CN112226155B

CN112226155B - Bionic fouling release type organic silicon marine antifouling paint and preparation method thereof

Info

Publication number: CN112226155B
Application number: CN202011017697.5A
Authority: CN
Inventors: 巴淼; 李莉; 陈麒安; 王玉丰; 孔俊俊
Original assignee: Changshu Institute of Technology
Current assignee: Changshu Institute of Technology
Priority date: 2020-09-24
Filing date: 2020-09-24
Publication date: 2021-11-30
Anticipated expiration: 2040-09-24
Also published as: CN112226155A

Abstract

The invention discloses a bionic fouling release type organic silicon marine antifouling paint and a preparation method thereof. The coating can be widely applied to marine ships, marine oil drilling platforms, deep sea detection equipment and facilities and the like, is particularly suitable for facilities statically immersed in a seawater environment, and can simulate a special microstructure (super-hydrophobic characteristic) on the skin surface of large fishes to realize effective inhibition on fouling organisms and simulate the mucus secretion characteristic of the large fishes to realize effective removal of adhered fouling organisms through precipitation and release of silicone oil. Meanwhile, the coating also has excellent mechanical properties, and is beneficial to wide popularization and application.

Description

Bionic fouling release type organic silicon marine antifouling paint and preparation method thereof

Technical Field

The invention belongs to the technical field of marine antifouling paints and underwater paints, and particularly relates to a bionic fouling release type organic silicon antifouling paint for inhibiting and protecting fouling adhesion on the surface of a marine ship and a preparation method thereof.

Background

Marine biofouling is a major problem in the development of marine industry in countries of the world, and painting an antifouling paint is the most effective and convenient method for solving the problem.

The organic silicon environment-friendly marine antifouling paint belongs to fouling release type marine antifouling paint, and effectively inhibits fouling organisms from adhering to the surface of a coating by virtue of low surface energy and unique non-polarity of an organic silicon film-forming coating. And the elastic modulus of the organic silicon coating is low, and the adhered organisms can fall off from the surface of the coating in a stripping mode with low energy consumption. For marine vessels, fouling organisms which are not firmly adhered can be easily removed by means of the scouring effect of the water flow caused by the relative movement of the vessel and the sea water. However, for oil drilling platforms standing on the ocean, oil transportation pipelines statically immersed in the seawater, marine fishery culture equipment and the like, the high-speed movement in the seawater is lacked, and the effective shedding of fouling organisms, namely the effective self-cleaning, cannot be realized only by the relative flow of water flow. In addition, the organic silicon-based antifouling coating has the common problems of poor mechanical property, poor bonding force with a base material and the like in the using process. Related improvement means comprise micro-nano powder reinforcement, polymer chemical modification and the like, however, the improvement means cannot solve the problem of preventing and controlling the adhesion of fouling organisms in a static seawater environment. For equipment that is statically submerged in seawater, antifouling is currently only possible by using antifouling coatings containing biological biocides, however for equipment that is involved in the marine farming industry, the use of biological biocides can have a toxic effect on the farmed organisms, and moreover the effective release of biological biocides also needs to be achieved by a scouring effect brought about by sufficient relative movement of the seawater, and thus cannot be carried out on a large scale in this industry. The environmental-friendly biological antifouling agent generally has the problem of high cost at present, which also limits the use of the agent in the static water area equipment industry. Although the most important application field of antifouling paints is many ships sailing in the water area environment, static equipment in the submerged water area environment is also the main field of application of antifouling paints, and there is a strong need in the field to develop an environmentally friendly antifouling paint that is highly effective against fouling and biological adhesion.

Disclosure of Invention

Aiming at the problems of low strength, requirement of seawater shearing motion to realize release of adhesion fouling organisms and poor antifouling effect under the condition of low water flow motion and the like of the fouling release type organic silicon antifouling paint, the invention provides a novel bionic fouling release type organic silicon antifouling paint which can simulate the super-hydrophobic characteristics of the skin surface of marine macroorganisms such as sharks, fishes and the like to reduce the adhesion of the fouling organisms, can realize an antifouling mechanism of spontaneous shedding of the adhesion fouling organisms by simulating the biological characteristics of mucus secreted by the skin surface, and ensures that the paint has excellent mechanical properties, suitable simulated mucus secretion rate, a special super-hydrophobic structure can be formed on the surface of a cured coating by introducing special nano powder, and has the advantages of excellent static antifouling property, spontaneous shedding of the adhesion fouling organisms and the like.

The technical scheme of the invention is as follows: the bionic fouling release type organic silicon marine antifouling paint for fouling protection of the surface of marine facilities comprises (1) 10-20 parts by weight of a component A; (2) 2-4 parts of a component B; (3) 0.5-1 part of a component C;

wherein the content of the first and second substances,

the component A comprises the following components in parts by weight:

the component B comprises the following components in parts by weight:

1.5-5.0 parts of crosslinking curing agent

5.0-15.0 parts of a solvent;

the component C comprises the following components in parts by weight:

0.5 to 2.5 portions of catalyst

2.0-8.0 parts of a solvent;

the pre-dispersion slurry is obtained by performing ultrasonic dispersion on the following raw materials in parts by weight:

80.0-100.0 parts of polysiloxane resin

0.5-2.0 parts of stabilized carbon nanotube

0.1-1.0 part of stabilized spherical nano ferroferric oxide.

Preferably, the pre-dispersion slurry is obtained by adding 80.0-100.0 parts of polysiloxane resin and 0.5-2.0 parts of stabilized carbon nano tubes into an ultrasonic dispersion machine, dispersing for 15-30 min at 1000-1500 rpm, reducing the rotating speed to 500-800 rpm, adding 0.1-1.0 part of stabilized nano ferroferric oxide into the dispersion machine, and continuously dispersing for 20-30 min.

Specifically, the carbon nano tube subjected to stabilizing treatment is obtained by adding 0.5-2.0 parts of carbon nano tube into 50-75 parts of 0.5mol/L sodium citrate solution, performing ultrasonic dispersion for 50-70 min, filtering, and then performing vacuum drying on a filter for 20-24 h.

Specifically, the stabilized nano ferroferric oxide is obtained by adding 0.1-1.0 part of spherical nano ferroferric oxide into 50-75 parts of 0.5mol/L sodium citrate solution, filtering after ultrasonic dispersion for 50-70 min, and then drying the filtrate in vacuum for 20-24 h.

Specifically, the polysiloxane resin is at least one of alpha, omega-dihydroxypolysiloxane, alpha, omega-dihydroxypolydimethylsiloxane and alpha, omega-dihydroxypolymethylsiloxane resin.

More specifically, the carbon nanotube is at least one of a hydroxylated multiwall carbon nanotube and a graphitized multiwall carbon nanotube, and the particle size of the carbon nanotube is not particularly limited, and is preferably in the range of 20 to 50 nm.

More specifically, the particle size of the spherical nano ferroferric oxide powder is not particularly limited, and the preferred particle size range is 20-50 nm.

More specifically, a 0.5mol/L disodium citrate solution is prepared by dissolving and dispersing disodium citrate in deionized water to form a stable solution with a concentration of 0.5 mol/L.

Preferably, the non-reactive silicone oil refers to oligosiloxanes in which the terminal and side functional groups do not undergo chemical reaction in the curing and crosslinking reaction, and specifically, the non-reactive silicone oil of the present invention is at least one of methyl silicone oil, methyl phenyl silicone oil and methyl alkyl silicone oil.

Preferably, the crosslinking curing agent is tetraethoxysilane, methyl triacetoxysilane, aminopropyltriethoxysilane, methyl tributanoneOxime compoundsAt least one of silanes.

Preferably, the catalyst is at least one of dibutyltin dilaurate, stannous octoate and organic bismuth.

Preferably, the auxiliary agent is at least one of a dispersing agent, a defoaming agent and a flatting agent.

Specifically, the dispersant is at least one of BYK141, BYK163, and tequila 903, 931.

Specifically, the antifoaming agent is at least one of BYK065, BYK066N, tequila 6500, 6600.

Specifically, the leveling agent is at least one of BYK349 and BYK377, and modesty 835 and 837.

Preferably, the filler is not particularly limited, and is preferably at least one of heavy calcium powder, talc powder, barium sulfate, titanium dioxide, and kaolin.

Preferably, the solvent is at least one of ketones, alcohols and aromatic hydrocarbons, preferably at least one of pentanedione, acetone, absolute ethanol, toluene and xylene.

According to the coating prepared by the technical scheme, A, B, C components are uniformly mixed according to the weight parts, the coating can be constructed by adopting methods such as brushing, spraying or rolling, and the like, and the coating is prepared by crosslinking and curing, and the specific construction method is not limited.

Compared with the prior environment-friendly organic silicon marine antifouling paint, the invention has the beneficial effects that:

1. the invention realizes the stabilization treatment of the powder by ultrasonically treating the carbon nano tube and the spherical nano tetraoxide three-body powder in 0.5mol/L sodium citrate solution, and can effectively realize the uniform dispersion of the powder and prevent the agglomeration of the powder in the dispersion process of the siloxane resin.

2. According to the invention, the spherical nano ferroferric oxide powder subjected to stabilization treatment is added, so that a super-hydrophobic special surface structure can be formed on the surface of the cured coating, and the super-hydrophobic characteristic of the skin surface of large marine organisms (such as whales) is effectively simulated by the structure, so that the adhesion capability of fouling organisms on the surface of the coating can be remarkably reduced.

3. The organic silicon antifouling paint contains the non-reactive micromolecular silicone oil, and in the curing service process of the paint, the non-reactive micromolecular silicone oil in the coating can be separated out between the coating and a seawater interface through migration, so that the smoothness of the surface of the coating is improved, the adhesion difficulty of fouling organisms is improved, the behavior that large marine organisms fall off and adhere to the fouling organisms through the release of mucus outwards from the skin is simulated, and the adhesion fouling release rate is obviously improved.

4. According to the invention, the carbon nano tube powder subjected to stabilizing treatment is added, so that the migration and precipitation rate of the silicone oil in the cured coating can be effectively controlled, and the effective antifouling service cycle of the antifouling coating is prolonged while enough precipitation amount of the silicone oil is ensured.

5. The invention weakens the firm adhesion of fouling organisms by constructing the super-hydrophobic surface, and reduces the bonding strength of the adhesion fouling organisms by effectively separating out the silicone oil, thereby realizing the self-shedding of the adhesion fouling organisms, namely realizing the self-cleaning of the antifouling coating in a static seawater environment.

6. The bionic fouling release type organic silicon marine antifouling paint can be applied to various marine ships, marine oil drilling platforms, deep sea detection equipment and facilities and the like.

7. According to the invention, the carbon nano tube and the spherical nano ferroferric oxide are added into the coating, so that the coating has excellent mechanical properties and higher hardness, and the coating is ensured to have stronger wear resistance and scratch resistance.

Detailed Description

The present invention will be described below by way of examples, but the present invention is not limited to the following examples, and various changes can be made within the scope of the present invention and the spirit thereof, and these are included in the technical scope of the present invention.

The bionic fouling release type organic silicon marine antifouling paint for fouling protection of the surface of marine facilities comprises (1) 10-20 parts by weight of a component A; (2) 2-4 parts of a component B; (3) 0.5-1 part of a component C;

wherein the content of the first and second substances,

the preparation method of the component A comprises the following steps: adding the pre-dispersed slurry and the non-reactive silicone oil into a dispersion machine, dispersing for 5-15 min at 500-800 rpm, increasing the rotating speed to 1000-1500 rpm, and then sequentially adding the auxiliary agent, the filler and the solvent into the dispersion machine, and dispersing for 15-30 min.

The preparation method of the component B, the curing agent and the solvent can be carried out by adopting a conventional method.

The preparation method of the component C, the catalyst and the solvent can be carried out by conventional methods.

According to the marine antifouling paint, the component A is used as a main film forming component and plays a role in finally curing to form a film, the component B is used as a curing agent component and plays a role in curing and crosslinking, and the component C is used as a catalyst component and promotes the crosslinking reaction of the component A, B.

The alpha, omega-dihydroxy polydimethylsiloxane selected by the invention is purchased from DY series of Shandong Dayihua chemical industry Co., Ltd, and has the viscosity (25 ℃): 10000 mPa.s, but the silicone resin selected for use in the practice of the invention is not limited to the manufacturer and its specific performance parameters.

The silicone oil selected by the invention comprises methyl silicone oil, phenyl methyl silicone oil and methyl alkyl silicone oil, wherein the methyl silicone oil is purchased from Shandong Dayi chemical engineering Co., Ltd, and the phenyl methyl silicone oil and the methyl alkyl silicone oil are purchased from Shanghai Hualing resin Co., Ltd, but the silicone oil selected by implementing the invention is not limited to manufacturers and specific performance parameters thereof.

[ example 1 ] to [ example 4 ]

The formula is shown in table 1, and the specific preparation process is the same as follows:

(1) dividing 0.5mol/L disodium citrate solution into two groups with equal parts by weight, respectively marking the two groups as an A group and a B group, adding a carbon nano tube into the A group at 70 ℃ by using ultrasonic dispersion equipment, adding spherical nano ferroferric oxide into the B group, filtering after ultrasonic dispersion for 55min, and then carrying out vacuum drying on a filtrate for 20h to respectively obtain a carbon nano tube and spherical nano ferroferric oxide which are subjected to stabilization treatment;

(2) adding polysiloxane resin and carbon nano tubes subjected to stabilization treatment into a dispersion machine, dispersing for 20min at 1000rpm, then reducing the rotating speed to 500rpm, adding nano ferroferric oxide subjected to stabilization treatment into the dispersion machine, and continuously dispersing for 30min to obtain pre-dispersion slurry;

(3) adding the pre-dispersion slurry and non-reactive silicone oil into a dispersion machine, dispersing for 5min at 500rpm, then increasing the rotating speed to 1000rpm, sequentially adding the auxiliary agent, the filler and the solvent into the dispersion machine, dispersing for 30min, obtaining a component A, and then canning for later use;

(4) manually stirring the curing agent and the solvent to obtain the component B, canning for later use, manually stirring the catalyst and the solvent to obtain the component C, and canning for later use.

Before the prepared coating is used, A, B, C components are uniformly mixed and stirred according to the parts by weight, and the bionic fouling release type organic silicon marine antifouling coating is obtained after coating and curing.

TABLE 1

[ example 5 ]

The formulation was the same as in example 1, and the preparation process was as follows:

(1) dividing 0.5mol/L sodium citrate solution into two groups (group A and group B) with equal parts by weight, adding carbon nano tubes into the group A and spherical nano ferroferric oxide into the group B by using ultrasonic dispersion equipment at 75 ℃, filtering after ultrasonic dispersion for 50min, and then carrying out vacuum drying on a filtrate for 24h to respectively obtain the carbon nano tubes and the spherical nano ferroferric oxide which are subjected to stabilization treatment;

(2) adding polysiloxane resin and carbon nano tubes subjected to stabilization treatment into a dispersion machine, dispersing for 15min at 1200rpm, then reducing the rotating speed to 800rpm, adding nano ferroferric oxide subjected to stabilization treatment into the dispersion machine, and continuously dispersing for 20min to obtain pre-dispersion slurry;

(3) adding the pre-dispersion slurry and non-reactive silicone oil into a dispersion machine, dispersing for 10min at 800rpm, then increasing the rotating speed to 1300rpm, sequentially adding the auxiliary agent, the filler and the solvent into the dispersion machine, dispersing for 20min, obtaining a component A, and then canning for later use;

[ example 6 ]

(1) dividing 0.5mol/L sodium citrate solution into two groups with equal parts by weight, respectively marking as a group A and a group B, adding a carbon nano tube into the group A at the temperature of 80 ℃ by using ultrasonic dispersion equipment, adding spherical nano ferroferric oxide into the group B, filtering after ultrasonic dispersion for 70min, and then carrying out vacuum drying on a filtrate for 24h to respectively obtain a carbon nano tube and spherical nano ferroferric oxide which are subjected to stabilization treatment;

(2) adding polysiloxane resin and carbon nano tubes subjected to stabilization treatment into a dispersion machine, dispersing for 25min at 1500rpm, then reducing the rotating speed to 600rpm, adding nano ferroferric oxide subjected to stabilization treatment into the dispersion machine, and continuously dispersing for 25min to obtain pre-dispersion slurry;

(3) adding the pre-dispersion slurry and non-reactive silicone oil into a dispersion machine, dispersing for 12min at 700rpm, then increasing the rotating speed to 1500rpm, sequentially adding the auxiliary agent, the filler and the solvent into the dispersion machine, dispersing for 25min, obtaining a component A, and canning for later use;

Comparative example 1 (ordinary fouling release type silicone marine antifouling paint)

The common fouling release type organic silicon marine antifouling paint comprises the following raw materials in parts by weight: 100.0 parts of polysiloxane resin, 20.0 parts of pigment, 10.0 parts of filler, 4.0 parts of crosslinking curing agent, 1.0 part of catalyst, 1.0 part of auxiliary agent and 30.0 parts of solvent.

The polysiloxane resin is alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 10000mPa & s; the pigment is selected from industrial cuprous oxide; the filler is titanium dioxide; the cross-linking curing agent is tetraethoxysilane; the catalyst is dibutyltin dilaurate; the auxiliary agent is 0.5 part of BYK163 dispersant of Pico company and 0.5 part of defoaming agent of Germany modest company 6500; the solvent is selected from 20.0 parts of dimethylbenzene and 10.0 parts of acetone.

The preparation method of the common fouling release type organic silicon marine antifouling paint comprises the following steps:

(1) adding 100.0 parts of alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 10000 mPa.s, 20.0 parts of industrial-grade cuprous oxide and 10.0 parts of titanium dioxide into a dispersion machine, dispersing at 3000rpm for 30min at high speed, then adding 0.5 part of BYK163 dispersant of Bike company and 0.5 part of defoamer of Germany modest company into the dispersion machine at 2000rpm, dispersing for 20min, grinding by a sand mill until the fineness is less than 40 mu m to prepare pre-dispersion slurry, and canning for later use;

(2) uniformly mixing 4.0 parts of ethyl orthosilicate and 20.0 parts of dimethylbenzene to prepare a crosslinking curing agent component, canning for later use, and uniformly mixing 1.0 part of dibutyltin dilaurate and 10.0 parts of acetone to prepare a catalyst component, and canning for later use;

(3) the pre-dispersed slurry, the crosslinking curing agent component and the catalyst component are uniformly stirred according to the proportion before use, and the obtained coating is coated and cured to obtain the common fouling release type organic silicon marine antifouling coating.

Comparative example 2 (ordinary silicone marine antifouling paint with silicone oil fouling release type)

The common silicone oil-containing fouling release type organic silicon marine antifouling paint comprises the following raw materials in parts by weight: 100.0 parts of polysiloxane resin, 5.0 parts of non-reactive silicone oil, 10.0 parts of pigment, 20.0 parts of filler, 6.0 parts of crosslinking curing agent, 1.0 part of catalyst and 35.0 parts of solvent.

The polysiloxane resin is alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 10000mPa & s; the silicone oil is methyl silicone oil with the viscosity of 50mPa & s; the pigment is micron-sized ferroferric oxide; the filler is heavy calcium; the cross-linking curing agent is tetraethoxysilane; the catalyst is dibutyltin dilaurate; the solvent is 25.0 parts of absolute ethyl alcohol and 10.0 parts of pentanedione.

The preparation method of the common silicone marine antifouling paint containing silicone oil fouling release type comprises the following steps:

(1) adding 100.0 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 10000 mPas, 5.0 parts of methyl silicone oil with the viscosity of 50 mPas, 10.0 parts of micron-sized ferroferric oxide and 20.0 parts of heavy calcium carbonate powder into a dispersion machine, dispersing at a high speed of 3000rpm for 30min, grinding by a sand mill until the fineness is less than 40 mu m to prepare pre-dispersion slurry, and canning for later use;

(2) uniformly mixing 6.0 parts of ethyl orthosilicate and 25.0 parts of absolute ethyl alcohol to prepare a crosslinking curing agent component, canning for later use, and uniformly mixing 1.0 part of dibutyltin dilaurate and 10.0 parts of pentanedione to prepare a catalyst component, and canning for later use;

(3) the pre-dispersed slurry, the crosslinking curing agent component and the catalyst component are uniformly stirred according to the proportion before use, and the obtained coating is coated and cured to obtain the common silicone marine antifouling coating containing silicone oil fouling release type.

Comparative example 3

The formula is the same as that in example 1 except that the formula does not contain 0.5mol/L disodium citrate solution, the preparation process does not contain a link of ultrasonic dispersion treatment of the carbon nano tube and the spherical nano ferroferric oxide by the 0.5mol/L disodium citrate solution, and the preparation process is the same as that in example 1.

Comparative example 4

In the comparative example, the weight part of the spherical nano ferroferric oxide is 2.0 parts (the particle size is 20nm), and other components and the preparation process are the same as those in the example 1.

The marine antifouling coatings obtained in the examples and comparative examples were measured for water contact angle, shore hardness, elastic modulus and antifouling property, and the measurement results are shown in table 2.

1. Water contact angle

The contact angle of the coating surface was measured using an XG-CAMC3 type full-automatic contact angle measuring instrument manufactured by Shanghai Xuanyi instruments Ltd. And 3 mu L of deionized water is dripped on the surface of the coating, the dripping time is between 5 and 10 seconds, 6 points on each coating surface are selected for photographing, then the contact angle of the deionized water on the coating surface is measured by an angulometry, and the average value is taken as the measured contact angle value. Meanwhile, a rolling contact angle measuring module of the device is used, 6 points are selected on the surface of each coating to be tested, a rolling contact angle of liquid drops on the surface of the coating is measured by adopting an inclined plate method, and the average value is taken as the measured rolling contact angle value.

2. Shore hardness

The Shore hardness of the coating was measured using the HT220 Shore hardness tester available from Peak technologies, Inc. of the time of Beijing. And (3) testing the Shore durometer on the surface of the coating, and measuring 6 test points at different positions of each coating. Since the test conditions require the thickness of the test specimen to be measured to exceed 5mm, a coating of sufficient thickness is required to meet the test requirements.

3. Modulus of elasticity

The tensile test specimen (length 150mm, width 5mm and thickness 2mm) is prepared according to the molding requirements of national standard GB/T528-1998 by injection molding by using a polytetrafluoroethylene mold, and the tensile curve of the tensile test specimen is measured by using an XLM type electronic tensile tester produced by a Jinan optical power plant, and the tensile rate is 25 mm/min. And recording tensile test data of the tensile sample, and performing linear fitting on the tensile test data with the deformation rate not more than 0.5%, wherein the obtained fitting curve is the elastic modulus of the tensile sample. Each coating was tested 3 times and the average was taken.

5. Antifouling Property test

The hanging plate preparation is carried out according to the national standard GB5370-85 antifouling paint sample plate shallow sea immersion test method, and the shallow sea hanging plate test is carried out in Nantong sea area to evaluate the antifouling performance of the coating. The test was carried out on a southeast Tong-initiating harbor floating dock, and the prepared hanging plate was vertically immersed in seawater 1m to 2m from the sea level. And observing and checking the hanging plate after 3 months, and measuring the attachment degree of marine fouling organisms. The YLQ4660C-100A type ultrahigh pressure household full-automatic cleaning machine manufactured by Shanghai Yili electric appliances company Limited is used, under the pressure of 5MPa, a nozzle is 20cm away from the surface of a sample plate, water is sprayed to wash fouling organisms attached to the surface of the sample plate, and the degree of difficulty in stripping the fouling organisms and the surface state of a coating after the fouling organisms are clear are evaluated.

TABLE 2 Properties of the example coatings and the comparative example coatings

Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which are disclosed and guided by the above description. Therefore, the present invention is not limited to the above-described embodiments, and modifications to the present invention are also intended to fall within the scope of the appended claims.

Claims

1. A marine antifouling paint is characterized by comprising (1) 10-20 parts of a component A; (2) 2-4 parts of a component B; (3) 0.5-1 part of a component C;

wherein the content of the first and second substances,

the component A comprises the following components in parts by weight:

40.0-50.0 parts of pre-dispersed slurry

2.0-5.0 parts of non-reactive silicone oil

0.1-1.0 part of assistant

0.0 to 2.5 portions of filler

10.0-15.0 parts of a solvent;

the component B comprises the following components in parts by weight:

1.5-5.0 parts of crosslinking curing agent

5.0-15.0 parts of a solvent;

the component C comprises the following components in parts by weight:

0.5 to 2.5 portions of catalyst

2.0-8.0 parts of a solvent;

80.0-100.0 parts of polysiloxane resin

0.5-2.0 parts of stabilized carbon nanotube

0.1-1.0 part of stabilized spherical nano ferroferric oxide;

wherein the content of the first and second substances,

the carbon nano tube subjected to stabilization treatment is obtained by adding 0.5-2.0 parts of carbon nano tube into 50-75 parts of 0.5mol/L sodium citrate solution, performing ultrasonic dispersion for 50-70 min, filtering and drying in vacuum;

the stabilized spherical nano ferroferric oxide is obtained by adding 0.1-1.0 part of spherical nano ferroferric oxide into 50-75 parts of 0.5mol/L sodium citrate solution, performing ultrasonic dispersion for 50-70 min, filtering and performing vacuum drying;

the polysiloxane resin is alpha, omega-dihydroxy polydimethylsiloxane.

2. The marine antifouling paint as claimed in claim 1, wherein the pre-dispersion slurry is obtained by ultrasonically dispersing 80.0-100.0 parts of polysiloxane resin and 0.5-2.0 parts of stabilized carbon nanotubes at 1000-1500 rpm for 15-30 min, then reducing the rotation speed to 500-800 rpm, adding 0.1-1.0 part of stabilized spherical nano ferroferric oxide, and continuing to ultrasonically disperse for 20-30 min.

3. The marine antifouling paint according to claim 1, wherein the non-reactive silicone oil is at least one of methyl silicone oil, methylphenyl silicone oil and methyl alkyl silicone oil.

4. The marine antifouling paint according to claim 1, wherein the crosslinking curing agent is at least one of ethyl orthosilicate, methyl triacetoxysilane, aminopropyltriethoxysilane, and methyl tributyrinoxime silane.

5. The marine antifouling paint of claim 1, wherein the catalyst is at least one of dibutyltin dilaurate, stannous octoate, and organobismuth.

6. The marine antifouling paint according to claim 1, wherein the auxiliary agent is at least one of a dispersant, a defoaming agent and a leveling agent.

7. A marine antifouling paint according to claim 6, wherein the dispersant is at least one of BYK163, D.E. 903, 931.

8. A marine antifouling paint according to claim 6, wherein the defoaming agent is at least one of BYK065, BYK066N, and D.E. 6500 and 6600.

9. A marine antifouling paint according to claim 6, wherein the levelling agent is at least one of BYK349, BYK377, and D.E. 835, 837.

10. The marine antifouling paint of claim 1, wherein the filler is at least one of heavy calcium powder, talc, barium sulfate, titanium dioxide, and kaolin.

11. The marine antifouling paint according to claim 1, wherein the solvent is at least one of ketones, alcohols, and aromatic hydrocarbons.

12. The marine antifouling paint according to claim 1, wherein the solvent is at least one of pentanedione, acetone, absolute ethanol, toluene, and xylene.

13. A process for the preparation of a marine antifouling paint according to any of claims 1 to 12, wherein the a-component is prepared by the steps of: and ultrasonically dispersing the pre-dispersed slurry and the non-reactive silicone oil in 500-800 rpm for 5-15 min, then increasing the rotating speed to 1000-1500 rpm, sequentially adding the auxiliary agent, the filler and the solvent, and continuing to ultrasonically disperse for 15-30 min.

14. A marine antifouling coating, which is characterized in that A, B, C three components in the marine antifouling paint according to any one of claims 1 to 12 are uniformly mixed according to the parts by weight, are applied by brushing, spraying or rolling, and are crosslinked and cured to form the coating.