Application of p-hydroxybenzene compound as marine antifouling agent and antifouling agent and coating thereof

Abstract

The invention discloses application of a p-hydroxybenzene compound as a marine antifouling agent and the antifouling agent and a coating thereof. The p-hydroxybenzene series compound is used as the only effective component of the antifouling agent or is compounded with other antifouling agents, and is directly applied to the surface of the marine facility or is added into a coating to be sprayed, impregnated or coated, so that the adhesion of large marine fouling organisms including biological barnacle and sand siberian shellfish on the surface of the marine facility can be inhibited at low concentration; meanwhile, good lipophilicity is achieved, the antifouling paint is suitable for being prepared, the raw material synthesis technology is mature, the preparation technology is simple, cost is low, and a large number of raw materials are easy to obtain.

Description

Technical Field

[0001] The invention belongs to the technical field of marine antifouling coatings, and in particular relates to the use of a p-hydroxybenzene compound as a marine antifouling agent and the antifouling agent and coating. Background Art

[0002] In the marine environment, marine fouling organisms attaching and growing on the surface of artificial facilities will cause serious harm to human economic activities. Large marine fouling organisms such as barnacles and shellfish attaching to the surface of artificial facilities will increase the resistance of ships, reduce speed, increase fuel consumption, accelerate the corrosion of metal materials such as ships and platforms, and shorten the service life; in addition, it will also affect the optical or acoustic signal transmission of marine instruments, increase maintenance frequency and cost; marine fouling organisms attaching and clogging aquaculture nets will also cause the death of aquaculture organisms, causing great damage to the aquaculture industry. In short, the attachment of large marine fouling organisms to artificial facilities is a major problem for humans to develop and utilize the ocean.

[0003] It has been found that applying antifouling paint on the surface of facilities is an effective means to prevent and remove fouling organisms. Antifouling paint contains toxic substances, which can effectively prevent the attachment of marine organisms after being released to the coating surface. Organotin has been widely used as an effective antifouling agent, but this substance is highly toxic to all marine organisms, and is not easy to degrade, and is prone to cumulative effects, which seriously damages the ecological environment. The International Maritime Organization has completely banned the use of organotin compounds in antifouling paints on January 1, 2008. At present, the antifouling agent that replaces organotin is cuprous oxide. Copper is a heavy metal that accumulates continuously in the marine environment and will also have an adverse impact on the marine ecological environment. Some port cities in European and American countries have begun to restrict ships painted with copper-containing paints from entering the port. With the improvement of my country's environmental awareness, the production and use of antifouling paints containing cuprous oxide are also gradually restricted. Therefore, the development of efficient and low-toxic environmentally friendly antifouling agents is a current research hotspot. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art, provide the use of a series of p-hydroxybenzene compounds as a marine antifouling agent and the antifouling agent and coating thereof, and solve the problems in the above-mentioned background technology.

[0005] One of the technical solutions adopted by the present invention to solve the technical problem is: providing the use of a p-hydroxybenzene compound as a marine antifouling agent for inhibiting the attachment of large fouling organisms to the surface of marine facilities; the general formula of the p-hydroxybenzene compound is

[0006] Wherein R is an alkyl group or an aldehyde group.

[0007] The p-hydroxybenzene compound is p-cresol or p-hydroxybenzaldehyde

[0008] Among them, p-Cresol has a molecular formula of C7H8O, a molecular weight of 108.14, and a structural formula as shown below. p-Cresol is an important industrial organic compound. Related reports of natural sources include Cynanchum wilfordii and Streptomyces albospinus. The compound has anti-methicillin-resistant Staphylococcus aureus activity and is mainly used as a food flavoring, bactericide, mildew inhibitor, etc.

[0009] p-Hydroxybenzaldehyde, with a molecular formula of C7H6O2 and a molecular weight of 122.04, has a structural formula as shown below. p-Hydroxybenzaldehyde is widely distributed in nature and has been found in marine Bacillus sp., marine Penicillium sp., Lubomirskia baicalensis, Ranunculus ternatus, Zingiber zerumbet, Dendrobium officinale and Clausena excavata. This compound has good antibacterial activity against Escherichia coli and is mainly used as an important intermediate and bactericide in the pharmaceutical and spice industries.

[0010] In a preferred embodiment of the present invention, the large fouling organisms refer to the general term for animals and plants attached to all marine facilities, including barnacles, sand scallops, ascidians, oysters, sponges, coil worms, enteromorpha or mosses, etc.

[0011] In a preferred embodiment of the present invention, the p-hydroxybenzene compound is used as a single component antifouling agent (the only effective ingredient), or the p-hydroxybenzene compound is compounded with other antifouling agents, such as: with at least one of a copper-containing compound (e.g., cuprous oxide, copper thiocyanate, copper pyrithione), a zinc-containing compound (e.g., zinc oxide, zinc pyrithione), an isothiazolinone compound (e.g., 4,5-dichloro-2-octyl-4-isothiazoline-3-one), a triazine compound (e.g., N-cyclopropyl-N'-(1,1-dimethylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine), N-2,4,6-trichlorophenylmaleimide, pyridinetriphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, or N-(fluorodichloromethylthio)-phthalimide to prepare the antifouling agent.

[0012] In a preferred embodiment of the present invention, the antifouling coating is directly applied or added to the antifouling coating and applied to the surface of marine facilities. The application method includes spraying, dipping or coating.

[0013] In a preferred embodiment of the present invention, the marine facilities include ships (ships, boats, boats or boats, etc.), buoys, marine monitoring instruments, aquaculture facilities (nets or cages, etc.), aquaculture platforms, pipelines or other facilities immersed in the sea, etc. In the present invention, facilities mainly refer to artificial facilities.

[0014] The second technical solution adopted by the present invention to solve the technical problem is: to provide a marine antifouling agent, the only active ingredient of which is a p-hydroxybenzene compound, the general formula of which is Wherein R is an alkyl group or an aldehyde group.

[0015] The third technical solution adopted by the present invention to solve the technical problem is: providing a marine antifouling agent, which is a composite of a p-hydroxybenzene compound and at least one of an isothiazolinone compound, a triazine compound, N-2,4,6-trichlorophenylmaleimide, pyridine triphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole or N-(fluorodichloromethylsulfide)-phthalimide, wherein the general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

[0016] The fourth technical solution adopted by the present invention to solve the technical problem is: provide a marine antifouling coating, including a base material, a pigment, an additive and a solvent, and also including a marine antifouling agent, wherein the marine antifouling agent is a p-hydroxybenzene compound or a p-hydroxybenzene compound and a copper-containing compound (such as cuprous oxide, copper thiocyanate, copper pyrithione), a zinc-containing compound (such as zinc oxide, zinc pyrithione), an isothiazolinone compound (such as 4,5-dichloro-2-octyl-4-isothiazoline-3- A composition prepared by mixing at least one of 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, and 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, and 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole, wherein the general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

[0017] The base material includes (but is not limited to): acrylic resin, chloroether resin, chlorosulfonated polyethylene, chlorinated rubber, epoxy resin, polybutene, polyvinyl alcohol, polyvinyl acetate, amino resin. The pigment includes (but is not limited to): titanium dioxide, zinc oxide, iron red, talcum powder. The auxiliary agent mainly includes thixotropic agent, stabilizer and anti-settling agent. The solvent includes (but is not limited to): 200# coal tar solvent, xylene, cyclohexanone, n-butanol.

[0018] In a preferred embodiment of the present invention, the p-hydroxybenzene compound is p-cresol or p-hydroxybenzaldehyde, and the coating components are composed of the following components in parts by weight:

[0019]

[0020]

[0021] Compared with the background technology, this technical solution has the following advantages:

[0022] (1) High efficiency: p-cresol can significantly inhibit the attachment of large marine fouling organisms such as barnacles and sand scallops at low concentrations. Its half-inhibitory concentration EC 50 7.28 μg mL -1 and 5.54 μg mL -1 ; p-Hydroxybenzaldehyde can significantly inhibit the attachment of large marine fouling organisms barnacles at a relatively low concentration, and its half-inhibitory concentration EC 50 16.53 μg mL -1 .

[0023] (2) Environmental protection: The active ingredients of the present invention do not contain heavy metal compounds and do not pollute the marine environment. Secondly, p-hydroxybenzene compounds are usually easy to degrade (biodegrade, photodegrade), avoiding long-term impact on the marine ecological environment when released into the water environment.

[0024] (3) Good lipophilicity: p-cresol, p-hydroxybenzaldehyde, etc. are slightly soluble in water, soluble in organic solvents such as ether and chloroform, have good lipophilicity, are suitable for the preparation of antifouling coatings, and are easy to control their release rate, which can effectively avoid the phenomenon of explosive release, improve their utilization efficiency, and prolong the antifouling effect.

[0025] (4) Easy to obtain: The industrial synthesis technology of p-cresol, p-hydroxybenzaldehyde, etc. is mature, and its preparation process is simple and the cost is relatively low, which is suitable for large-scale preparation. It solves the problems of low yield, high cost and difficulty in practical promotion and application of natural products often encountered in the process of developing natural antifouling agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the effect of p-cresol on the attachment of the larvae of the barnacle Venus (***P<0.001).

[0027] Figure 2 The effect of p-cresol on the attachment of larvae of the foot disc of the sand slug (***P<0.001).

[0028] Figure 3 This is the effect of p-hydroxybenzaldehyde on the attachment of the larvae of the barnacle Venus (***P<0.001). DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0030] Example 1

[0031] This example uses p-cresol as a single-component antifouling agent, and its inhibitory effect on large marine fouling animals is detected as follows:

[0032] 1. Detection of the inhibitory effect of p-cresol on large marine fouling animal barnacles

[0033] Cultivation of larvae of barnacles: The adult barnacles collected from the sea area are cleaned and dried in the shade for 24 hours. They are placed in fresh seawater with a water temperature of 28°C and a salinity of 30 to induce spawning for about 2-5 hours. The barnacles release nauplii. The impurities in the seawater are filtered out with a 70-mesh sieve, and the nauplii are collected with a 150-mesh sieve. They are placed in 0.22μm membrane-filtered seawater with a water temperature of 28°C and a salinity of 30 for cultivation. The culture density is controlled to be about 2 larvae per milliliter. During the cultivation period, Platmonas subcordiformis is fed as bait every day. After 5-7 days of cultivation, the nauplii develop into Venus larvae, which are collected with a 120-mesh sieve for detection.

[0034] Antifouling activity test: p-cresol was dissolved in DMSO to prepare a 50 mg / mL stock solution. The antifouling activity test used a 24-well plate as the experimental container, and a control group and an experimental group were set up, with 3 parallels in each group. First, 1798 μL of membrane-filtered seawater was added to each well, and then 200 μL of membrane-filtered seawater containing about 20 larvae of the barnacle Venus was aspirated with a pipette and added to each well. 2 μL of DMSO was added to each well of the control group, and 2 μL of DMSO solution of natural products was added to each well of the experimental group. The preliminary experimental results showed that 0.1% DMSO had no significant effect on the attachment of the larvae of the barnacle Venus. 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 with an inverted microscope. The number of attached larvae and the number of unattached larvae were recorded to calculate the attachment rate.

[0035] The results of the effect of p-cresol on the attachment of Venus larvae are shown in the attached figure. Figure 1 The half-inhibitory concentration EC was calculated as50 7.28 μg mL -1 , which confirmed that p-cresol has a good inhibitory effect on the attachment of the larvae of the barnacle Venus.

[0036] 2. Detection of the inhibitory effect of p-cresol on the larvae of the large marine fouling shellfish, the sand screen shell

[0037] Cultivation of sand sifting mussel larvae: The adult sand sifting mussels collected from the sea area are cleaned and the byssus threads are cut off. After drying in the shade for 12 hours, they are placed in fresh seawater with a water temperature of 32°C and a salinity of 20 to induce spawning for 2-5 hours. The parent mussels discharge sperm and eggs, and wait for them to be fertilized to form fertilized eggs. The fertilized eggs are collected with a 400-mesh sieve and placed in membrane-filtered seawater with a water temperature of 28°C and a salinity of 20 for cultivation. After 1 day of cultivation, when they develop into face disc larvae, they are fed with Isochrysis galbana. During the cultivation period, the water is changed every day, and the culture density is controlled to be about 2 larvae per milliliter. After 7-8 days of cultivation, the face disc larvae develop into foot face disc larvae. The foot face disc larvae are collected with a 120-mesh sieve for detection.

[0038] Antifouling activity test: p-cresol was dissolved in DMSO to prepare a 50 mg / mL stock solution. The antifouling activity test used a 24-well plate as the experimental container, and a control group and an experimental group were set up, with 3 parallels in each group. First, 1798 μL of membrane-filtered seawater was added to each well, and then 200 μL of membrane-filtered seawater containing about 20 sand screen mussel foot disc larvae was aspirated with a pipette and added to each well. 2 μL of DMSO was added to each well of the control group, and 2 μL of DMSO solution of natural products was added to each well of the experimental group. 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 with an inverted microscope. The attached larvae had atrophy on their face discs, and it was seen that they stretched their feet to crawl or secreted foot threads to attach. The number of attached larvae and the number of unattached larvae were recorded to calculate the attachment rate.

[0039] The results of the effect of p-cresol on the attachment of larvae of the foot disc of sand scallops are shown in the attached figure. Figure 2 The half-inhibitory concentration EC was calculated as 50 5.54 μg mL -1 , which confirmed that p-cresol had a good inhibitory effect on the attachment of the larvae of the foot disc of the sand scallop.

[0040] Example 2

[0041] The p-cresol antifouling agent of Example 1 was added to the coating. The weight ratio of each raw material of the antifouling coating of this example is as follows:

[0042]

[0043] The preparation method of the coating of this embodiment comprises the following steps:

[0044] Add xylene solvent in proportion to the high-speed dispersion container, start the high-speed disperser, and adjust the speed to 400r / min. Slowly add rosin and stir until the rosin is completely dissolved. Add chloroether resin in proportion and continue to stir at a low speed until the resin is completely dissolved. Add organic bentonite, titanium dioxide, talcum powder and p-cresol antifouling agent in proportion, adjust the speed to 1200r / min, and stir for 10 minutes. Use a basket sand mill to grind the paint to a fineness of less than 60μm, and then test the fineness and viscosity to obtain the antifouling paint. The antifouling paint is applied to the surface of marine facilities by dipping, spraying or coating.

[0045] The antifouling performance test of the coating in this embodiment is as follows:

[0046] The 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. After 3 months of hanging board in the sea area, the paint film was intact, without shedding or blistering, and no obvious fouling organisms were attached.

[0047] Example 3

[0048] This embodiment is a marine antifouling agent, which uses p-hydroxybenzaldehyde as the only active ingredient. Its inhibitory effect on large marine fouling animal barnacles is tested as follows:

[0049] Cultivation of larvae of barnacles: The adult barnacles collected from the sea area are cleaned and dried in the shade for 24 hours. They are placed in fresh seawater with a water temperature of 28°C and a salinity of 30 to induce spawning for about 2-5 hours. The barnacles release nauplii. The impurities in the seawater are filtered out with a 70-mesh sieve, and the nauplii are collected with a 150-mesh sieve. They are placed in 0.22μm membrane-filtered seawater with a water temperature of 28°C and a salinity of 30 for cultivation. The culture density is controlled to be about 2 larvae per milliliter. During the cultivation period, Platmonas subcordiformis is fed as bait every day. After 5-7 days of cultivation, the nauplii develop into Venus larvae, which are collected with a 120-mesh sieve for detection.

[0050] Antifouling activity test: p-Hydroxybenzaldehyde was dissolved in DMSO to prepare a 50 mg / mL stock solution. The antifouling activity test used a 24-well plate as the experimental container, and set up a control group and an experimental group, with 3 parallels in each group. 1798 μL of membrane-filtered seawater was added to each well, and then 200 μL of membrane-filtered seawater containing about 20 larvae of the barnacle Venus was aspirated with a pipette and added to each well. 2 μL of DMSO was added to each well of the control group, and 2 μL of DMSO solution of natural products was added to each well of the experimental group. The preliminary experimental results showed that 0.1% DMSO had no significant effect on the attachment of the larvae of the barnacle Venus. 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 with an inverted microscope. The number of attached larvae and the number of unattached larvae were recorded, and the attachment rate was calculated.

[0051] The results of the effect of p-hydroxybenzaldehyde on the attachment of larvae of the barnacle Venus are shown in the attached figure. Figure 1 The half-inhibitory concentration EC was calculated as 50 16.53 μg mL -1 , which confirmed that p-hydroxybenzaldehyde has a good inhibitory effect on the attachment of the larvae of the barnacle Venus.

[0052] Example 4

[0053] The marine antifouling agent of Example 3 was added to the coating, and the weight ratio of each component was as follows:

[0054] 13 parts by weight of chloroether resin

[0055] Rosin 12 parts by weight

[0056] 8 parts by weight of titanium dioxide

[0057] 1 part by weight of organic bentonite

[0058] 11 parts by weight of talc

[0059] 20 parts by weight of p-hydroxybenzaldehyde

[0060] 35 parts by weight of xylene

[0061] The preparation method of the coating of this embodiment comprises the following steps:

[0062] Add xylene solvent in proportion to the high-speed dispersion container, start the high-speed disperser, and adjust the speed to 400r / min. Slowly add rosin and stir until the rosin is completely dissolved, add chloroether resin in proportion, continue to stir at a low speed until the resin is completely dissolved, add organic bentonite, titanium dioxide, talcum powder and p-hydroxybenzaldehyde antifouling agent in proportion, adjust the speed to 1200r / min, and stir for 10 minutes. Use a basket sand mill to grind the paint to a fineness of less than 60μm, and after testing the fineness and viscosity, the antifouling paint can be obtained.

[0063] The antifouling performance test of the coating in this embodiment is as follows:

[0064] The 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. After 3 months of hanging board in the sea area, the paint film was intact, without shedding or blistering, and no obvious fouling organisms were attached.

[0065] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Use of a p-hydroxybenzene compound as a marine antifouling agent, characterized in that: Used to inhibit the attachment of large fouling organisms to the surface of marine facilities; the general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

2. The use of the p-hydroxybenzene compound as a marine antifouling agent according to claim 1, characterized in that: The p-hydroxybenzene compound is p-cresol or p-hydroxybenzaldehyde.

3. The use of the p-hydroxybenzene compound as a marine antifouling agent according to claim 1, characterized in that: The macrofouling organisms include biogenic barnacles and sand scallops.

4. The use of the p-hydroxybenzene compound as a marine antifouling agent according to claim 1, characterized in that: The p-hydroxybenzene compound is used as a single-component antifouling agent, or the p-hydroxybenzene compound is compounded with at least one of isothiazolinone compounds, triazine compounds, N-2,4,6-trichlorophenylmaleimide, pyridinetriphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole or N-(fluorodichloromethylsulfide)-phthalimide to prepare the antifouling agent.

5. The use of the p-hydroxybenzene compound as a marine antifouling agent according to claim 1, characterized in that: It is applied directly or added to antifouling paint and applied to the surface of marine facilities. The application methods include spraying, dipping or coating.

6. The use of the p-hydroxybenzene compound as a marine antifouling agent according to claim 1, characterized in that: The marine facilities include aquaculture equipment, marine monitoring instruments, aquaculture platforms, buoys or ships.

7. A marine antifouling agent, characterized in that: is a p-hydroxybenzene compound, the general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

8. A marine antifouling agent, characterized in that: The invention relates to a composition comprising a p-hydroxybenzene compound and at least one of an isothiazolinone compound, a triazine compound, N-2,4,6-trichlorophenylmaleimide, pyridine triphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole or N-(fluorodichloromethylsulfide)-phthalimide. The general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

9. A marine antifouling coating, characterized in that: The invention comprises a base material, a pigment, an auxiliary agent and a solvent, and also comprises a marine antifouling agent, wherein the marine antifouling agent is a p-hydroxybenzene compound or a composite of a p-hydroxybenzene compound and at least one of isothiazolinone compounds, triazine compounds, N-2,4,6-trichlorophenylmaleimide, pyridine triphenylborane, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyl-pyrrole or N-(fluorodichloromethylsulfide)-phthalimide, and the general formula of the p-hydroxybenzene compound is Wherein R is an alkyl group or an aldehyde group.

10. A marine antifouling paint according to claim 9, characterized in that: The p-hydroxybenzene compound is p-cresol or p-hydroxybenzaldehyde, and the coating components are composed of the following components in parts by weight:

Images