CN114574054A - Water-based antifouling treatment agent - Google Patents
Water-based antifouling treatment agent Download PDFInfo
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- CN114574054A CN114574054A CN202210246626.5A CN202210246626A CN114574054A CN 114574054 A CN114574054 A CN 114574054A CN 202210246626 A CN202210246626 A CN 202210246626A CN 114574054 A CN114574054 A CN 114574054A
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- agent
- asymmetric
- aqueous
- nano particles
- antifouling
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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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a water-based antifouling treatment agent which is prepared by mixing water-based polymer emulsion, asymmetric amphiphilic nano particles, a curing agent and an auxiliary agent in proportion. The invention adopts asymmetric amphiphilic nano particles to modify the antifouling treatment agent, so that the hydrophilic part of the antifouling treatment agent has good compatibility with the aqueous emulsion, and the hydrophobic part is exposed in the interface between the polymer and air after being cured to form a dendritic structure. The treating agent is crosslinked by isocyanate to obtain a super-hydrophobic antifouling coating with a micro/nano composite structure; the coating has high water contact angle, excellent self-cleaning property and lyophobic property, low adhesive force and excellent antifouling property. The compatibility of the nano particles and the aqueous polymer emulsion is improved by adopting the asymmetric amphiphilic nano particles, and the adhesive force between the treating agent and the surface of the treated object is improved.
Description
Technical Field
The invention relates to the technical field of antifouling treatment agents, and particularly relates to an aqueous antifouling treatment agent.
Background
The antifouling treatment agent with better antifouling effect in the current market mainly comprises two categories of paint containing low-toxicity safe antifouling agent and antifouling paint with low surface energy, wherein the low surface energy mainly refers to organosilicon series and organofluorine series. In general, compounds containing fluorine and silicon have properties such as water-and oil-repellency, chemical resistance, lubricity, releasability, and antifouling property because the surface energy thereof is very small. By utilizing its properties, the water-and oil-repellent antifouling agent is industrially widely used as a water-and oil-repellent antifouling agent for surfaces of a wide variety of materials such as glass, metal, resin, paper, fiber and the like, a lubricant for magnetic recording media, an oil-repellent agent for precision equipment, a release agent, a cosmetic, a protective film and the like.
Although pure organosilicon or organofluorine materials have certain antifouling effect, the disadvantages are obvious. The fluorine-and silicon-containing compound has non-adhesive properties and non-adhesive properties to other substrates due to its low surface energy, and even if it can be applied to the surface of a substrate, it cannot form a coating film and make it adhere thereto. The organic silicon resin has the defects of poor cohesiveness, low strength and other mechanical properties, and the curing temperature is high, so that the construction is inconvenient and the price is expensive. Therefore, it is necessary to chemically modify silicones to overcome the above-mentioned disadvantages.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide an aqueous antifouling agent.
The technical scheme adopted by the invention for solving the technical problem is as follows: the water-based antifouling treatment agent is prepared by mixing water-based polymer emulsion, asymmetric amphiphilic nano particles, a curing agent and an auxiliary agent in proportion.
Further, the aqueous polymer emulsion is one or a combination of two of aqueous polyacrylic emulsion and aqueous polyurethane emulsion.
Further, the asymmetric amphiphilic nanoparticles are silica nanoparticles and titanium dioxide nanoparticles with hydrophilicity and hydrophobicity; the dosage of the asymmetric amphiphilic nano particles is 1-10 wt% of the dosage of the aqueous polymer emulsion.
Further, the preparation of the asymmetric amphiphilic nanoparticles comprises the following steps:
s1, preparation of Pickering emulsion: adding a nano particle aqueous solution into paraffin for emulsification, coating nano particles on the surface of a paraffin pellet, and inlaying the nano particles on the surface of a paraffin microsphere to form interface protection;
s2, asymmetric modification of the surface of the nanoparticle: adding a hydrophobic silane coupling agent into the Pickering emulsion in S1, and carrying out silylation modification on the surface of the nano-particles on the surface of the paraffin to obtain nano-particles with asymmetric structures;
s3, post-processing: and (3) centrifugally washing the modified asymmetric-structure nano particles, and drying in vacuum to obtain the asymmetric amphiphilic nano particles.
Furthermore, the hydrophobic silane coupling agent is a fluorocarbon silane coupling agent and a silane coupling agent containing long-chain alkane.
Wherein the general formula of the long-chain alkyl silane coupling agent is R- (CH)2)n-SiX3N is 4 to 18, X is methoxy or ethoxy, R is one of hydrogen, cyano, phenyl, amino, methoxy, epoxy, isocyanate or vinyl, and specific examples thereof include butyltrimethoxysilane, hexyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, 4-cyanobutyltrimethylsilane, 4-phenylbutyltriethoxysilane and the like.
The fluorocarbon silane coupling agent is selected from (3,3, 3-trifluoropropyl) methyldimethoxysilane, (3,3, 3-trifluoropropyl) methyldiethoxysilane, (3,3, 3-trifluoropropyl) trimethoxysilane, (3,3, 3-trifluoropropyl) triethoxysilane, and nonafluorohexyltrimethoxysilane.
Further, the mass concentration range of the nano particle water solution is 2-10%; the mass ratio of the nanoparticles to the hydrophobic silane coupling agent is 20/1-2/1; the mass ratio of the nano particles to the paraffin is 1/5-1/20.
Further, the curing agent is hydrophilic polyisocyanate, and the amount of the curing agent is 1-10 wt% of the amount of the aqueous polymer emulsion. The hydrophilic polyisocyanate curing agent includes, but is not limited to
XP 2759、
XP 2655、
XP 2547、
XP 2451。
Further, the auxiliary agent comprises a leveling agent, an antifoaming agent and a thickening agent.
The invention has the beneficial effects that: compared with the prior art, the water-based antifouling treatment agent provided by the invention has the following advantages:
1) because the used nano particles have asymmetric, hydrophilic-hydrophobic characteristics, the anti-fouling treatment agent is modified by the asymmetric amphiphilic nano particles, so that the hydrophilic part of the anti-fouling treatment agent has good compatibility with the aqueous emulsion, and the hydrophobic part is exposed in a polymer and air interface after being cured to form a dendritic structure. The treating agent is crosslinked by isocyanate to obtain a super-hydrophobic antifouling coating with a micro/nano composite structure; the coating has high water contact angle, excellent self-cleaning property and lyophobic property, low adhesive force and excellent antifouling property.
2) The compatibility of the nano particles and the aqueous polymer emulsion is improved by adopting the asymmetric amphiphilic nano particles, and the adhesive force of the treating agent and the surface of the treated object is improved.
Drawings
Fig. 1 is a reaction scheme of the synthesis of asymmetric amphiphilic nanoparticles in example 1.
Detailed Description
The invention is further illustrated by the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
Asymmetric amphiphilic nanoparticle synthesis
S1, taking 1g SiO at room temperature2The nano particles are added into 20mL of deionized water and are subjected to ultrasonic dispersion for 30 min. Stirring and heating to 75 ℃, then adding 10g of paraffin, and homogenizing and emulsifying at a high speed after the paraffin is melted. Cooling to below 25 deg.C to obtain PiA cocking emulsion.
S2, dispersing 0.2g of butyltrimethoxysilane in a methanol solution, adding the solution into a Pickering emulsion of silicon dioxide, continuously stirring, adding a small amount of ammonia water for catalysis, and maintaining the reaction for 24 hours. And (3) carrying out silylation modification on the surface of the nano particle on the paraffin surface to obtain the nano particle with the asymmetric structure.
S3, post-processing: and carrying out modification on the asymmetric-structure nano particles. And after the reaction is finished, dissolving the paraffin spheres after the reaction is finished by using a solvent, performing centrifugal separation, washing by using absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the asymmetric amphiphilic nanoparticles.
The reaction scheme is shown in figure 1.
Example 2
Asymmetric amphiphilic nanoparticle synthesis
S1, taking 2g TiO at room temperature2The nano particles are added into 20mL of deionized water and are subjected to ultrasonic dispersion for 30 min. Stirring and heating to 75 ℃, then adding 15g of paraffin, and homogenizing and emulsifying at a high speed after the paraffin is melted. After cooling to below 25 ℃, a Pickering emulsion was obtained.
S2, dispersing 1g of (3,3, 3-trifluoropropyl) methyldimethoxysilane in a methanol solution, adding the solution into Pickering emulsion of titanium dioxide, continuing stirring, adding a small amount of ammonia water for catalysis, and maintaining the reaction for 24 hours. And (3) carrying out silylation modification on the surface of the nano particle on the paraffin surface to obtain the nano particle with the asymmetric structure.
S3, post-processing: and carrying out modification on the asymmetric-structure nano particles. And after the reaction is finished, dissolving the paraffin spheres after the reaction is finished by using a solvent, performing centrifugal separation, washing by using absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the asymmetric amphiphilic nanoparticles.
The reaction scheme is shown in figure 1.
Examples 3 to 6
Synthesis of aqueous antifouling treatment agent
The mixture ratio of the examples 3 to 6 and the comparative examples 1 to 2 is shown in table 1, and the components are mixed according to the proportion, stirred and evenly coated on PU leather, and cured for 10 minutes at 130 ℃. The surface tension (water drop angle), adhesion, were tested as shown in table 2.
TABLE 1
The thickener is a nonionic hydrophobic modified polyurethane rheological thickener, and the defoaming agent is an organic silicon defoaming agent.
TABLE 2
The test result shows that the water-based antifouling treatment agent prepared by using the asymmetric amphiphilic nano particles has high contact angle and good adhesion.
The above embodiments are only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (8)
1. An aqueous antifouling agent, characterized in that: the antifouling treatment agent is prepared by mixing aqueous polymer emulsion, asymmetric amphiphilic nano particles, a curing agent and an auxiliary agent in proportion.
2. An aqueous antifouling agent according to claim 1, wherein: the water-based polymer emulsion is one or the combination of two of water-based polyacrylic acid emulsion and water-based polyurethane emulsion.
3. An aqueous antifouling agent according to claim 1, wherein: the asymmetric amphiphilic nanoparticles are silica nanoparticles and titanium dioxide nanoparticles with hydrophilicity and hydrophobicity; the dosage of the asymmetric amphiphilic nano particles is 1-10 wt% of the dosage of the aqueous polymer emulsion.
4. The aqueous antifouling treatment agent according to claim 3, wherein the asymmetric amphiphilic nanoparticles are prepared by:
s1, preparing Pickering emulsion: adding a nano particle aqueous solution into paraffin for emulsification, coating nano particles on the surface of a paraffin pellet, and inlaying the nano particles on the surface of a paraffin microsphere to form interface protection;
s2, asymmetric modification of the surface of the nanoparticle: adding a hydrophobic silane coupling agent into the Pickering emulsion in S1, and carrying out silylation modification on the surface of the nano-particles on the surface of the paraffin to obtain nano-particles with asymmetric structures;
s3, post-processing: and (3) carrying out centrifugal washing on the modified asymmetric-structure nano particles, and drying in vacuum to obtain the asymmetric amphiphilic nano particles.
5. An aqueous antifouling agent according to claim 4, wherein: the hydrophobic silane coupling agent is a fluorocarbon silane coupling agent and a silane coupling agent containing long-chain alkane.
6. An aqueous antifouling agent according to claim 4, wherein: the mass concentration range of the nano particle aqueous solution is 2-10%; the mass ratio of the nanoparticles to the hydrophobic silane coupling agent is 20/1-2/1; the mass ratio of the nano particles to the paraffin is 1/5-1/20.
7. An aqueous antifouling agent according to claim 1, wherein: the curing agent is hydrophilic polyisocyanate, and the using amount of the curing agent is 1-10 wt% of that of the aqueous polymer emulsion.
8. An aqueous antifouling agent according to claim 1, wherein: the auxiliary agent comprises a leveling agent, a defoaming agent and a thickening agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210246626.5A CN114574054A (en) | 2022-03-14 | 2022-03-14 | Water-based antifouling treatment agent |
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| CN202210246626.5A CN114574054A (en) | 2022-03-14 | 2022-03-14 | Water-based antifouling treatment agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116478568A (en) * | 2023-03-24 | 2023-07-25 | 辽宁顺风新材料科技有限公司 | Amphiphilic nano silicon dioxide filler for improving water resistance of water-based paint and preparation method thereof |
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Patent Citations (9)
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| CN108192454A (en) * | 2017-12-29 | 2018-06-22 | 西安交通大学 | A kind of water-and acrylate Polymer/nano particle hybrid and the hydrophobic coating and preparation method based on it |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116478568A (en) * | 2023-03-24 | 2023-07-25 | 辽宁顺风新材料科技有限公司 | Amphiphilic nano silicon dioxide filler for improving water resistance of water-based paint and preparation method thereof |
| CN116478568B (en) * | 2023-03-24 | 2024-04-26 | 辽宁顺风新材料科技有限公司 | Amphiphilic nano silicon dioxide filler for improving water resistance of water-based paint and preparation method thereof |
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