Application of clothianidin in preparation of marine antifouling agent

Abstract

The invention discloses an application of clothianidin in preparation of a marine antifouling agent. According to the invention, clothianidin is applied to the marine antifouling coating, so that the defects of high toxicity and poor environmental protection property of an antifouling agent in the prior art are overcome, the coating shows remarkable advantages in the aspects of economy and practicability, and an innovative solution is provided for green development of a marine antifouling technology.

Description

Technical Field

[0001] The invention belongs to the technical field of marine antifouling, and particularly relates to the application of clothianidin in the preparation of a marine antifouling agent. Background Art

[0002] Marine fouling refers to the attachment and growth of marine organisms on artificial structures submerged in seawater. This phenomenon has a significant adverse impact on marine economic activities. Large fouling organisms, such as barnacles, shellfish, and ascidians, in particular, can cause a variety of problems when they attach to the surfaces of ships, docks, buoys, ocean monitoring equipment, and aquaculture facilities. First, fouling organisms attached to ship surfaces increase navigation resistance, resulting in reduced speed and increased fuel consumption. Second, these organisms accelerate the corrosion of metal materials, shortening the service life of facilities. Furthermore, fouling organisms can clog pipes or the mesh of aquaculture nets, hindering water exchange, interfering with the normal operation of marine instruments, and even causing the death of aquacultured organisms. This leads to high maintenance costs and economic losses for industries such as marine transportation, energy development, and aquaculture. Therefore, preventing the attachment and growth of large marine fouling organisms on artificial structures is of great significance to ensuring the sustainable development of the marine economy.

[0003] To address the problem of marine fouling, antifouling coatings are widely used on the surfaces of marine facilities as a cost-effective solution. These coatings usually contain toxic substances that are released onto the coating surface to prevent or kill fouling organisms, thereby inhibiting their attachment. In the past, organotin compounds (such as tributyltin, TBT) were widely used due to their high antifouling properties. However, these compounds are extremely toxic to marine organisms and degrade slowly in the environment. They accumulate in the food chain and cause serious damage to the marine ecosystem. Based on this, the International Maritime Organization completely banned the use of antifouling coatings containing organotin compounds in 2008, prompting the industry to seek alternative technologies.

[0004] At present, the mainstream antifouling coatings on the market mainly use cuprous oxide as an antifouling agent. Cuprous oxide can effectively inhibit the attachment of marine organisms and has a good application effect within a certain range. However, as a heavy metal compound, its large-scale use poses a potential threat to the marine environment. Copper elements may accumulate in seabed sediments, have toxic effects on non-target organisms, and thus disrupt the ecological balance of the ocean. In recent years, some European and American countries have begun to ban or restrict the entry of ships containing copper antifouling coatings into ports. my country has also gradually strengthened environmental supervision of copper-containing antifouling agents, promoting the research and development of low-toxic and environmentally friendly antifouling technologies.

[0005] In recent years, the scientific research field has explored a variety of new anti-fouling technologies, including the use of natural products (such as seaweed extracts), enzymes, and surface modification technologies (such as super-hydrophobic coatings) to prevent the attachment of marine organisms. However, these methods face many challenges in practical applications. For example, the extraction cost of natural products is high and the output is limited, which makes it difficult to meet the needs of industrialization; the stability of enzymes is insufficient, and the anti-fouling effect is limited by environmental conditions; the durability of surface modification technology and its broad-spectrum inhibition ability against various fouling organisms need to be improved. In addition, existing antifouling agents still have shortcomings in terms of balancing high efficiency, environmental protection and economy, and it is difficult to fully meet the needs of the modern marine industry. Summary of the Invention

[0006] The present invention aims to overcome the defects of the prior art and provide the use of clothianidin in the preparation of marine antifouling agents.

[0007] The technical solutions of the present invention are as follows:

[0008] Application of clothianidin in the preparation of marine antifouling agents.

[0009] In a preferred embodiment of the present invention, the marine antifouling agent further comprises at least one of isothiazolinone compounds, bromopyrrole carbonitrile, triazine compounds, N-2,4,6-trichlorophenylmaleimide and pyridine triphenyl borane.

[0010] In a preferred embodiment of the present invention, the marine antifouling agent is applied to the surface of marine artificial facilities by spraying, dipping or coating to prevent the attachment of macrofouling organisms thereon.

[0011] Further preferably, the large fouling organisms are barnacles, and the marine artificial facilities include docks, ships, buoys, marine monitoring instruments, breeding platforms and breeding facilities.

[0012] A marine antifouling agent, the active ingredient of which includes clothianidin.

[0013] In a preferred embodiment of the present invention, the active ingredient is only clothianidin.

[0014] In a preferred embodiment of the present invention, the active ingredient further comprises at least one of isothiazolinone compounds, bromopyrrole carbonitrile, triazine compounds, N-2,4,6-trichlorophenylmaleimide and pyridine triphenylborane.

[0015] A marine antifouling coating composition, the raw materials of which include the above-mentioned marine antifouling agent.

[0016] In a preferred embodiment of the present invention, the raw materials further include zinc acrylate resin, rosin, pigment, organic bentonite, talc and organic solvent.

[0017] Further preferably, the mass ratio of the zinc acrylate resin, rosin, pigment, organic bentonite, talc, marine antifouling agent and organic solvent is 30:12:8:1:13:20:16.

[0018] The beneficial effects of the present invention are:

[0019] 1. The clothianidin in the present invention can significantly inhibit the attachment of large marine fouling organisms at a relatively low concentration, especially showing excellent antifouling activity against barnacles. Experiments show that its half-maximal inhibitory concentration (EC 50 ) is 10.93 μg / mL, which can effectively prevent the attachment of barnacle larvae and provide reliable anti-fouling protection for marine facilities.

[0020] 2. Compared to traditional antifouling agents containing heavy metals (such as cuprous oxide), clothianidin in this invention is an organic compound that contains no heavy metals and is readily biodegradable. Its use can significantly reduce the risk of pollution to marine ecosystems, prevent the accumulation of heavy metals in seabed sediments, comply with current environmental regulations, and help maintain marine ecological balance.

[0021] 3. The clothianidin of the present invention has good lipophilicity and is slightly soluble in water but readily soluble in organic solvents. This property makes it easy to mix with the coating base and can be evenly dispersed in the coating. In practical applications, the release rate of clothianidin is controllable, avoiding the sudden release of the antifouling agent (burst release phenomenon), thereby improving the utilization efficiency of the antifouling agent and extending the service life of the antifouling coating. In practical applications, antifouling coatings containing clothianidin have been tested for antifouling performance in marine areas for 3-12 months and found to have significant antifouling effectiveness, with no loss of antifouling effectiveness due to burst release.

[0022] 4. As a neonicotinoid insecticide widely used in agriculture, clothianidin in the present invention has mature industrial synthesis technology, simple production processes, readily available raw materials, and low costs. Compared with some natural antifouling agents, clothianidin can be produced on a large scale without complex extraction processes, offering significant economic advantages and ensuring its widespread application in marine antifouling.

[0023] 5. Clothianidin in the present invention can be used as a single antifouling agent or in combination with other antifouling agents (such as isothiazolinone compounds or bromopyrrole carbonitrile). This flexibility enables it to be effective in different application scenarios and potentially achieve a broader antifouling effect through combination.

[0024] 6. The sea area hanging board test verified that after the antifouling coating containing clothianidin of the present invention was immersed in the marine environment for 3 months, the paint film on the coating surface was intact and no obvious fouling organisms were observed, proving its high efficiency and stability in practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The effect of clothianidin in Example 1 of the present invention on the attachment of barnacle Venus larvae is shown.

[0026] Figure 2 The antifouling effect of the clothianidin-containing marine antifouling coating composition in Example 2 of the present invention in a sea area test is shown.

[0027] Figure 3 The antifouling effect of the marine antifouling coating composition containing clothianidin and bromopyrrole carbonitrile in Example 3 of the present invention in the sea area test is shown. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further illustrated and described below through specific implementation methods in conjunction with the accompanying drawings.

[0029] Example 1 Detection of the inhibitory effect of clothianidin on large marine fouling animals barnacles

[0030] (1) Culture of barnacle larvae: Adult barnacles collected from the sea area were cleaned, dried in the shade for 24 hours, and then placed in fresh seawater at a temperature of 28°C and a salinity of 30°C to induce spawning for about 2–5 hours. The barnacles released nauplii. Impurities in the seawater were filtered with a 70-mesh sieve, and the nauplii were collected with a 150-mesh sieve. The nauplii were cultured in membrane-filtered (0.22 μm) seawater at a temperature of 28°C and a salinity of 30°C. The culture density was controlled to be approximately 2 nauplii per milliliter. Platmonas subcordiformis was fed daily as bait during the culture period. After 5–7 days of culture, the nauplii developed into Venus larvae, which were collected with a 120-mesh sieve for detection.

[0031] (2) Antifouling activity test: Dissolve clothianidin in DMSO to prepare a 50 mg / mL stock solution. The antifouling activity test used a 24-well plate as the experimental container, set up a control group and an experimental group, and set up 3 parallels for each group. Add 1798 μL of membrane-filtered seawater to each well, and then use a pipette to draw 200 μL of membrane-filtered seawater containing about 20 barnacle Venus larvae and add it to each well. Add 2 μL of DMSO to each well of the control group, and add 2 μL of DMSO solutions of different concentrations of clothianidin to each well of the experimental group. The detection concentration gradient was set to 1, 10, 25 and 50 μg / mL. The experimental results showed that 0.1% DMSO had no significant effect on the attachment of barnacle Venus larvae. The 24-well plate was placed in a dark environment at 28°C. When the attachment rate of the larvae in the control group reached more than 80%, the attachment of the larvae in each well was observed using an inverted microscope. The number of attached larvae and the number of unattached larvae were recorded and the attachment rate was calculated.

[0032] The results of the effect of clothianidin on the attachment of barnacle larvae are shown in the attached Figure 1The half-inhibitory concentration EC was calculated as 50 10.93 μg mL -1 , which confirmed that clothianidin had a good inhibitory effect on the attachment of barnacle larvae.

[0033] Example 2 Detection of antifouling effect of clothianidin in sea area

[0034] The marine antifouling coating composition prepared in this embodiment has the following weight ratios of the raw materials:

[0035]

[0036] The specific preparation method comprises the following steps:

[0037] (1) Add xylene in proportion to the high-speed dispersion container, start the high-speed disperser, and adjust the speed to 400 r / min;

[0038] (2) Slowly add rosin to the material obtained in step (1), stir at 400 r / min until the rosin is completely dissolved, then add zinc acrylate resin, and continue stirring at a low speed of 400 r / min until it is completely dissolved;

[0039] (3) adding organic bentonite, titanium dioxide, talc and clothianidin in sequence to the material obtained in step (2), adjusting the speed to 1200 r / min, and stirring for 10 min;

[0040] (4) Grinding the material obtained in step (3) to a fineness of less than 60 μm using a basket sand mill, and testing the fineness and viscosity to obtain a marine antifouling coating composition.

[0041] The antifouling performance test of the marine antifouling coating composition prepared in this example is as follows:

[0042] Shallow sea hanging board refers to the national standard GB / T 5370-2007, and the hanging board test was carried out in the waters of Xiamen, Fujian. Figure 2 As shown, after 3 months of hanging in the sea area, the paint film is intact, without peeling or blistering, and no obvious large-scale fouling organisms are attached.

[0043] Example 3 Detection of antifouling effect in sea areas after the combination of clothianidin and bromopyrrole nitrile

[0044] The marine antifouling coating composition prepared in this embodiment has the following weight ratios of the raw materials:

[0045]

[0046] The specific preparation method comprises the following steps:

[0047] (1) Add xylene in proportion to the high-speed dispersion container, start the high-speed disperser, and adjust the speed to 400 r / min;

[0048] (2) Slowly add rosin to the material obtained in step (1), stir at 400 r / min until the rosin is completely dissolved, then add zinc acrylate resin, and continue stirring at a low speed of 400 r / min until it is completely dissolved;

[0049] (3) adding organic bentonite, titanium dioxide, talc, clothianidin and bromopyrrole nitrile to the material obtained in step (2) in sequence, adjusting the speed to 1200 r / min, and stirring for 10 minutes;

[0050] (4) Grinding the material obtained in step (3) to a fineness of less than 60 μm using a basket sand mill, and testing the fineness and viscosity to obtain a marine antifouling coating composition.

[0051] The antifouling performance test of the marine antifouling coating composition prepared in this example is as follows:

[0052] Shallow sea hanging board refers to the national standard GB / T 5370-2007, and the hanging board test was carried out in the waters of Xiamen, Fujian. Figure 3 As shown, after 12 months of hanging in the sea area, the paint film is intact, without peeling or blistering, and no obvious large-scale fouling organisms are attached.

[0053] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made within the scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. Application of clothianidin in the preparation of marine antifouling agents.

2. The use according to claim 1, characterized in that: The marine antifouling agent further comprises at least one of isothiazolinone compounds, bromopyrrole carbonitrile, triazine compounds, N-2,4,6-trichlorophenylmaleimide and pyridine triphenyl borane.

3. The use according to claim 1 or 2, characterized in that: The marine antifouling agent is applied to the surface of marine artificial facilities by spraying, dipping or coating to prevent the attachment of macrofouling organisms thereon.

4. The use according to claim 3, characterized in that: The large fouling organisms are barnacles, and the marine artificial facilities include docks, ships, buoys, marine monitoring instruments, breeding platforms and breeding facilities.

5. A marine antifouling agent, characterized in that: Its active ingredients include clothianidin.

6. A marine antifouling agent according to claim 5, characterized in that: Its active ingredient is only clothianidin.

7. A marine antifouling agent according to claim 5, characterized in that: The effective components thereof further include at least one of isothiazolinone compounds, bromopyrrole nitrile, triazine compounds, N-2,4,6-trichlorophenylmaleimide and pyridine triphenylborane.

8. A marine antifouling coating composition, characterized in that: The raw materials include the marine antifouling agent according to any one of claims 5 to 7.

9. A marine antifouling coating composition according to claim 8, characterized in that: Its raw materials also include zinc acrylate resin, rosin, pigment, organic bentonite, talc and organic solvent.

10. A marine antifouling coating composition according to claim 9, characterized in that: The mass ratio of the zinc acrylate resin, rosin, pigment, organic bentonite, talc, marine antifouling agent and organic solvent is 30:12:8:1:13:20:16.

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