CN113502129B - Transparent antifouling patch and preparation method and application thereof - Google Patents

Transparent antifouling patch and preparation method and application thereof Download PDF

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CN113502129B
CN113502129B CN202110849955.4A CN202110849955A CN113502129B CN 113502129 B CN113502129 B CN 113502129B CN 202110849955 A CN202110849955 A CN 202110849955A CN 113502129 B CN113502129 B CN 113502129B
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hydrogel
solution
antifouling
patch
transparent
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CN113502129A (en
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周峰
冯海燕
于波
杨武芳
麻拴红
马延飞
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Lanzhou Institute of Chemical Physics LICP of CAS
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2429/00—Presence of polyvinyl alcohol
    • C09J2429/006—Presence of polyvinyl alcohol in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a transparent antifouling patch and a preparation method and application thereof, belonging to the technical field of antifouling materials. Firstly, preparing a transparent PVA hydrogel sheet containing glycerin by a freezing method, then pretreating the hydrogel by tannic acid, and then introducing Cu with an antifouling effect by the tannic acid2+Coating the prepared adhesive glue containing phenolic hydroxyl on one surface of hydrogel to finally obtain the asymmetric adhesive transparent patch with the antifouling function. The transparent antifouling patch prepared by the invention has higher transmittance, better underwater adhesion performance, excellent mechanical strength and biological and oil pollution prevention performance, can be used on the surface of a numerical display part of marine monitoring equipment, and can effectively prevent marine fouling problems on a lens caused by algae, oil stains and the like in the sea.

Description

Transparent antifouling patch and preparation method and application thereof
Technical Field
The invention relates to the technical field of antifouling materials, in particular to a transparent antifouling patch and a preparation method and application thereof.
Background
The ocean reserves immeasurable resources, and the development and utilization of ocean resources become important development strategies in many countries. However, the marine industry and marine activities inevitably encounter problems with marine pollution. As marine microorganisms attach, the hulls become rough, increase in weight, cause significant increases in sailing resistance and fuel consumption, and cause billions of dollars of economic loss and increases in greenhouse gases each year. Marine organisms attached to the hull of a ship may invade a new sea area and compete with the original organisms, thereby affecting ecological balance. Crude oil leakage events occur frequently, and tens of millions of tons of crude oil are released into the ocean each year. Solving the adhesion of oil to the surface of the instrument is becoming a big problem. Optical sensors with transparent windows are the "eye" in the field of marine exploration. The use of marine monitoring systems provides a number of advantages to humans. Marine fouling on the system optics makes underwater work harder.
To solve the marine antifouling problem of the optical sensor, various methods have been developed. Paints containing biological bactericides or toxic components are widely used for marine antifouling. The development of marine antifouling paint has gone through three stages, namely, conventional antifouling paint, tin-containing self-polishing antifouling paint and tin-free self-polishing antifouling paint. The tin-containing self-polishing antifouling paint has good antifouling effect and long antifouling time, but has serious pollution to the marine environment, so the tin-containing self-polishing antifouling paint is forbidden by the international maritime organization; the tin-free self-polishing antifouling paint replaces tin with copper and the like, and has relatively small pollution to marine environment. Hydrogels have been developed for use in marine antifouling because of their extremely low adhesion to proteins, oily substances, bacteria, etc. due to their hydrophilicity and high water content. Chinese patent No. CN201910440525.X discloses a hydrogel composed of a hydrophilic network and a hydrophobic network for marine antifouling, and Chinese patent No. CN202010652873.6 discloses a high-adhesiveness hydrogel coating, but the existing hydrogel has the problem of poor light transmittance.
Disclosure of Invention
In view of the above, the present invention aims to provide a transparent antifouling patch, and a preparation method and an application thereof. The antifouling patch prepared by the method has high light transmission.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a transparent antifouling patch, which comprises the following steps:
mixing polyvinyl alcohol, water and glycerol, and freezing to obtain hydrogel;
mixing the hydrogel with a tannic acid solution for pretreatment to obtain pretreated hydrogel;
dissolving the pretreated hydrogel with soluble Cu2+Treating with a salt solution to obtain a hydrogel substrate;
mixing dopamine methacrylamide with a hydrophobic monomer to perform free radical polymerization reaction to obtain an adhesive containing phenolic hydroxyl, wherein the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate;
mixing the adhesive containing phenolic hydroxyl with an organic solvent to obtain an adhesive solution;
and coating the adhesive glue solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
Preferably, the average polymerization degree of the polyvinyl alcohol is 1750 +/-50, and the mass percentage of the polyvinyl alcohol in the total mass of the polyvinyl alcohol and the water is 5-20%.
Preferably, the mixed solution obtained by mixing the polyvinyl alcohol, the water and the glycerol has a mass fraction of 30-50% of the glycerol.
Preferably, the freezing is cyclic freezing, the number of the cyclic freezing is two, the temperature of each cyclic freezing is-30 ℃, and the time is independently 2-12 h.
Preferably, the time for mixing the hydrogel and the tannic acid solution is 0.5-24 h.
Preferably, the soluble Cu2+The salt solution is CuCl2Solutions or CuSO4And (3) solution.
Preferably, the soluble Cu2+The time of the salt solution treatment is 5min to 12 h.
Preferably, the molar ratio of the dopamine methacrylamide to the hydrophobic monomer is 1: 20-1: 5.
The invention also provides a transparent antifouling patch prepared by the preparation method in the technical scheme, which comprises a hydrogel substrate and an adhesive solution loaded on one side of the hydrogel substrate;
the hydrogel substrate is composed of polyvinyl alcohol, water, glycerol, tannic acid solution and soluble Cu2+Preparing salt; the adhesive glue solution is prepared by mixing adhesive glue containing phenolic hydroxyl and an organic solvent, the adhesive glue containing the phenolic hydroxyl is prepared by mixing dopamine methacrylamide and a hydrophobic monomer for free radical polymerization, and the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate。
The invention also provides the application of the transparent antifouling patch in underwater antifouling.
The invention provides a preparation method of a transparent antifouling patch, which comprises the following steps: mixing a polyvinyl alcohol (PVA) aqueous solution and glycerol, and freezing to obtain hydrogel; mixing the hydrogel with a tannic acid solution for pretreatment to obtain pretreated hydrogel; dissolving the pretreated hydrogel with soluble Cu2+Treating with a salt solution to obtain a hydrogel substrate; mixing dopamine methacrylamide with a hydrophobic monomer to perform free radical polymerization reaction to obtain an adhesive containing phenolic hydroxyl, wherein the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate; mixing the adhesive containing phenolic hydroxyl with an organic solvent to obtain an adhesive solution; and coating the adhesive glue solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
The preparation method comprises the steps of preparing a transparent PVA hydrogel sheet containing glycerol by using a freezing method, pretreating the hydrogel by using tannic acid, and introducing Cu with an antifouling effect by using the tannic acid2+Coating the prepared adhesive glue containing phenolic hydroxyl on one surface of hydrogel to finally obtain the asymmetric adhesive transparent patch with the antifouling function. According to the invention, glycerin is added into the hydrogel through intermolecular hydrogen bonds, so that the crystal size of the hydrogel is reduced, but the area of a crystal region is unchanged, and the hydrogel has good light transmittance; tannic acid is introduced into hydrogel via hydrogen bond interaction, and can be used for introducing Cu while improving strength2+Media of metal ions, Cu2+Has marine antifouling property; using tannic acid and metal ion Cu2+The coordination of (2) enables the hydrogel to generate strong interaction with the adhesive glue which is coated on the surface of the hydrogel and contains phenolic hydroxyl, thereby obtaining the transparent paster which can be adhered and has antifouling effect. Cu contained in hydrogel2+Has antifouling effect on algae; the hydrophilicity of the PVA hydrogel renders it oleophobic underwater. In mussel secretion, Dopamine (DOPA) in raw material of adhesive glue containing phenolic hydroxyl group is key for realizing fast strong wet adhesionThe group can generate interaction with any substrate, including metal coordination with metal oxide, hydrophobic interaction with a hydrophobic interface and hydrophilic interaction with a hydrophilic interface, so that the transparent antifouling patch prepared by the invention has good adhesion on various substrates under water.
The transparent anti-fouling patch prepared by the preparation method provided by the invention has high transmittance, good underwater adhesion performance, excellent mechanical strength and biological and oil pollution prevention performance, can be used on the surface of a numerical display part of marine monitoring equipment, can effectively prevent marine fouling problems of algae, oil stains and the like in the sea on a lens, and meets the normal use requirements of the transparent anti-fouling patch.
Drawings
FIG. 1 is a flow chart of the present invention for preparing the transparent anti-fouling patch;
FIG. 2 is a sectional electron microscope image of the hydrogel and the adhesive gel prepared in example 1;
FIG. 3 is a graph showing the change in swelling ratio of the hydrogel substrate prepared in example 1 when it is placed in seawater;
FIG. 4 is a photograph of the transparent anti-fouling patch prepared in example 1 applied to a protective lens on an underwater oleophobic field.
Detailed Description
The invention provides a preparation method of a transparent antifouling patch, which comprises the following steps;
mixing polyvinyl alcohol, water and glycerol, and freezing to obtain hydrogel;
mixing the hydrogel with a tannic acid solution for pretreatment to obtain pretreated hydrogel;
dissolving the pretreated hydrogel with soluble Cu2+Treating with a salt solution to obtain a hydrogel substrate;
mixing dopamine methacrylamide with a hydrophobic monomer to perform free radical polymerization reaction to obtain an adhesive containing phenolic hydroxyl, wherein the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate;
mixing the adhesive containing phenolic hydroxyl with an organic solvent to obtain an adhesive solution;
and coating the adhesive glue solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
The hydrogel is obtained by mixing polyvinyl alcohol, water and glycerol and then freezing.
In the present invention, the average polymerization degree of the polyvinyl alcohol is preferably 1750 ± 50, and the percentage of the mass of the polyvinyl alcohol to the total mass of the polyvinyl alcohol and water is preferably 5% to 20%, and more preferably 10% to 15%.
In the present invention, the mass fraction of glycerin in the mixed solution obtained by mixing the polyvinyl alcohol, water, and glycerin is preferably 30% to 50%, and more preferably 40% to 50%.
In the invention, the freezing is preferably cyclic freezing, the number of times of cyclic freezing is preferably two, the temperature of each cyclic freezing is preferably-30 ℃, and the time is independently preferably 2-12 h. In the present invention, it is preferable that the first freezing is performed after natural thawing at room temperature and then freezing is performed.
In the present invention, the polyvinyl alcohol, water and glycerin are preferably mixed in the order of melting the polyvinyl alcohol and water, and then mixing the melted polyvinyl alcohol and glycerin.
After the hydrogel is obtained, the hydrogel is mixed with the tannic acid solution for pretreatment, and the pretreated hydrogel is obtained.
In the present invention, the mass fraction of the tannic acid solution is preferably 0.5% to 5%, and more preferably 1% to 3%. The invention uses tannic acid to treat hydrogel and then uses the tannic acid to introduce Cu with antifouling effect2+。
In the invention, the time for mixing the hydrogel and the tannic acid solution is preferably 0.5-24 h, more preferably 1-12 h, and most preferably 1-6 h.
In the present invention, the hydrogel is preferably soaked in the tannic acid solution.
After the pretreatment hydrogel is obtained, the invention uses soluble Cu for the pretreatment hydrogel2+And (4) treating with a salt solution to obtain the hydrogel substrate.
In the present invention, the soluble Cu2+The salt solution is preferably CuCl2Solutions or CuSO4And (3) solution.
In the present invention, the soluble Cu2+The concentration of the salt solution is preferably 0.05-0.5 mol/L.
In the present invention, the soluble Cu2+The time for the salt solution treatment is preferably 5min to 12 hours, more preferably 1 to 10 hours, and most preferably 1 to 6 hours.
The invention preferably soaks the pre-treated hydrogel in the soluble Cu2+In a salt solution.
According to the invention, dopamine methacrylamide and a hydrophobic monomer are mixed for free radical polymerization reaction to obtain the adhesive containing phenolic hydroxyl, wherein the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate.
In the invention, the molar ratio of the dopamine methacrylamide to the hydrophobic monomer is preferably 1: 20-1: 5, and more preferably 1: 10-1: 5.
The present invention does not specifically limit the specific parameters of the radical polymerization reaction, and may be implemented by methods known to those skilled in the art, specifically, the invention refers to the schemes disclosed in Lee H, Lee B P, Messersmith P B.A reversible wet/dry adhesive impregnated by muscles and geckos [ J ] Nature,2007,448(7151): 338-341.
After the adhesive containing the phenolic hydroxyl is obtained, the adhesive containing the phenolic hydroxyl is mixed with an organic solvent to obtain an adhesive solution.
In the present invention, the organic solvent is preferably methanol, dichloromethane or ethyl acetate.
In the invention, the concentration of the adhesive glue solution is preferably 20-50 mg/mL, and more preferably 30-40 mg/mL. The present invention is not limited to the specific mixing method, and the mixing method may be a method known to those skilled in the art.
After obtaining the hydrogel substrate and the adhesive solution, the invention coats the adhesive solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
In the invention, the thickness of the single-side coating is preferably 2-10 microns.
In the present invention, the hydrogel substrate is preferably dried and then coated with the adhesive gel solution, and the present invention does not specifically limit the drying manner, and the hydrogel substrate may be dried to remove moisture from the surface thereof.
The invention also provides a transparent antifouling patch prepared by the preparation method in the technical scheme, which comprises a hydrogel substrate and an adhesive solution loaded on one side of the hydrogel substrate; the hydrogel substrate is composed of polyvinyl alcohol, water, glycerol, tannic acid solution and soluble Cu2+Preparing salt; the adhesive glue solution is prepared by mixing adhesive glue containing phenolic hydroxyl and an organic solvent, the adhesive glue containing the phenolic hydroxyl is prepared by mixing dopamine methacrylamide and a hydrophobic monomer and carrying out free radical polymerization reaction, and the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate.
FIG. 1 is a flow chart of the present invention for preparing the transparent anti-fouling patch, in which a polyvinyl alcohol aqueous solution and glycerin are mixed and then frozen to obtain a hydrogel (polyvinyl alcohol hydrogel), the hydrogel is mixed with a tannic acid solution for pretreatment, and then soluble Cu is used for the pretreatment2+And (3) treating with a salt solution to obtain a hydrogel substrate, and coating the adhesive glue solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
The invention also provides the application of the transparent antifouling patch in underwater antifouling.
In the present invention, the application is preferably to apply the transparent anti-fouling patch to the surface of a numerical display component of a marine monitoring device, such as underwater goggles in particular.
In the invention, in the application, the side of the transparent antifouling patch coated with the adhesive glue solution is contacted with the ocean monitoring equipment.
In order to further illustrate the present invention, the following will describe in detail the transparent antifouling patch and the preparation method and application thereof provided by the present invention with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
10 parts of polyvinyl alcohol (having an average polymerization degree of 1750), 40 parts of glycerin and 50 parts of deionized water were weighed and placed in a flask, and PVA was dissolved by heating and refluxing. And then pouring the obtained solution between glass templates, wherein the gap height is 0.36mm, freezing at-30 ℃, standing for 12 hours, taking out, thawing at room temperature, and freezing at-30 ℃ for 12 hours to obtain the polyvinyl alcohol hydrogel.
Preparing 1% tannic acid solution by mass fraction, and soaking the obtained hydrogel in the tannic acid solution for 1 hour. Preparing 0.1mol/L CuCl2The solution, the hydrogel after tannic acid treatment is put into CuCl2Soaking in the solution for 5 min. 7.5g of methoxyethyl acrylate, 1.7g of dopamine methacrylamide and 106mg of azobisisobutyronitrile were added to 20mL of dimethylformamide and subjected to radical polymerization at 70 ℃ to obtain an adhesive. The adhesive gel was dissolved in methylene chloride to give a 50mg/mL adhesive gel solution, and a layer of adhesive gel solution (thickness 2 μm) was applied to the surface of the surface-dried hydrogel substrate to give a transparent anti-fouling patch, which was designated as sample A.
Example 2
10 parts of polyvinyl alcohol (with the average polymerization degree of 1750), 50 parts of glycerol and 40 parts of deionized water are weighed and placed in a flask, a reflux condensing device is set up, and the PVA is dissolved by heating to 135 ℃. And then pouring the obtained solution between glass templates, wherein the gap height is 0.36mm, freezing at-30 ℃, standing for 12 hours, taking out, thawing at room temperature, and freezing at-30 ℃ for 12 hours to obtain the polyvinyl alcohol hydrogel.
Preparing 1% tannic acid solution by mass fraction, and soaking the obtained hydrogel in the tannic acid solution for 1 hour. Preparing 0.1mol/L CuCl2The solution, the hydrogel after tannic acid treatment is put into CuCl2Soaking in the solution for 1 h. 7.5g of methoxyethyl acrylate, 1.7g of dopamine methacrylamide and 106mg of azobisisobutyronitrile were added to 20mL of dimethylformamide and subjected to radical polymerization at 70 ℃ to obtain an adhesive. Dissolving the adhesive gum in dichloromethane to obtain 50mg/mL adhesive gum solution, and drying on surfaceThe surface of the hydrogel substrate was coated with a layer of adhesive glue solution (10 microns thick) to produce a transparent anti-fouling patch, designated sample B.
Example 3
10 parts of polyvinyl alcohol (with the average polymerization degree of 1750), 50 parts of glycerol and 40 parts of deionized water are weighed and placed in a flask, a reflux condensing device is set up, and the PVA is dissolved by heating to 135 ℃. And then pouring the obtained solution between glass templates, wherein the gap height is 0.36mm, freezing at-30 ℃, standing for 2 hours, taking out, thawing at room temperature, and freezing at-30 ℃ for 12 hours to obtain the polyvinyl alcohol hydrogel.
Preparing 1% tannic acid solution by mass fraction, and soaking the obtained hydrogel in the tannic acid solution for 1 hour. Preparing 0.1mol/L CuCl2The solution, the hydrogel after tannic acid treatment is put into CuCl2Soaking in the solution for 3 h. 7.5g of methoxyethyl acrylate, 1.7g of dopamine methacrylamide and 106mg of azobisisobutyronitrile were added to 20mL of dimethylformamide and subjected to radical polymerization at 70 ℃ to obtain an adhesive. The adhesive gel was dissolved in methylene chloride to give a 50mg/mL adhesive gel solution, and a layer of adhesive gel solution (thickness 2 μm) was applied to the surface of the surface-dried hydrogel substrate to give a transparent anti-fouling patch, which was designated as sample C.
Example 4
10 parts of polyvinyl alcohol (with the average polymerization degree of 1750), 50 parts of glycerol and 40 parts of deionized water are weighed and placed in a flask, a reflux condensing device is set up, and the PVA is dissolved by heating to 135 ℃. And then pouring the obtained solution between glass templates, wherein the gap height is 0.36mm, freezing at-30 ℃, standing for 2 hours, taking out, thawing at room temperature, and freezing at-30 ℃ for 12 hours to obtain the polyvinyl alcohol hydrogel.
Preparing 1% tannic acid solution by mass fraction, and soaking the obtained hydrogel in the tannic acid solution for 1 hour. Preparing 0.1mol/L CuCl2The solution, the hydrogel after tannic acid treatment is put into CuCl2Soaking in the solution for 3 h. 10g of methoxyethyl acrylate, 1.7g of dopamine methacrylamide and 106mg of azobisisobutyronitrile were added to 20mL of dimethylformamide and free-radically polymerized at 70 DEGAnd obtaining the adhesive. The adhesive gel was dissolved in methylene chloride to give a 50mg/mL adhesive gel solution, and a layer of adhesive gel solution (thickness 2 μm) was applied to the surface of the surface-dried hydrogel substrate to give a transparent anti-fouling patch, which was designated as sample D.
The transmittance, underwater oil contact angle, antifouling property and mechanical strength of the transparent antifouling patch prepared in the embodiment 1-3 are evaluated, and the results are shown in table 1, so that the transparent antifouling patch prepared by the invention has high transmittance, excellent mechanical strength and biological and oil pollution prevention properties, can be used on the surface of a numerical display part of a marine monitoring device, can effectively prevent marine fouling on a lens caused by algae, oil stains and the like in the sea, and meets the normal use requirements of the transparent antifouling patch.
TABLE 1 Performance test results of the transparent antifouling patches prepared in examples 1 to 3
Sample (I) Light transmittance Oil contact angle (o) Mechanical Strength (MPa) Algal density (/ mm)2)
A 86％ 147 1.48 147
B 79％ 146 1.75 72
C 73％ 143 1.86 70
Blank space - - - 1568
The adhesion strength of the transparent antifouling patches prepared in examples 1 and 4 was measured (the adhesion strength of hydrogel was measured using glass as a substrate), and the adhesion strength obtained by applying 20KPa was shown in table 2, which indicates that the transparent antifouling patches prepared according to the present invention have good underwater adhesion properties.
Table 2 adhesion strength data of transparent antifouling patches prepared in examples 1 and 4
Figure BDA0003182062170000081
Figure BDA0003182062170000091
FIG. 2 is a sectional electron microscope image of the hydrogel and the adhesive gel prepared in example 1.
FIG. 3 is a graph showing the change in swelling ratio of the hydrogel substrate prepared in example 1, which is placed in seawater, and illustrates that the hydrogel substrate prepared in the present invention can be restored to its original shape by absorbing water and stably exist in seawater.
Fig. 4 is a photograph of the transparent anti-fouling patch prepared in example 1 applied to an underwater oleophobic field of a protective lens, and it can be known that the transparent anti-fouling patch provided by the present invention can be applied to the surface of a transparent lens of an underwater detection system, and can effectively prevent marine fouling caused by algae, oil stains, etc. in the sea on the lens.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. A preparation method of a transparent antifouling patch is characterized by comprising the following steps:
mixing polyvinyl alcohol, water and glycerol, and freezing to obtain hydrogel;
mixing the hydrogel with a tannic acid solution for pretreatment to obtain pretreated hydrogel;
dissolving the pretreated hydrogel with soluble Cu2+Treating with a salt solution to obtain a hydrogel substrate;
mixing dopamine methacrylamide with a hydrophobic monomer to perform free radical polymerization reaction to obtain an adhesive containing phenolic hydroxyl, wherein the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate;
mixing the adhesive containing phenolic hydroxyl with an organic solvent to obtain an adhesive solution;
and coating the adhesive glue solution on one side of the hydrogel substrate to obtain the transparent antifouling patch.
2. The production method according to claim 1, wherein the polyvinyl alcohol has an average degree of polymerization of 1750 ± 50, and the mass percentage of the polyvinyl alcohol to the total mass of the polyvinyl alcohol and water is 5% to 20%.
3. The method according to claim 1 or 2, wherein the mixed solution of the polyvinyl alcohol, water and glycerin contains 30 to 50% by mass of glycerin.
4. The preparation method according to claim 1, wherein the freezing is cyclic freezing, the cyclic freezing is performed twice, the temperature of each cyclic freezing is-30 ℃, and the time is independently 2-12 h.
5. The method according to claim 1, wherein the time for mixing the hydrogel with the tannic acid solution is 0.5 to 24 hours.
6. The method of claim 1, wherein the soluble Cu is2+The salt solution is CuCl2Solutions or CuSO4And (3) solution.
7. The method according to claim 1 or 6, wherein the soluble Cu is2+The time of the salt solution treatment is 5min to 12 h.
8. The preparation method according to claim 1, wherein the molar ratio of the dopamine methacrylamide to the hydrophobic monomer is 1: 20-1: 5.
9. The transparent antifouling patch prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising a hydrogel substrate and an adhesive glue solution loaded on one side of the hydrogel substrate;
the hydrogel substrate is composed of polyvinyl alcohol, water, glycerol, tannic acid solution and soluble Cu2+Preparing salt; the adhesive glue solution is prepared by mixing adhesive glue containing phenolic hydroxyl and an organic solvent, the adhesive glue containing the phenolic hydroxyl is prepared by mixing dopamine methacrylamide and a hydrophobic monomer and carrying out free radical polymerization reaction, and the hydrophobic monomer is methoxyethyl acrylate or methyl methacrylate.
10. Use of the transparent antifouling patch according to claim 9 for underwater antifouling.
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