Free radical self-release antifouling agent containing oxime urethane group as well as preparation method and application of free radical self-release antifouling agent

Abstract

The invention discloses a free radical self-release antifouling agent containing an oxime urethane group and a preparation method and application thereof, the antifouling agent has a structure as shown in formula (I), R1 is derived from isocyanate, and R2 and R3 are derived from oxime-containing substances; the free radical self-release antifouling agent is mainly prepared from oxime and isocyanate groups through a reaction. The preparation process is simple and convenient, the cost is low, and large-scale controllable preparation can be realized; according to the invention, oxime urethane groups are cracked in seawater through a strong electron-withdrawing effect of imine bonds to generate free radicals, so that attachment of fouling organisms can be effectively inhibited; the free radical self-release anti-fouling agent containing the oxime urethane group can be used as a coating additive to play an anti-fouling role, can generate intermolecular force with matrix resin to realize stable release, and is degradable, excellent in anti-fouling effect and wide in application prospect. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of antifouling materials, and in particular to a free radical self-releasing antifouling agent containing oxime urethane groups, and a preparation method and application thereof. Background Art

[0002] Marine biofouling refers to the adhesion of various types of fouling organisms to the surface of marine equipment, including ships and offshore platforms, and has become a serious global problem. The firm attachment of marine organisms to the hull promotes the corrosion of metal materials, significantly increases navigation resistance, and leads to additional energy consumption; fouling organisms enter different areas due to ship transportation, which leads to species invasion. Preventing marine biofouling is a key research direction for human marine activities. In the past century, a variety of antifouling materials and antifouling technologies have been developed. The active antifouling strategy of coating antifouling coatings on the surface is the simplest, most economical and efficient way to solve marine fouling. However, the antifouling properties of most antifouling coatings are derived from the antifouling agents with toxic properties doped in the coatings, especially the widely used cuprous oxide and some antifouling agents containing metallic zinc, which usually have toxic effects on many non-target organisms (such as fish and shrimp), affect the metabolism of organisms, and cause harm to their brains, livers, plasma and gonads, causing serious impacts on the environment. Therefore, the development of green and environmentally friendly antifouling agents with intrinsic antifouling properties has become one of the important ways to solve this problem. In addition, the problem of marine microplastics is becoming increasingly serious. Non-degradable or low-degradation organic polymer-based antifouling materials are one of the sources of marine microplastics. It is necessary to develop degradable antifouling agents.

[0003] Oxime urethane groups are usually obtained by the reaction of oxime and isocyanate groups. From the perspective of chemical structure, it is a combination of a carbamate group (-NH-COO-) and an imine bond (C=N). The strong electron-withdrawing effect of the imine bond makes it unstable and easily cleaved and degraded to form small molecule monomers. For example, patents CN115487352 A, CN117487115A, and CN117402581A disclose several materials containing oxime urethane groups. However, such materials also face some problems in actual use. On the one hand, such materials disclosed are usually constructed as polymer elastomers, which can only be partially degraded and still pose a huge safety hazard to nature; on the other hand, the degradation products (small molecule monomers) of such materials have weak antifouling ability, and in actual use, additional antifouling agents are usually required to enhance the antifouling ability of the coating. Summary of the invention

[0004] In view of this, in order to solve the above technical problems, the purpose of the present invention is to provide a free radical self-releasing antifouling agent containing oxime urethane groups and a preparation method and application thereof. The antifouling agent is based on the ability of oxime urethane groups to undergo hydrolysis reactions to generate free radicals, thereby inhibiting the adhesion of fouling organisms to the surface of marine facilities.

[0005] The technical solutions adopted are:

[0006] The present invention discloses a free radical self-releasing antifouling agent containing an oxime aminoester group, wherein the antifouling agent has the structure shown below:

[0007]

[0008] Among them, R1 is derived from isocyanate substances, and R2 and R3 are derived from oxime-containing substances.

[0009] Further, the isocyanate substance includes any one or more combinations of cyclohexyl isocyanate, octadecyl isocyanate, tert-butyl isocyanate, furan methyl isocyanate, m-toluene isocyanate, cycloheptyl isocyanate, o-toluene isocyanate, p-toluene isocyanate, 2,4-xylyl isocyanate, phenylethyl isocyanate, 2-propyl phenyl isocyanate, hexadecyl isocyanate, cyclopropyl isocyanate, 3-phenylpropyl isocyanate, pentadecyl isocyanate, 3,5-dimethylphenyl isocyanate, 4-octylphenyl isocyanate, cyclooctyl isocyanate, pyridine-3-isocyanate, and 2-tert-butylphenyl isocyanate;

[0010] And / or, the oxime-containing substance includes any one or more combinations of butanone oxime, diacetyl monoxime, butyraldehyde oxime, formaldehyde oxime, acetone oxime, acetaldehyde oxime, cyclohexanone oxime, acetophenone oxime, propionaldehyde oxime, α-benzaldehyde oxime, acetamide oxime, cyclooctanone oxime, diacetophenone oxime, 2-furanaldehyde oxime, cycloheptanone oxime, glutaraldehyde dioxime, glyoxime, 2,4-pentanedione dioxime, 1,4-benzoquinone dioxime, methylglyoxime, 1,2-cyclohexanedione dioxime, dimethyl ketone dioxime, and butanedione oxime;

[0011] And / or, the free radical self-releasing antifouling agent containing oxime urethane groups is mainly prepared by reacting isocyanate substances with oxime-containing substances.

[0012] A method for preparing the free radical self-releasing antifouling agent containing oxime aminoester groups of the present invention comprises the following steps:

[0013] In a protective atmosphere, isocyanate substances are reacted with oxime-containing substances to prepare a free radical self-releasing antifouling agent containing oxime urethane groups.

[0014] Furthermore, the method specifically comprises the following steps: dispersing the oxime-containing substance in a solvent, then introducing an inert gas and heating the solvent, dropping an isocyanate substance, and then reacting the solvent;

[0015] The molar ratio of isocyanate to oxime functional groups in the reaction system is 1:1-1.5; the mass ratio of the sum of the isocyanate and oxime substances to the solvent is 1:5-100; the solvent includes any one or more combinations of N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, tetrahydrofuran, chloroform, and acetone;

[0016] and / or, the reaction temperature is 40 to 80° C.; and / or, the reaction time is 2 to 10 hours;

[0017] Furthermore, the preparation method also includes the following steps: after the reaction is completed, purifying the obtained product; the purification treatment includes any one or more combinations of co-precipitation, separation, and drying; the reagents used in the purification treatment include cyclohexane and / or petroleum ether.

[0018] An antifouling material of the present invention comprises the free radical self-releasing antifouling agent containing oxime urethane groups as claimed in claim 1 or 2;

[0019] The antifouling material also includes a resin system; wherein the mass ratio of the free radical self-releasing antifouling agent containing oxime urethane groups and a polyphenol structure to the resin system is 1-25:50.

[0020] An antifouling agent metal complex of the present invention comprises the free radical self-releasing antifouling agent containing an oxime urethane group according to claim 1 or 2 and a metal ion complexed with the antifouling agent, and the antifouling agent metal complex has the structure shown below:

[0021]

[0022] Wherein, M is a metal ion; preferably, the metal ion includes Ag + , Cu 2+ , Fe 3+ 、Zn 2+ Any one or more combinations of .

[0023] The preparation method of an antifouling agent metal complex of the present invention is as follows:

[0024] (1) Preparation of free radical self-releasing antifouling agent containing oxime urethane groups

[0025] The oxime-containing substance is dissolved in a solvent, then added into a reaction kettle, an inert gas is introduced and heated to 40-80°C, then the isocyanate substance is weighed, and it is ensured that the molar ratio of the isocyanate functional group to the oxime functional group in the raw material system is 1:1-1.5, and the mass ratio of the sum of the isocyanate and oxime substances to the solvent is 1:5-100, and the reaction is slowly dropped and reacted for 2-10 hours. After purification for 3-5 times, it is placed in a vacuum drying oven at 30-80°C for drying, and after cooling to room temperature, a free radical self-releasing antifouling agent containing an oxime urethane group is obtained.

[0026] (2) Preparation of free radical self-releasing antifouling agents containing oxime amine ester groups to complex metal ions

[0027] The green antifouling agent is dissolved in a solvent, and then a metal ion salt is weighed and slowly added, and it is ensured that the molar ratio of the oxime-carbamate functional group to the metal ion in the raw material system is 1:0.5-2, and the mass ratio of the sum of the isocyanate and the oxime substance to the solvent is 1:5-100. The mixture is stirred for 2-10 hours, filtered 1-3 times, and placed in a vacuum drying oven at 30-80°C for drying, and cooled to obtain a free radical self-releasing antifouling agent complexed with metal ions containing an oxime carbamate group.

[0028] In some more specific embodiments, the purification method involved in step (1) is preferably a purification method that combines co-precipitation and centrifugation / filtration, which has a higher purification efficiency.

[0029] In some more specific embodiments, the amount of metal ion salt added in step (2) is adjustable, the purpose of which is to coordinate the degradation ability of the antifouling agent and to synergistically release the metal ions to enhance the antifouling ability.

[0030] The free radical self-releasing antifouling agent containing oxime aminoester groups prepared in the present invention has a simple structure and is degraded in a water environment / seawater environment. The generated free radicals will not accumulate in the environment, thereby avoiding toxic effects on harmless organisms.

[0031] In the present invention, by introducing metal ions such as Zn having antibacterial and antifouling capabilities, the antifouling capability of the material can be improved, thus playing a role in enhancing antifouling.

[0032] Compared with other antifouling agent products or antifouling materials, the free radical self-releasing antifouling agent containing oxime urethane groups has a simple structure, is easy to degrade, has good solubility, is easy to mix with resin matrix and other antifouling agents, and is conducive to compatibility and dispersion with antifouling matrix resin. Moreover, the degradation rate of the antifouling agent is controllable, and it can also coordinate with metal ions to achieve multiple antifouling effects. In addition, this type of antifouling agent has both good antifouling characteristics and environmentally friendly characteristics.

[0033] The antifouling coating of the present invention is prepared by mixing the free radical self-releasing antifouling agent containing oxime urethane groups according to claim 1 or 2 with a solvent to form a solution, then mixing the antifouling agent solution with a coating system and applying the solution to the surface of a substrate to obtain the antifouling coating.

[0034] Furthermore, the material of the substrate sample is wood, metal, plastic or glass; and the coating is drip coating, spin coating or spray coating.

[0035] Application of the free radical self-releasing antifouling agent containing oxime aminoester groups, the antifouling material, the antifouling agent metal complex or the antifouling coating in the field of marine antifouling or antibacterial.

[0036] In the above technical solution,

[0037] The present invention prepares an antifouling agent by using oxime-containing substances and isocyanate as raw materials. In the marine environment, the oxime-carbamate bond of the coating undergoes a hydrolysis reaction with seawater and releases free radicals to inhibit the attachment of fouling organisms. The coating has good antifouling performance and can meet the marine antifouling and antibacterial requirements.

[0038] In summary, compared with the prior art, the present invention has the following advantages:

[0039] 1. The oxime-carbamate bond of the antifouling agent of the present invention undergoes a hydrolysis reaction with seawater, and free radicals with antifouling properties are released, further inhibiting the attachment of fouling organisms.

[0040] 2. The antifouling agent of the present invention has a simple preparation process, low cost, and a simple molecular structure. It can be rapidly degraded in nature without microplastic pollution.

[0041] 3. The free radical self-releasing antifouling agent or antifouling coating containing oxime urethane groups prepared by the present invention has a multi-synergistic antifouling mechanism, and has a broader spectrum, higher efficiency and more stable antifouling characteristics compared to materials that rely only on a single antifouling effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the electron paramagnetic resonance image of acetone oxime p-toluamide antifouling agent;

[0043] Figure 2 It is the UV spectrophotometer diagram after mixing different masses of acetone oxime p-toluamide and 1,1-diphenyl-2-trinitrophenylhydrazine;

[0044] Figure 3 This is a microscope picture of the experimental results of acetone oxime-toluamide inhibiting the dichromatina;

[0045] Figure 4 It is the first day anti-D-bacterial rate of acetone oxime toluamide;

[0046] Figure 5 It is the third day anti-D-biloba rate of acetone oxime toluamide;

[0047] Figure 6 This is a digital picture of the antibacterial test results of acetone oxime toluamide;

[0048] Figure 7 is the anti-E. coli rate of acetone oxime toluamide;

[0049] Figure 8 is the rate of acetone oxime against toluidine against Aureococcus aureus;

[0050] Fig. 9 This is the electron paramagnetic resonance image of dimethylglyoxime p-toluamide antifouling agent;

[0051] Fig.10 It is the UV spectrophotometer diagram after mixing different masses of dimethylglyoxime p-toluene amino ester and 1,1-diphenyl-2-trinitrophenylhydrazine;

[0052] Fig.11 This is a microscope picture of the experimental results of diacetyl oxime-toluamide inhibiting the dichaete algae;

[0053] Fig.12 It is the first day anti-D-bacterium rate of diacetyl oxime toluamide;

[0054] Fig.13 It is the third day anti-D-bacterium rate of diacetyl oxime toluamide;

[0055] Fig.14 This is a digital picture of the antibacterial test results of dimethylglyoxime p-toluamide;

[0056] Fig.15 is the anti-Escherichia coli rate of dimethylglyoxime toluene ester;

[0057] Fig.16 is the rate of diacetyl oxime against toluene amino ester against golden spores;

[0058] Fig.17 This is a microscope picture of the experimental results of the inhibition of diacetyl oxime p-toluamide complexed with metal ions on the growth of diacetyl algae;

[0059] Fig.18 This is a digital picture of the antibacterial test results of dimethylglyoxime p-toluamide complexed with metal ions. DETAILED DESCRIPTION

[0060] The present invention is described in detail below through specific examples, but the use and purpose of these exemplary implementation modes are only used to illustrate the present invention, and do not constitute any form of limitation on the actual protection scope of the present invention, nor limit the protection scope of the present invention to them.

[0061] Example 1

[0062] The method for preparing a free radical self-releasing antifouling agent containing oxime amino ester groups in this embodiment comprises the following steps:

[0063] S1. Take 50 mmol acetone oxime and add it to a 100 mL three-necked flask, add 50 mL acetone to dissolve, introduce nitrogen, and heat to 70 ° C;

[0064] S2. Weigh 50 mmol of p-toluene isocyanate and add it dropwise into the system. The whole system is reacted for 6 hours at 70°C in a nitrogen atmosphere. The reaction product solution is added dropwise into an excess of petroleum ether to obtain a large amount of white precipitate. Place it in a vacuum drying oven and vacuum dry it for 12 hours to obtain an acetone oxime p-toluene amino ester antifouling agent.

[0065] The structure of the prepared target compound is shown in the following formula (1):

[0066]

[0067] Electron paramagnetic resonance spectrometer test: Figure 1 This is the electron paramagnetic resonance image of acetone oxime p-toluene amino ester in deionized water, and the generation of alkyl free radicals can be observed.

[0068] Free radical quenching experimental test: Figure 2 This is a UV spectrophotometer comparison chart of different masses of acetone oxime p-toluene amino ester and 1,1-diphenyl-2-trinitrophenylhydrazine mixed in a water / ethanol mixed solution for 24 hours. The obvious color change proves that acetone oxime p-toluene amino ester produces free radicals.

[0069] Laboratory static diatom inhibition experiment: different qualities of antifouling agents and glass slides were immersed in the liquid of the double-browed algae for 1 day and 3 days. After taking out the samples, the unattached algae were removed and the algae attachment on the coating was photographed under an optical microscope. Figure 3 This is a microscope picture of the antifouling agent's anti-Dinocampus algae test results. Compared with the control group, the adhesion of Dinocampus algae on the coating surface is significantly reduced. Figure 4 and Figure 5 It is the first day / third day anti-diatom rate of the antifouling agent. Three areas of each coating were randomly selected for shooting and finally compared with the blank sample. The inhibition rates of diatoms on the first day were calculated as 94.3%, 100%, and 100%, respectively. The inhibition rates of diatoms on the third day were calculated as 91.5%, 100%, and 100%, respectively.

[0070] Laboratory static antibacterial experiment: Antifouling agents of different qualities and glass slides were co-cultured with bacteria (Escherichia coli, Staphylococcus aureus) at 37°C for 12h and 24h. After dilution to equal concentration, the bacterial solution was spread on solid culture medium by plate spreading method (each sample was spread in parallel 3 times), and incubated at 37°C for 12h and 24h. The plates were taken out and the number of bacteria adhering to the coating surface was determined by plate counting. Figure 6 This is a digital picture of the antibacterial test results of the antifouling agent. It can be seen that the number of colonies on the coating surface is significantly reduced compared to the blank. The colony counting method is used to calculate the number of colonies on the sample and the blank. Figure 7 and Figure 8 It is the anti-Escherichia coli / Aureus coccus rate of the antifouling agent. The calculated antibacterial rates of Escherichia coli are 73.8%, 86.3%, and 94%, respectively; the calculated antibacterial rates of Aureus coccus are 52.5%, 87.4%, and 97.5%, respectively.

[0071] Example 2

[0072] The method for preparing a free radical self-releasing antifouling agent containing oxime amino ester groups in this embodiment comprises the following steps:

[0073] S1. Take 50 mmol of diacetyl oxime and add it to a 100 mL three-necked flask, add 50 mL of acetone to dissolve, introduce nitrogen, and heat to 70 ° C;

[0074] S2. Weigh 100 mmol of p-toluene isocyanate and add it dropwise to the system. The whole system is reacted at 70°C under nitrogen atmosphere for 6 hours. The reaction product solution is added dropwise to an excess of petroleum ether to obtain a large amount of white precipitate. Place it in a vacuum drying oven and vacuum dry it for 12 hours to obtain dimethylglyoxime p-toluene amino ester antifouling agent. The structure of the prepared target compound is shown in the following formula (2):

[0075]

[0076] Electron paramagnetic resonance spectrometer test: Fig. 9 This is the electron paramagnetic resonance image of diacetyl oxime p-toluamide in deionized water, and the generation of alkyl radicals can be observed.

[0077] Free radical quenching experimental test: Fig.10 This is a comparison chart of different masses of dimethylglyoxime p-toluene amino ester and 1,1-diphenyl-2-trinitrophenylhydrazine in a water / ethanol mixed solution after 24 hours. The obvious color change proves that dimethylglyoxime p-toluene amino ester produces free radicals.

[0078] Laboratory static diatom inhibition experiment: different qualities of antifouling agents and glass slides were immersed in the liquid of the double-browed algae for 1 day and 3 days. After taking out the samples, the unattached algae were removed and the algae attachment on the coating was photographed under an optical microscope. Fig.11 This is a microscope picture of the antifouling agent's anti-Dinocampus algae test results. Compared with the control group, the adhesion of Dinocampus algae on the coating surface is significantly reduced. Fig.12 and Fig.13 It is the first day / third day anti-diatom rate of the antifouling agent. Three areas of each coating were randomly selected for shooting and finally compared with the blank sample. The inhibition rates of diatoms on the first day were calculated as 20%, 65.9%, and 90.6%, respectively. The inhibition rates of diatoms on the third day were calculated as 55.6%, 70.6%, and 96.3%, respectively.

[0079] Laboratory static antibacterial experiment: Antifouling agents of different qualities and glass slides were co-cultured with bacteria (Escherichia coli, Staphylococcus aureus) at 37°C for 12h and 24h. After dilution to equal concentration, the bacterial solution was spread on solid culture medium by plate spreading method (each sample was spread in parallel 3 times), and incubated at 37°C for 12h and 24h. The plates were taken out and the number of bacteria adhering to the coating surface was determined by plate counting. Fig.14 This is a digital picture of the antibacterial test results of the antifouling agent. It can be seen that the number of colonies on the coating surface is significantly reduced compared to the blank. The colony counting method is used to calculate the number of colonies on the sample and the blank. Fig.15 and Fig.16 It is the anti-Escherichia coli / Aureus coccus rate of the antifouling agent. The calculated antibacterial rates of Escherichia coli are 75.4%, 80.3%, and 87.7%, respectively; the calculated antibacterial rates of Aureus coccus are 85.5%, 95.8%, and 100%, respectively.

[0080] Example 3

[0081] The method for preparing a free radical self-releasing antifouling agent complexed with metal ions containing oxime amino ester groups in this embodiment comprises the following steps:

[0082] S1. Take 50 mmol of diacetyl oxime and add it to a 100 mL three-necked flask, add 50 mL of acetone to dissolve, introduce nitrogen, and heat to 70 ° C;

[0083] S2. Weigh 100 mmol of p-toluene isocyanate and add it dropwise into the system. The whole system is reacted for 6 hours at 70°C in a nitrogen atmosphere. The reaction product solution is added dropwise into an excess of petroleum ether to obtain a large amount of white precipitate. Place it in a vacuum drying oven and vacuum dry it for 12 hours to obtain a dimethylglyoxime p-toluene amino ester antifouling agent.

[0084] S3. Weigh 10 mmol of dimethylglyoxime p-toluene amino ester antifouling agent and dissolve it in 50 mL of methanol, then add 10 mmol of CuCl2·2H2O, stir for 4 hours, filter, and vacuum dry to obtain dimethylglyoxime p-toluene amino ester complexed metal ions.

[0085] Laboratory static diatom inhibition experiment: different qualities of antifouling agents and glass slides were immersed in the liquid of the double-browed algae for 1 day and 3 days. After taking out the samples, the unattached algae were removed and the algae attachment on the coating was photographed under an optical microscope. Fig.11 This is a microscope picture of the antifouling agent's anti-Dinocampus algae test results. Compared with the control group, the adhesion of Dinocampus algae on the coating surface is significantly reduced.

[0086] Laboratory static antibacterial experiment: Antifouling agents of different qualities and glass slides were co-cultured with bacteria (Escherichia coli, Staphylococcus aureus) at 37°C for 12h and 24h. After dilution to equal concentration, the bacterial solution was spread on solid culture medium by plate spreading method (each sample was spread in parallel 3 times), and incubated at 37°C for 12h and 24h. The plates were taken out and the number of bacteria adhering to the coating surface was determined by plate counting. Fig.14 This is a digital picture of the antibacterial test results of the antifouling agent. It can be seen that the number of colonies on the coating surface is significantly reduced compared to the blank.

[0087] Comparative Example 1

[0088] The method is the same as Example 1, except that the p-toluene isocyanate in Example 1 is replaced by cyclohexyl isocyanate, and the oily material is obtained after purification and drying. This is quite different from the acetone oxime p-toluene amino ester antifouling agent of the present invention, and the free radical generation efficiency is higher, and the antifouling performance is greatly improved.

[0089] Comparative Example 2

[0090] The method is the same as that in Example 1, except that the p-toluene isocyanate in Example 1 is replaced by octadecyl isocyanate. Compared with the acetone oxime p-toluene amino ester antifouling agent of the present invention, it exhibits obvious hydrophobicity.

[0091] Comparative Example Technical Description: The antifouling ability of the free radical self-releasing antifouling agent containing oxime urethane groups of the present invention is jointly determined by isocyanate and oxime-containing substances.

[0092] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0093] The series of detailed descriptions listed above are only specific descriptions of feasible embodiments of the present invention. They are not intended to limit the scope of protection of the present invention. All equivalent embodiments or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A free radical self-releasing antifouling agent containing an oxime aminoester group, characterized in that: The antifouling agent has the structure shown below: Among them, R1 is derived from isocyanate substances, and R2 and R3 are derived from oxime-containing substances.

2. The free radical self-releasing antifouling agent containing oxime urethane groups according to claim 1, characterized in that: The isocyanate substances include any one or more combinations of cyclohexyl isocyanate, octadecyl isocyanate, tert-butyl isocyanate, furanyl methyl isocyanate, m-toluene isocyanate, cycloheptyl isocyanate, o-toluene isocyanate, p-toluene isocyanate, 2,4-xylyl isocyanate, phenylethyl isocyanate, 2-propyl phenyl isocyanate, hexadecyl isocyanate, cyclopropyl isocyanate, 3-phenylpropyl isocyanate, pentadecyl isocyanate, 3,5-dimethylphenyl isocyanate, 4-octylphenyl isocyanate, cyclooctyl isocyanate, pyridine-3-isocyanate, and 2-tert-butylphenyl isocyanate; And / or, the oxime-containing substance includes any one or more combinations of butanone oxime, diacetyl monoxime, butyraldehyde oxime, formaldehyde oxime, acetone oxime, acetaldehyde oxime, cyclohexanone oxime, acetophenone oxime, propionaldehyde oxime, α-benzaldehyde oxime, acetamide oxime, cyclooctanone oxime, diacetophenone oxime, 2-furanaldehyde oxime, cycloheptanone oxime, glutaraldehyde dioxime, glyoxime, 2,4-pentanedione dioxime, 1,4-benzoquinone dioxime, methylglyoxime, 1,2-cyclohexanedione dioxime, dimethyl ketone dioxime, and butanedione oxime; And / or, the free radical self-releasing antifouling agent containing oxime urethane groups is mainly prepared by reacting isocyanate substances with oxime-containing substances.

3. A method for preparing the free radical self-releasing antifouling agent containing oxime aminoester groups according to claim 1 or 2, characterized in that: The steps include: In a protective atmosphere, isocyanate substances are reacted with oxime-containing substances to prepare a free radical self-releasing antifouling agent containing oxime urethane groups.

4. The preparation method according to claim 3, characterized in that: The method comprises the following steps: dispersing an oxime-containing substance in a solvent, then introducing an inert gas and heating the solvent, dripping an isocyanate substance, and then reacting the solvent; The molar ratio of isocyanate to oxime functional groups in the reaction system is 1:1-1.5; the mass ratio of the sum of the isocyanate and oxime substances to the solvent is 1:5-100; the solvent includes any one or more combinations of N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, tetrahydrofuran, chloroform, and acetone; And / or, the reaction temperature is 40-80° C.; and / or, the reaction time is 2-10 h.

5. The preparation method according to claim 4, characterized in that: The preparation method further comprises the following steps: after the reaction is completed, purifying the obtained product; the purification process comprises any one or more combinations of coprecipitation, separation, and drying; and the reagents used in the purification process comprise cyclohexane and / or petroleum ether.

6. An antifouling material, characterized in that: A free radical self-releasing antifouling agent comprising an oxime urethane group as claimed in claim 1 or 2; The antifouling material also includes a resin system; The mass ratio of the free radical self-releasing antifouling agent containing oxime urethane groups and polyphenol structure to the resin system is 1-25:

50.

7. An antifouling agent metal complex, characterized in that The invention comprises the free radical self-releasing antifouling agent containing oxime urethane group according to claim 1 or 2 and the metal ion complexed with the antifouling agent, and the antifouling agent metal complex has the structure shown below: Wherein, M is a metal ion; preferably, the metal ion includes Ag + , Cu 2+ , Fe 3+ 、Zn 2+ Any one or more combinations of .

8. An antifouling coating, characterized in that: The free radical self-releasing antifouling agent containing oxime urethane groups according to claim 1 or 2 is mixed with a solvent to form a solution, and then the antifouling agent solution is mixed with a coating system and applied to the surface of a substrate to prepare an antifouling coating.

9. The antifouling coating according to claim 8, characterized in that: The material of the substrate sample is wood, metal, plastic or glass; the coating is drop coating, spin coating or spray coating.

10. Use of the free radical self-releasing antifouling agent containing oxime urethane groups according to claim 1 or 2, the antifouling material according to claim 6, the antifouling agent metal complex according to claim 7 or the antifouling coating according to claim 8 or 9 in the field of marine antifouling or antibacterial.

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