epoxy resin, and the specific method comprises the steps of mixing the epoxy resin, a triethylamine hydrochloride aqueous solution and ethanol, reacting under a heating condition, and carrying out post-treatment on a reaction product to obtain the quaternary ammonium salt modified epoxy resin.
Further, in the step (11), the mass percentage of triethylamine hydrochloride in the triethylamine hydrochloride aqueous solution is 5%; the mass ratio of the epoxy resin to the triethylamine hydrochloride aqueous solution to the ethanol is 20: 3-5: 160 to 240.
Further, in the step (11), after mixing the epoxy resin, the triethylamine hydrochloride aqueous solution and the ethanol, reacting for 5-10 hours at the temperature of 80-90 ℃;
in the step (11), the post-treatment comprises solvent removal and vacuum drying; the solvent removal is carried out under reduced pressure, and the vacuum drying temperature is not higher than 60 ℃.
Further, in the step (12), titanium dioxide is modified by using a silane coupling agent containing quaternary ammonium salt to prepare quaternary ammonium salt modified titanium oxide, and the specific method is that the silane coupling agent containing quaternary ammonium salt and titanium dioxide are placed in an ethanol solution, fully mixed and reacted at normal temperature, and the reaction product is post-treated to obtain quaternary ammonium salt modified titanium oxide.
Further, in the step (12), the silane coupling agent containing quaternary ammonium salt is dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride; the mass ratio of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, titanium dioxide and ethanol is 1: 1-5: 30, of a nitrogen-containing gas;
in the step (12), the post-treatment comprises suction filtration, ethanol washing and vacuum drying; the temperature of the vacuum drying is not higher than 80 ℃.
Further, in the step (12), the particle size of the titanium oxide is 5-10 micrometers.
Further, in the step (13), the specific method for mixing the quaternary ammonium salt modified epoxy resin, the quaternary ammonium salt modified titanium oxide, the butyl acetate and the n-butyl alcohol is to add glass beads, stir at a rotating speed of 500-1000 r/min for 2-4 h, and remove the glass beads after the stirring is finished.
Further, in the step (13), the particle size of the glass beads is 1.5-3 mm, and the total mass of the glass beads is 2-3 times of the mass of the quaternary ammonium salt modified titanium oxide.
A preparation method of a quaternary ammonium salt antibacterial anticorrosive coating comprises the following steps:
(1) mixing the component A and the component B in the quaternary ammonium salt antibacterial anticorrosive paint according to claim 1, and spraying the mixture on the surface of a substrate for 4-6 times at a spraying pressure of 0.2-0.4 MPa to obtain an initial uncured coating; the thickness of the initial coating is 30-60 mu m;
(2) and curing the initial coating at room temperature for more than or equal to 72 hours to obtain the quaternary ammonium salt antibacterial anticorrosive coating.
The application of the quaternary ammonium salt antibacterial anticorrosive coating is characterized in that the quaternary ammonium salt antibacterial anticorrosive coating obtained by the preparation method of the quaternary ammonium salt antibacterial anticorrosive coating is applied to a space cabin.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, quaternary ammonium salt modification is carried out on the epoxy resin through quaternary amination reaction to obtain a resin system with bactericidal performance, so that the dissolution of quaternary ammonium salt micromolecules can be reduced, the stability of the antibacterial effect of the resin system is effectively improved, and the resin material obtains long-acting antibacterial performance;
(2) according to the invention, a layer of quaternary ammonium salt ions is coated on the surface of the titanium dioxide filler by utilizing the hydrolysis-condensation reaction of the silane coupling agent, so that the titanium dioxide filler with antibacterial property is obtained. The method is simple and convenient to operate, the yield is high, and the quaternary ammonium salt ions can be tightly combined on the surface of the titanium dioxide filler in a chemical bond mode, so that the antibacterial performance of the filler can be obviously enhanced;
(3) according to the invention, different quaternary ammonium salt molecules are adopted to respectively carry out quaternary ammonium salt modification on the resin system and the filler to obtain the dual quaternary ammonium salt modified antibacterial anticorrosive coating, and the quaternary ammonium salt molecules with different configurations can broaden the antibacterial spectrum performance of the antibacterial coating and can obviously improve the antibacterial effect of the coating;
(4) according to the invention, the epoxy resin and the polyamide curing agent which are good in binding force, environment-friendly and excellent in corrosion resistance are used as a basic system, and antibacterial modification is carried out on the basis, so that the antibacterial property of the coating can be improved on the basis of not influencing the physical and chemical properties of the coating, and the use requirement in a space station cabin is met;
(5) the quaternary ammonium salt antibacterial and anticorrosive coating prepared by the method has good antibacterial and mildewproof effects on aspergillus niger, escherichia coli and the like, the antibacterial rate is more than 99%, and the mildewproof grade is superior to the grade-1 standard;
(6) after 480 hours of neutral salt spray, the prepared space station quaternary ammonium salt antibacterial anticorrosive coating has uniform and complete coating surface and no cracking and corrosion phenomena;
(7) after a thermal cycle test, the prepared quaternary ammonium salt antibacterial anticorrosive coating for the space station has the advantages that the appearance of the coating is consistent with that of the original coating, the coating does not peel, bubble or fall off, the binding force meets the requirement, the coating has good vacuum volatility, toxic gas and organic gaseous pollutants are not generated during combustion, the coating is green and environment-friendly, and the coating has wide application prospects in the field of space stations.
Drawings
FIG. 1 is an IR spectrum of a quaternary ammonium salt modified E51 epoxy resin in example 1 of the present invention; 1639.49 shows a strong absorption peak in C-N indicating successful grafting of the quaternary ammonium salt to E51 epoxy resin.
FIG. 2 is a graph showing the antibacterial effect of the quaternary ammonium salt-modified titanium dioxide particles of different concentrations on Escherichia coli in example 1 of the present invention, wherein (a) is 0%; (b) 0.1 percent; (c) 0.2 percent; (d) 0.3 percent; (e) 0.4 percent; (f) 0.5 percent; (g) is 1%; (h) is 2%;
FIG. 3 is an illustration of the effect of a sample of the space station quaternary ammonium salt antibacterial anticorrosive coating sprayed in example 1 of the present invention;
FIG. 4 is a comparison of the antibacterial effect of the quaternary ammonium salt antibacterial anticorrosive coating on Aspergillus niger in the space station in example 1 of the present invention; wherein (a) is a blank aluminum test piece; (b) an aluminum coupon coated with an antibacterial coating.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention relates to a quaternary ammonium salt antibacterial anticorrosive paint for a space station, which comprises the following components in parts by mass:
the preparation method of the quaternary ammonium salt antibacterial and mildewproof coating for the space station comprises the following steps:
(1) weighing the following raw materials in parts by mass:
1-1.5 parts of quaternary ammonium salt modified epoxy resin, 1-1.5 parts of quaternary ammonium salt modified titanium oxide, 4-5 parts of butyl acetate and 0.4-0.8 part of n-butyl alcohol.
(2) And mixing the weighed raw materials to obtain the component A in the quaternary ammonium salt antibacterial anticorrosive paint.
(3) And before spraying the coating, adding a polyamide resin curing agent which is a component B and is uniformly diluted by a solvent, wherein the polyamide resin curing agent is 0.5-1 part by weight, the butyl acetate is 1-2 parts by weight, and the n-butyl alcohol is 0.1-0.2 part by weight.
Further, the quaternary ammonium salt modified epoxy resin is obtained by modifying epoxy resin with triethylamine hydrochloride. The method comprises the following specific steps: selecting epoxy resin meeting the use requirements in a cabin of a space station, and modifying the epoxy resin by adopting triethylamine hydrochloride to obtain quaternary ammonium salt: putting a certain amount of epoxy resin, triethylamine hydrochloride aqueous solution (the mass percentage of the triethylamine hydrochloride is 5%) and ethanol into a three-neck flask, wherein the mass ratio of the epoxy resin to the triethylamine hydrochloride aqueous solution to the ethanol is 20: 3-5: 160 to 240. Heating to 80-90 ℃ under stirring, and reacting for 5-10 h. After the reaction is finished, removing a large amount of solvent under the condition of reduced pressure, and drying for 12 hours in a vacuum oven (the temperature is controlled to be not higher than 60 ℃).
Furthermore, the particle size of the titanium oxide filler is 5-10 microns.
Further, the quaternary ammonium salt modified titanium oxide is obtained by modifying titanium dioxide by using a silane coupling agent containing quaternary ammonium salt. The method specifically comprises the steps of placing dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride and titanium dioxide in an ethanol solution, wherein the mass ratio of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, titanium dioxide to ethanol is 1: 1-5: and 30, stirring the mixture by using a magnetic stirrer to fully mix the mixture, reacting the mixture for 8 hours at normal temperature, performing suction filtration by using a Buchner funnel, washing the mixture by using ethanol, and drying the mixture for 12 hours in a vacuum oven (the temperature is controlled to be not higher than 80 ℃).
Further, the weighed raw materials are mixed in the step (2), glass beads are added and stirred for 2-4 hours at the rotating speed of 500-1000 r/min, and the glass beads are removed after stirring is finished.
Furthermore, the particle size of the glass beads is 1.5-3 mm, and the total mass of the glass beads is 2-3 times that of the quaternary ammonium salt titanium oxide filler.
A preparation method of a quaternary ammonium salt antibacterial anticorrosive coating for a space station comprises the steps of mixing a component A and a component B in the quaternary ammonium salt antibacterial anticorrosive coating, spraying the coating on the surface of a substrate for 4-6 times, controlling the thickness of the coating to be 30-60 mu m, and then standing for 72 hours at room temperature for curing.
The quaternary ammonium salt antibacterial anticorrosive coating obtained by the preparation method of the quaternary ammonium salt antibacterial anticorrosive coating for the space station can be used as an antibacterial anticorrosive coating to be applied in a space cabin.
Example 1:
in this embodiment, a preparation method of the quaternary ammonium salt antibacterial anticorrosive paint for the space station comprises the following steps:
1) synthesis of quaternary ammonium salt modified E51 epoxy resin: 100g of epoxy resin, 16g of triethylamine hydrochloride aqueous solution and 1000g of ethanol are put into a three-neck flask, heated to 80 ℃ under the condition of stirring and reacted for 8 hours. After the reaction is finished, a large amount of solvent is removed under the condition of reduced pressure, and the reaction product is dried in a vacuum oven at 60 ℃ for 12 hours to finally obtain 96.7g of quaternary ammonium salt modified E51 epoxy resin with the yield of 94.5 percent.
2) Synthesis of quaternary ammonium salt modified titanium dioxide: adding 2g of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride and 100g of titanium dioxide (the particle size is 5-10 micrometers) into 3000g of ethanol solution, stirring by using a magnetic stirrer to fully mix, reacting for 8 hours at normal temperature, performing suction filtration by using a Buchner funnel, washing with ethanol, and drying in a vacuum oven for 12 hours (the temperature is controlled below 80 ℃) to finally obtain 98.5g of quaternary ammonium salt modified titanium dioxide with the yield of 96.5%.
3) Respectively mixing and stirring quaternary ammonium salt modified epoxy resin, quaternary ammonium salt modified titanium oxide, butyl acetate and n-butyl alcohol according to a proportion to obtain a component A in the coating, adding glass beads for dispersion and stirring, wherein the using amount of the filler and the stirring and dispersion conditions are as follows:
4) after the dispersion is finished, filtering the component A by adopting a 120-mesh copper net, and filtering the original stirring container and the copper net by adopting a butyl acetate solvent, wherein the total content of butyl acetate is not more than 500 percent of the content of the quaternary ammonium salt modified epoxy resin.
The copper mesh is 120 meshes.
5) Before spraying, a polyamide resin curing agent which is uniformly diluted, namely a component B, is added. Wherein, the polyamide resin curing agent comprises 10g of polyamide resin curing agent, 10g of butyl acetate and 2g of n-butyl alcohol. The preparation of the quaternary ammonium salt antibacterial anticorrosive paint for the space station is finished.
6) Before spraying, the surface of the aluminum alloy substrate can be polished, roughened, sandblasted and the like, and the spraying conditions are as follows:
7) and curing the coating, wherein the curing process is that the coating is placed for 72 hours at room temperature. And finishing the preparation of the quaternary ammonium salt antibacterial anticorrosive coating of the space station.
FIG. 1 is an IR spectrum of a quaternary ammonium salt modified E51 epoxy resin in example 1 of the present invention; 1639.49 shows a strong absorption peak in C-N indicating successful grafting of the quaternary ammonium salt to E51 epoxy resin; as shown in fig. 2, the antibacterial performance of the material is remarkably improved with the increase of the concentration of the quaternary ammonium salt modified titanium dioxide particles; as shown in fig. 3, the sprayed quaternary ammonium salt antibacterial anticorrosive coating sample piece of the space station has uniform and consistent surface coating color and no bubbling and shedding phenomenon; as shown in FIG. 4, the antibacterial effect of the coating on Aspergillus niger is compared, and no mold is adhered to and grown on the surface of the aluminum test piece coated with the antibacterial coating.
The quaternary ammonium salt antibacterial and anticorrosive coating prepared by the method has good antibacterial and mildewproof effects on aspergillus niger, escherichia coli and the like, the antibacterial rate is more than 99%, and the mildewproof grade is superior to the grade-1 standard; after 480 hours of neutral salt spray, the surface of the coating is uniform and complete and has no cracking and corrosion phenomena; the coating is subjected to a thermal cycle test at a temperature of between 196 ℃ below zero and 150 ℃ for not less than 100 times according to GJB 2502.8 (spacecraft thermal control coating test method part 8), the appearance of the coating is consistent with that of the original coating, the coating does not peel, bubble or fall off, and the binding force meets the requirement; according to a material volatilization performance test method in vacuum of QJ 1558A-2012, the total loss of vacuum TML is less than 0.6%, and the vacuum condensable volatile matter CVCM is less than 0.09%, so that the coating meets the volatilization standard; the coating meets the release standard of toxic gas according to a smoke density test method of the non-metallic material in the cabin of the HB 6575-2014 civil aircraft and a test method of the toxic gas generated by the combustion of the non-metallic material in the cabin of the HB7066-1994 civil aircraft, wherein carbon monoxide is less than or equal to 3500ppm, hydrogen fluoride is less than or equal to 100ppm, hydrogen chloride is less than or equal to 150ppm, nitrogen oxide is less than or equal to 100ppm, sulfur dioxide is less than or equal to 100ppm, and hydrogen cyanide is less than or equal to 150 ppm; the coating has a CO content of less than or equal to 25 mu g/g according to GJB 2704A-2015 general Specification for thermal control coatings of spacecrafts; the total content of removed organic gaseous pollutants is less than or equal to 100 mug/g, the qualified requirement of the odor-emitting index is not less than 1.5 grade, and the method is green and environment-friendly.
The application binding force test base material of the quaternary ammonium salt antibacterial anticorrosive coating prepared by the invention is shown in the following table:
TABLE 1 coating substrate with quaternary ammonium salt antibacterial and antiseptic coating for space station
| Relating to the kind of the substrate | To describe in detail |
| Metal species | Aluminum alloy, magnesium alloy, titanium alloy, aluminum-based silicon carbide. |
| Composite material | Epoxy glass fiber reinforced plastic, carbon fiber and polyether ether ketone. |
According to the coating adhesion testing method of the coating testing method of QJ 990.14-1986, the quaternary ammonium salt antibacterial anticorrosive coating of the space station is respectively subjected to a bonding force test on the surfaces of base materials such as aluminum alloy, magnesium alloy, titanium alloy, aluminum-based silicon carbide, epoxy glass steel, carbon fiber, polyether ether ketone and the like, the test result is qualified, and the square coatings on the surfaces of all the base materials do not fall off after the grid test.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are not particularly limited to the specific examples described herein.
Claims (12)
1. The quaternary ammonium salt antibacterial anticorrosive paint is characterized by comprising a component A and a component B, wherein the component A and the component B respectively comprise the following components in parts by mass:
a component A:
1-1.5 parts of quaternary ammonium salt modified epoxy resin;
1-1.5 parts of quaternary ammonium salt modified titanium oxide;
4-5 parts of butyl acetate;
0.4-0.8 part of n-butyl alcohol;
b, component B:
0.5-1 part of polyamide resin curing agent;
1-2 parts of butyl acetate;
and 0.1-0.2 part of n-butyl alcohol.
2. A preparation method of a quaternary ammonium salt antibacterial anticorrosive paint is characterized by comprising the following steps:
step (1): the preparation of the component A specifically comprises the following steps:
(11) preparing quaternary ammonium salt modified epoxy resin;
(12) preparing quaternary ammonium salt modified titanium oxide;
(13) mixing quaternary ammonium salt modified epoxy resin, quaternary ammonium salt modified titanium oxide, butyl acetate and n-butyl alcohol to obtain a component A in the quaternary ammonium salt antibacterial anticorrosive paint; the mass parts of the quaternary ammonium salt modified epoxy resin are 1-1.5, the mass parts of the quaternary ammonium salt modified titanium oxide are 1-1.5, the mass parts of butyl acetate are 4-5, and the mass parts of n-butyl alcohol are 0.4-0.8;
step (2): preparing the component B, specifically, uniformly dispersing a polyamide resin curing agent in butyl acetate and n-butyl alcohol; the polyamide resin curing agent is 0.5-1 part by mass, the butyl acetate is 1-2 parts by mass, and the n-butyl alcohol is 0.1-0.2 part by mass;
and (3): mixing the component A and the component B.
3. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 2, characterized in that in the step (11), the epoxy resin is modified by triethylamine hydrochloride to prepare the quaternary ammonium salt modified epoxy resin, and the specific method comprises the steps of mixing the epoxy resin, triethylamine hydrochloride aqueous solution and ethanol, reacting under heating condition, and post-treating the reaction product to obtain the quaternary ammonium salt modified epoxy resin.
4. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 3, characterized in that in the step (11), the mass percent of triethylamine hydrochloride in the triethylamine hydrochloride aqueous solution is 5%; the mass ratio of the epoxy resin to the triethylamine hydrochloride aqueous solution to the ethanol is 20: 3-5: 160 to 240.
5. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 3, characterized in that in the step (11), the epoxy resin, the triethylamine hydrochloride aqueous solution and the ethanol are mixed and then react for 5-10 hours at 80-90 ℃;
in the step (11), the post-treatment comprises solvent removal and vacuum drying; the solvent removal is carried out under reduced pressure, and the vacuum drying temperature is not higher than 60 ℃.
6. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 2, characterized in that in the step (12), titanium dioxide is modified by using a silane coupling agent containing quaternary ammonium salt to prepare quaternary ammonium salt modified titanium oxide, and the specific method is that the silane coupling agent containing quaternary ammonium salt and titanium dioxide are placed in an ethanol solution, fully mixed and reacted at normal temperature, and the reaction product is subjected to post-treatment to obtain quaternary ammonium salt modified titanium oxide.
7. The method for preparing a quaternary ammonium salt antibacterial anticorrosive paint according to claim 6, wherein in the step (12), the silane coupling agent containing the quaternary ammonium salt is dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride; the mass ratio of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride, titanium dioxide and ethanol is 1: 1-5: 30, of a nitrogen-containing gas;
in the step (12), the post-treatment comprises suction filtration, ethanol washing and vacuum drying; the temperature of the vacuum drying is not higher than 80 ℃.
8. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 6, wherein in the step (12), the particle size of titanium oxide is 5-10 micrometers.
9. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 2, characterized in that in the step (13), the specific method for mixing the quaternary ammonium salt modified epoxy resin, the quaternary ammonium salt modified titanium oxide, the butyl acetate and the n-butyl alcohol is to add glass beads, stir the mixture for 2 to 4 hours at a rotation speed of 500 to 1000r/min, and remove the glass beads after the stirring is finished.
10. The preparation method of the quaternary ammonium salt antibacterial anticorrosive paint according to claim 9, wherein in the step (13), the particle size of the glass beads is 1.5-3 mm, and the total mass of the glass beads is 2-3 times of that of the quaternary ammonium salt modified titanium oxide.
11. A preparation method of a quaternary ammonium salt antibacterial anticorrosive coating is characterized by comprising the following steps:
(1) mixing the component A and the component B in the quaternary ammonium salt antibacterial anticorrosive paint according to claim 1, and spraying the mixture on the surface of a substrate for 4-6 times at a spraying pressure of 0.2-0.4 MPa to obtain an initial uncured coating; the thickness of the initial uncured coating is 30-60 mu m;
(2) and curing the initial uncured coating in a room temperature environment for more than or equal to 72 hours to obtain the quaternary ammonium salt antibacterial anticorrosive coating.
12. The application of the quaternary ammonium salt antibacterial anticorrosive coating is characterized in that the quaternary ammonium salt antibacterial anticorrosive coating obtained by the preparation method of the quaternary ammonium salt antibacterial anticorrosive coating in claim 11 is applied to a space cabin.
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| CN114517024B (en) * | 2022-03-01 | 2022-12-30 | 九牧厨卫股份有限公司 | Bactericidal paint, bactericidal coating and application thereof, bactericidal ceramic product and preparation method thereof |
| CN114539885B (en) * | 2022-04-13 | 2022-08-16 | 中国科学院宁波材料技术与工程研究所 | Special high-permeability moisture-curing seal primer for concrete and preparation method and application thereof |
| CN114702869A (en) * | 2022-05-16 | 2022-07-05 | 武汉轻工大学 | Epoxy resin quaternary ammonium salt antibacterial coating and preparation method thereof |
| CN115521685B (en) * | 2022-10-08 | 2023-10-27 | 北京星驰恒动科技发展有限公司 | Paint, preparation method of paint and space capsule |
| CN115975476B (en) * | 2022-12-26 | 2024-02-09 | 北京卫星制造厂有限公司 | Low-vacuum volatile antibacterial decorative coating, preparation method and application thereof |
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| JPH05140482A (en) * | 1991-11-14 | 1993-06-08 | Nippon Paint Co Ltd | Antibacterial coating composition |
| EP1371699A3 (en) * | 2002-06-14 | 2004-01-14 | Rohm And Haas Company | Polymeric nanoparticle and antimicrobial coating formulations |
| CN103788287B (en) * | 2014-01-28 | 2015-11-18 | 浙江大学 | A kind of antibacterial modified low surface energy type marine antifouling coating resin and preparation method thereof |
| CN108912945A (en) * | 2017-04-05 | 2018-11-30 | 中国科学院宁波材料技术与工程研究所 | Antibacterial and mouldproof antiseptic fire-retardation integration nano functional coating, its preparation method and application |
| CN111944369A (en) * | 2020-07-30 | 2020-11-17 | 马鞍山市金韩防水保温工程有限责任公司 | Antibacterial anticorrosive paint for building exterior wall and preparation method thereof |
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