CN110183918B - Preparation method of long-acting anti-sticking coating - Google Patents
Preparation method of long-acting anti-sticking coating Download PDFInfo
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- CN110183918B CN110183918B CN201910462274.5A CN201910462274A CN110183918B CN 110183918 B CN110183918 B CN 110183918B CN 201910462274 A CN201910462274 A CN 201910462274A CN 110183918 B CN110183918 B CN 110183918B
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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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
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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
- C09D5/16—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
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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Abstract
The invention relates to a preparation method of a long-acting anti-sticking coating, belonging to the technical field of coatings. The technical proposal of the invention adopts the sepiolite as the raw material and carries out modification, because the sepiolite contains a large amount of magnesium, aluminum ions are filled into a sepiolite material framework, and the aluminum ions gradually replace magnesium ions and enter into a sepiolite crystal lattice, so that the sepiolite framework has excellent structural performance and is compounded with acrylic acid to prepare the water-absorbing gel material, meanwhile, because of the adoption of plasma initiation, a large amount of HO generated in the plasma initiation process can be added into a polymer chain, so that the sepiolite-based hydrogel has more excellent hydrophilicity and adsorption performance, and HO is added into the network structure of the sepiolite to form effective structural modification with the magnesium ion framework material, after the HO is effectively filled into the coating, the water is effectively absorbed in the air, and micro structural concave-convex is formed on the surface of the coating formed by the water absorption, so that the pollution resistance and durability of the material are effectively improved.
Description
Technical Field
The invention relates to a preparation method of a long-acting anti-sticking coating, belonging to the technical field of coatings.
Background
With the rapid development of economy and the increasing demand of people for information, various phenomena of messy advertisement pasting are emerging, and the small advertisements pasted on the surfaces of buildings are not easy to tear off, so that the urban psoriasis is extremely discordant. Because the small advertisements in cities are firmly adhered to the surfaces of urban facilities, the residual small advertisements cannot be cleaned by the existing cleaning technology and cleaning agent, and patch type pollution and turbid pollution left after cleaning are caused, so that the urban persistent ailment not only brings huge burden to sanitation workers, but also seriously affects the attractiveness of the cities.
In cities, small advertisements which are randomly pasted can be seen anywhere whether telegraph poles, lamp boxes, bus stop boards and guardrails on streets or walls, stairs, security doors and newspaper boxes in corridors, so that the psoriasis in the cities is caused, the appearance and appearance of the cities are seriously influenced, various illegal behaviors are bred and spread, the regulation is difficult, the moisture regain is fast, and the public masses are extremely painful. However, as the city is too big, managers whip badly, especially the actions of messy pasting and coating occur at night, so the regulation and treatment activities often fall into a strange circle of 'regulation, moisture regain, re-regulation and re-moisture regain', in order to solve the problem, people adopt a plurality of methods, invent a plurality of coatings on the surfaces of the buildings or structures to achieve the purpose of sticking prevention or doodling prevention, and achieve certain effect. The coatings are mostly prepared by compounding organic siloxane or mineral oil with other materials by utilizing the non-stick property of organic silicon or mineral oil, such as acrylic siloxane anti-graffiti coatings, mineral oil anti-graffiti coatings, siloxane modified acrylic polyurethane anti-graffiti coatings and various anti-graffiti coatings added with siloxane auxiliary agents. In the anti-graffiti coatings, some active ingredients of the anti-graffiti are only physically mixed with other ingredients in a paint film, and after the anti-graffiti coatings are used for a period of time, the active ingredients which are freely distributed on the surface of the paint film are wiped off, so that the anti-graffiti function is reduced, even disappears, and dust is adhered to the surface of the paint film due to the free distribution of the active ingredients. Other paint such as oil polyurethane or oil fluorocarbon anti-doodling paint solves the problems of anti-sticking and anti-doodling durability, but the paint is an oil product and pollutes the urban environment in the process of construction and drying.
In recent years, the loss caused by malicious graffiti pasting is more and more concerned by people, the city appearance and the landscape are influenced, the graffiti and various stickers are removed, time and labor are wasted, the base material is easily damaged, and a large amount of funds are consumed. The phenomenon of random scrawling and sticking happens occasionally and is difficult to avoid, so that the development of the coating with the scrawling and sticking resisting functions is very necessary.
The main performance difference of the anti-graffiti anti-sticking paint and other paints is that the surface of a base material coated by the paint has low adhesive force and is difficult to be attached by pollutants. Reducing contaminant adhesion, both to reduce contaminant adhesion to the substrate and to consider how to easily separate contaminants from the substrate interface. Anti-graffiti coatings should generally have the following characteristics: environmental protection, low toxicity, good coating property, excellent adhesion to a substrate, good recoatability, chemical resistance, durability, wear resistance, good weather resistance, stain resistance, easy cleaning and the like.
The anti-graffiti coating can be divided into a permanent type and a self-damage type according to the functional types, the permanent type anti-graffiti coating is a polyurethane coating, mainly because the polyurethane coating has high hardness, wear resistance and durability, long life, and easy graffiti cleaning, and the same point can tolerate multiple cleaning treatments without the damage signs of the coating, so the polyurethane coating is the most popular surface protection coating. With the improvement of the anti-graffiti and anti-sticking performance requirements of people on the paint and the national restrictions on VOC discharge, the development of high-performance waterborne polyurethane anti-graffiti paint becomes a necessary trend.
The graffiti is oily and aqueous, the coating film has good hydrophobicity and lipophobicity, and in order to remove the graffiti by a simple wiping method, the surface of the coating film is flat and smooth, and the Gibbs free energy of the surface is low. The improvement of the graffiti resistance of the coating film is mainly achieved through two basic ways of improving the surface property of the coating film to make the coating film difficult to adsorb and easy to remove pollutants, and improving the compactness of the coating film to make the pollutants difficult to permeate.
At present, organic silicon and fluororesin are mainly utilized to improve the surface property of the water-based polyurethane coating, reduce the Gibbs free energy of the surface and endow the finish with anti-adhesion property. The organic siloxane has a unique chemical structure and lower surface energy, so that the organic siloxane is enriched on the surface in the film forming process, and can endow the modified polymer coating film with excellent water resistance, oil stain resistance, weather resistance, high and low temperature service performance and good mechanical performance.
CN101585995B discloses an oily anti-graffiti anti-sticking coating prepared by taking hydroxy acrylic resin, fluorocarbon resin, hydroxy-containing polydimethylsiloxane resin and hexamethyl diisocyanate biuret as main raw materials; CN101565579B discloses an anti-doodling and anti-sticking coating which takes fluorocarbon resin and aliphatic polyisocyanate curing agent as a composition; US5387434 reports an anti-graffiti coating composition comprising a water soluble wax, sodium silicate, rosin and a binder, which is removed by hot water under high pressure and then washed, followed by application of a layer of the coating.
In the prior art, a paint film formed after the traditional paint is cured has the problems of insufficient hardness, poor temperature resistance, easy cracking and the like, and can not achieve the antifouling and anti-doodling effects when being polluted by doodling or dirt. Therefore, prime is to need a coating capable of preventing doodling and pollution.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem that after the existing anti-sticking coating is used for a period of time, the effective components which are freely distributed on the surface of a paint film are wiped off to cause the reduction and even disappearance of the anti-sticking function, the preparation method of the long-acting anti-sticking coating is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) adding the halloysite nanotube into the composite antifouling agent according to the mass ratio of 1:8, stirring, mixing, ball-milling, filtering by using a screen, collecting sieved particles, washing, drying, grinding and sieving to obtain modified load particles;
(2) taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of aluminum chloride, 2-3 parts by weight of aluminum nitrate and 25-30 parts by weight of aluminum sulfate with the mass fraction of 1% in a mortar, grinding and dispersing, collecting dispersed slurry, filtering and collecting filter cakes, washing, drying and grinding to obtain modified sepiolite particles;
(3) respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of modified sepiolite particles, 6-8 parts by weight of methyl propanesulfonic acid and 3-5 parts by weight of N, N' -methylene bisacrylamide, placing the materials into a three-neck flask, stirring and mixing the materials, placing the materials into a reaction solution at 45-50 ℃ for heat preservation reaction to obtain a reaction solution, dropwise adding acrylic acid into the reaction solution, stirring and mixing the materials after the dropwise adding is finished, and collecting a mixed solution;
(5) inserting an electrode into the mixed solution, performing discharge treatment, performing heat preservation reaction, standing and cooling to room temperature, collecting gel liquid, performing vacuum freeze drying, performing ball milling and sieving to obtain modified particles, respectively weighing 45-50 parts by weight of dimethylbenzene, 6-8 parts by weight of modified load particles, 15-20 parts by weight of acrylic resin, 10-15 parts by weight of modified particles, 6-8 parts by weight of pigment and 6-8 parts by weight of auxiliary agent, placing the materials in a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating.
The preparation method of the composite antifouling agent in the step (1) comprises the following steps:
respectively weighing 45-50 parts of bromopyrrole carbonitrile, 10-15 parts of cuprous oxide, 3-5 parts of copper pyrithione and 10-15 parts of trichlorophenylmaleimide in parts by weight, placing the materials in a triangular flask, stirring, mixing, and placing the mixture under 200-300W for ultrasonic dispersion for 10-15 min to obtain the composite antifouling agent.
The screen mesh filtration in the step (1) adopts a screen mesh with the aperture of 0.25-0.28 μm.
And (2) washing in the step (1) is respectively washing with acetone and deionized water for 3-5 times.
The particle size of the modified load particles in the step (1) is 500 meshes.
15% of the mass fraction in the step (2).
The mass fractions of the aluminum chloride and the aluminum nitrate in the step (2) are both 15 percent.
And (3) mixing the acrylic acid and the reaction liquid according to the mass ratio of 1: 8.
And (3) the acrylic acid drop acceleration rate is 2-3 mL/min.
The discharge treatment voltage in the step (3) is 450-480V
And (4) the auxiliary agent is prepared by respectively weighing 45-50 parts by weight of BYK-A515 defoaming agent, 25-30 parts by weight of BYK333 flatting agent and 15-20 parts by weight of BYK-190 dispersing agent, and stirring and mixing.
Compared with other methods, the method has the beneficial technical effects that:
(1) the technical scheme of the invention adopts sepiolite as a raw material and carries out modification, because the sepiolite contains a large amount of magnesium, aluminum ions are filled into a framework of the sepiolite material, the aluminum ions gradually replace the magnesium ions and enter the crystal lattice of the sepiolite, so that the sepiolite framework has excellent structural performance and is compounded with acrylic acid to prepare the water-absorbing gel material, meanwhile, because plasma initiation is adopted, a large amount of HO generated in the plasma initiation process can be added into a polymer chain, so that the hydrophilicity and the adsorption performance of the sepiolite-based hydrogel are more excellent, HO is added into a network structure of the sepiolite to form effective structural modification with the magnesium ion framework material, water is effectively adsorbed in the air after the sepiolite is effectively filled into a coating, and micro structural concave-convex parts are formed on the surface of the coating formed by adsorbing water, so as to form an effective stain-resistant structure, thereby effectively improving the stain resistance and durability of the material;
(2) the technical scheme of the invention is that the nano halloysite is used as the loaded particle loaded antifouling agent for modification, the halloysite is a nano tubular material formed by curling natural silicate layers, the layers are not compact, in the loading process, part of the antifouling agent enters gaps of the silicate layers under the vacuum action and can be slowly released into a polymer matrix in the using process, secondly, as the halloysite surface is negatively charged, a small amount of antifouling agent is adsorbed on the outer surface of the halloysite nanotube in the loading process in an electrostatic adsorption mode, the acting force causes that the antifouling agent is not completely washed away in the washing process, substances adsorbed on the outer surface of the halloysite are released in the early stage of product use in preference to substances adsorbed in the tube and between the layers, the nano halloysite can be used as the antifouling early stage of the material, and the desorption process of molecules can be equivalent to the reverse process of the adsorption process, the desorption process starts from the outermost molecules in the pipe, under the action of potential energy (concentration difference), the outermost molecules begin to separate from the constraint of the halloysite pipe and slowly migrate out of the pipe, the closer to the inner wall of the pipe, the larger the electrostatic acting force of the pipe wall molecules on the antifouling agent, the more effectively slow release and the antifouling performance improvement are realized, the antifouling agent in the material is slowly released to the surface of the material, the attachment of stains on the surface of the material can be effectively inhibited, the constraint is generated on the antifouling agent material through the nano halloysite particles, the migration rate of the antifouling agent in the polymer matrix is slowed, the over-fast spraying condition of the antifouling agent is further improved, and the long-acting performance of the antifouling agent material is improved on the other hand.
Detailed Description
Respectively weighing 45-50 parts by weight of bromopyrrole carbonitrile, 10-15 parts by weight of cuprous oxide, 3-5 parts by weight of copper pyrithione and 10-15 parts by weight of trichlorophenylmaleimide, placing the mixture in a triangular flask, stirring, mixing, placing the mixture under 200-300W, performing ultrasonic dispersion for 10-15 min to obtain a composite antifouling agent, adding halloysite nanotubes into the dispersion liquid according to the mass ratio of 1:8, stirring, mixing, ball-milling for 3-5 h at room temperature according to 200-300 r/min, sieving by using a 0.25-0.28 mu m sieve, collecting sieved particles, washing by using acetone and deionized water for 3-5 times, performing vacuum freeze drying, and grinding by using a 500-mesh sieve to obtain modified load particles; taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of 15% aluminum chloride, 2-3 parts by weight of 15% aluminum nitrate and 25-30 parts by weight of 1% aluminum sulfate, placing the materials into a mortar, grinding and dispersing, collecting dispersed slurry, filtering, collecting filter cakes, washing the filter cakes with deionized water until washing liquid is neutral, and carrying out vacuum freeze drying and grinding to obtain modified sepiolite particles; respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of modified sepiolite particles, 6-8 parts by weight of methylpropanesulfonic acid and 3-5 parts by weight of N, N' -methylenebisacrylamide, placing the mixture into a three-neck flask, stirring and mixing, reacting for 1-2 hours at 45-50 ℃ to obtain a reaction solution, dropwise adding acrylic acid into the reaction solution according to the mass ratio of 1:8, controlling the dropwise adding rate to be 2-3 mL/min, stirring and mixing after the dropwise adding is completed, collecting a mixed solution, inserting an electrode into the mixed solution, discharging at 450-480V for 120-150 seconds, stopping discharging, placing the mixture into a 70-80 ℃ for reacting for 2-3 hours at a constant temperature, standing and cooling to room temperature, collecting a gel solution, performing vacuum freeze drying, and performing ball milling through a 200-mesh sieve to obtain modified particles; respectively weighing 45-50 parts by weight of dimethylbenzene, 6-8 parts by weight of modified load particles, 15-20 parts by weight of acrylic resin, 10-15 parts by weight of modified particles, 6-8 parts by weight of pigment and 6-8 parts by weight of auxiliary agent, placing the materials into a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating; the auxiliary agent is prepared by respectively weighing 45-50 parts by weight of BYK-A515 defoaming agent, 25-30 parts by weight of BYK333 flatting agent and 15-20 parts by weight of BYK-190 dispersing agent and stirring and mixing.
Example 1
Respectively weighing 45 parts of bromopyrrole carbonitrile, 10 parts of cuprous oxide, 3 parts of copper pyrithione and 10 parts of trichlorophenyl maleimide in parts by weight, placing the mixture into a triangular flask, stirring, mixing, placing the mixture under 200W for ultrasonic dispersion for 10min to obtain a composite antifouling agent, adding halloysite nanotubes into dispersion liquid according to the mass ratio of 1:8, stirring, mixing, placing the mixture at room temperature, performing ball milling for 3h at a speed of 200r/min, sieving with a 0.25 mu m sieve, collecting sieved particles, washing with acetone and deionized water for 3 times respectively, performing vacuum freeze drying, and grinding with a 500-mesh sieve to obtain modified load particles; taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 45 parts of deionized water, 10 parts of aluminum chloride with the mass fraction of 15%, 2 parts of aluminum nitrate with the mass fraction of 15% and 25 parts of aluminum sulfate with the mass fraction of 1% in a mortar, grinding and dispersing, collecting dispersed slurry, filtering and collecting filter cakes, washing the filter cakes with the deionized water until washing liquid is neutral, and carrying out vacuum freeze drying and grinding to obtain modified sepiolite particles; respectively weighing 45 parts by weight of deionized water, 10 parts by weight of modified sepiolite particles, 6 parts by weight of methylpropanesulfonic acid and 3 parts by weight of N, N' -methylenebisacrylamide, placing the materials into a three-neck flask, stirring and mixing the materials, placing the materials at 45 ℃ for heat preservation reaction for 1 hour to obtain a reaction solution, dropwise adding acrylic acid into the reaction solution according to the mass ratio of 1:8, controlling the dropwise adding rate to be 2mL/min, stirring and mixing the materials after the dropwise adding is finished, collecting the mixed solution, inserting an electrode into the mixed solution, discharging at 450V for 120s, stopping discharging, placing the materials at 70 ℃ for heat preservation reaction for 2 hours, standing and cooling the mixed solution to room temperature, collecting gel liquid, performing vacuum freeze drying, and performing ball milling on the gel liquid, and screening the gel liquid by a 200-mesh sieve to obtain modified particles; respectively weighing 45 parts of dimethylbenzene, 6 parts of modified load particles, 15 parts of acrylic resin, 10 parts of modified particles, 6 parts of pigment and 6 parts of auxiliary agent in parts by weight, placing the materials into a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating; the auxiliary agent is prepared by respectively weighing 45 parts by weight of BYK-A515 defoaming agent, 25 parts by weight of BYK333 flatting agent and 15 parts by weight of BYK-190 dispersing agent, and stirring and mixing.
Example 2
Respectively weighing 48 parts by weight of bromopyrrole carbonitrile, 13 parts by weight of cuprous oxide, 4 parts by weight of copper pyrithione and 13 parts by weight of trichlorophenylmaleimide, placing the mixture into a triangular flask, stirring, mixing, placing the mixture under 250W, performing ultrasonic dispersion for 13min to obtain a composite antifouling agent, adding halloysite nanotubes into dispersion liquid according to the mass ratio of 1:8, stirring, mixing, ball-milling for 4h at room temperature at a speed of 250r/min, sieving by using a 0.27 mu m sieve, collecting sieved particles, washing by using acetone and deionized water for 4 times respectively, performing vacuum freeze drying, and grinding by using a 500-mesh sieve to obtain modified load particles; taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 47 parts of deionized water, 13 parts of aluminum chloride with the mass fraction of 15%, 2.5 parts of aluminum nitrate with the mass fraction of 15% and 27 parts of aluminum sulfate with the mass fraction of 1% in a mortar, grinding and dispersing, collecting dispersed slurry, filtering and collecting filter cakes, washing the filter cakes with the deionized water until washing liquid is neutral, and carrying out vacuum freeze drying and grinding to obtain modified sepiolite particles; respectively weighing 47 parts by weight of deionized water, 13 parts by weight of modified sepiolite particles, 7 parts by weight of methylpropanesulfonic acid and 4 parts by weight of N, N' -methylenebisacrylamide, placing the materials into a three-neck flask, stirring and mixing the materials, placing the materials at 47 ℃ for heat preservation reaction for 1.5 hours to obtain reaction liquid, dropwise adding acrylic acid into the reaction liquid according to the mass ratio of 1:8, controlling the dropwise adding rate to be 2.5mL/min, stirring and mixing the materials after the dropwise adding is finished, collecting the mixed liquid, inserting an electrode into the mixed liquid, discharging at 465V for 135s, stopping discharging, placing the materials at 75 ℃ for heat preservation reaction for 2.5 hours, standing and cooling the materials to room temperature, collecting gel liquid, carrying out vacuum freeze drying, and carrying out ball milling on the gel liquid, and sieving the gel; respectively weighing 47 parts of dimethylbenzene, 7 parts of modified load particles, 17 parts of acrylic resin, 13 parts of modified particles, 7 parts of pigment and 7 parts of auxiliary agent in parts by weight, placing the materials into a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating; the auxiliary agent is prepared by respectively weighing 47 parts by weight of BYK-A515 defoaming agent, 27 parts by weight of BYK333 flatting agent and 17 parts by weight of BYK-190 dispersing agent, and stirring and mixing.
Example 3
Respectively weighing 50 parts by weight of bromopyrrole carbonitrile, 15 parts by weight of cuprous oxide, 5 parts by weight of copper pyrithione and 15 parts by weight of trichlorophenylmaleimide, placing the mixture into a triangular flask, stirring, mixing, placing the mixture under 300W, performing ultrasonic dispersion for 15min to obtain a composite antifouling agent, adding halloysite nanotubes into dispersion liquid according to a mass ratio of 1:8, stirring, mixing, placing the mixture at room temperature, performing ball milling for 5h at a speed of 300r/min, sieving by using a 0.28 mu m sieve, collecting sieved particles, washing by using acetone and deionized water for 5 times respectively, performing vacuum freeze drying, and grinding by using a 500-mesh sieve to obtain modified load particles; taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 50 parts by weight of deionized water, 15 parts by weight of aluminum chloride with the mass fraction of 15%, 3 parts by weight of aluminum nitrate with the mass fraction of 15% and 30 parts by weight of aluminum sulfate with the mass fraction of 1%, placing the deionized water, the aluminum chloride, the aluminum nitrate and the aluminum sulfate into a mortar, grinding, dispersing, collecting dispersed slurry, filtering, collecting filter cakes, washing the filter cakes with deionized water until washing liquid is neutral, and carrying out vacuum freeze drying and grinding to obtain modified sepiolite particles; respectively weighing 50 parts by weight of deionized water, 15 parts by weight of modified sepiolite particles, 8 parts by weight of methylpropanesulfonic acid and 5 parts by weight of N, N' -methylenebisacrylamide, placing the materials into a three-neck flask, stirring and mixing the materials, placing the materials at 50 ℃ for heat preservation reaction for 2 hours to obtain reaction liquid, dropwise adding acrylic acid into the reaction liquid according to the mass ratio of 1:8, controlling the dropwise adding rate to be 3mL/min, stirring and mixing the materials after the dropwise adding is finished, collecting mixed liquid, inserting an electrode into the mixed liquid, discharging at 480V for 150s, stopping discharging, placing the materials at 80 ℃ for heat preservation reaction for 3 hours, standing and cooling the mixed liquid to room temperature, collecting gel liquid, performing vacuum freeze drying, and performing ball milling on the gel liquid, and screening the gel liquid by a 200-mesh sieve to obtain modified particles; respectively weighing 50 parts of dimethylbenzene, 8 parts of modified load particles, 20 parts of acrylic resin, 15 parts of modified particles, 8 parts of pigment and 8 parts of auxiliary agent in parts by weight, placing the materials in a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating; the auxiliary agent is prepared by respectively weighing 50 parts by weight of BYK-A515 defoaming agent, 30 parts by weight of BYK333 flatting agent and 20 parts by weight of BYK-190 dispersing agent, and stirring and mixing.
The long-acting anti-sticking coating prepared by the invention and the commercially available anti-sticking coating are detected, and the specific detection results are shown in the following table 1:
the test method comprises the following steps:
TABLE 1 characterization of Long-acting anti-sticking coating Properties
As can be seen from Table 1, the long-acting anti-sticking coating prepared by the invention has the advantages of good anti-sticking performance, excellent antifouling performance, good durability, wide market value and wide application prospect.
Claims (10)
1. A preparation method of a long-acting anti-sticking coating is characterized by comprising the following specific preparation steps:
(1) adding the halloysite nanotube into the composite antifouling agent according to the mass ratio of 1:8, stirring, mixing, ball-milling, filtering by using a screen, collecting sieved particles, washing, drying, grinding and sieving to obtain modified load particles;
(2) taking and crushing sepiolite, collecting sepiolite particles, respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of aluminum chloride, 2-3 parts by weight of aluminum nitrate and 25-30 parts by weight of aluminum sulfate with the mass fraction of 1% in a mortar, grinding and dispersing, collecting dispersed slurry, filtering and collecting filter cakes, washing, drying and grinding to obtain modified sepiolite particles;
(3) respectively weighing 45-50 parts by weight of deionized water, 10-15 parts by weight of modified sepiolite particles, 6-8 parts by weight of methyl propanesulfonic acid and 3-5 parts by weight of N, N' -methylene bisacrylamide, placing the materials into a three-neck flask, stirring and mixing the materials, placing the materials into a reaction solution at 45-50 ℃ for heat preservation reaction to obtain a reaction solution, dropwise adding acrylic acid into the reaction solution, stirring and mixing the materials after the dropwise adding is finished, and collecting a mixed solution;
(4) Inserting an electrode into the mixed solution, performing discharge treatment, performing heat preservation reaction, standing and cooling to room temperature, collecting gel liquid, performing vacuum freeze drying, performing ball milling and sieving to obtain modified particles, respectively weighing 45-50 parts by weight of dimethylbenzene, 6-8 parts by weight of modified load particles, 15-20 parts by weight of acrylic resin, 10-15 parts by weight of modified particles, 6-8 parts by weight of pigment and 6-8 parts by weight of auxiliary agent, placing the materials in a stirrer, and stirring and mixing to obtain the long-acting anti-sticking coating.
2. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: the preparation method of the composite antifouling agent in the step (1) comprises the following steps:
respectively weighing 45-50 parts of bromopyrrole carbonitrile, 10-15 parts of cuprous oxide, 3-5 parts of copper pyrithione and 10-15 parts of trichlorophenylmaleimide in parts by weight, placing the materials in a triangular flask, stirring, mixing, and placing the mixture under 200-300W for ultrasonic dispersion for 10-15 min to obtain the composite antifouling agent.
3. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: the screen mesh filtration in the step (1) adopts a screen mesh with the aperture of 0.25-0.28 μm.
4. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: and (2) washing in the step (1) is respectively washing with acetone and deionized water for 3-5 times.
5. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: the particle size of the modified load particles in the step (1) is 500 meshes.
6. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: 15% of the mass fraction in the step (2).
7. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: the mass fractions of the aluminum chloride and the aluminum nitrate in the step (2) are both 15 percent.
8. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: and (3) mixing the acrylic acid and the reaction liquid according to the mass ratio of 1: 8.
9. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: and (4) discharging the material at the step (3) with the voltage of 450-480V.
10. The method for preparing the long-acting anti-sticking coating according to claim 1, wherein the method comprises the following steps: and (4) the auxiliary agent is prepared by respectively weighing 45-50 parts by weight of BYK-A515 defoaming agent, 25-30 parts by weight of BYK333 flatting agent and 15-20 parts by weight of BYK-190 dispersing agent, and stirring and mixing.
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| CN1902244A (en) * | 2003-12-31 | 2007-01-24 | 3M创新有限公司 | Water- and oil-repellent fluoroacrylates |
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| 利用埃洛石纳米管负载防污剂制备防污复合材料;公聪聪;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180430(第4期);第12、13、15-17页 * |
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