1. The composite antifouling paint capable of controllably releasing cuprous oxide is characterized by comprising the following components in parts by weight: 60-70 parts of base material, 5-10 parts of composite antifouling agent, 2-5 parts of antirust agent, 1-3 parts of diluent and 10-15 parts of filler.

2. The composite antifouling paint capable of controllably releasing cuprous oxide as claimed in claim 1, wherein said binder is fluorosilicone resin.

3. The composite antifouling paint capable of controllably releasing cuprous oxide as claimed in claim 1, wherein said composite antifouling agent is a composite nanocarrier coated cuprous oxide antifouling agent, wherein the composite nanocarrier is prepared from boron nitride nanosheets, trimethoxysilane and polyethylene glycol diacrylate.

4. The composite antifouling paint capable of controllably releasing cuprous oxide as claimed in claim 1, wherein said rust inhibitor is a mixture of talc, red iron oxide, aluminum tripolyphosphate and zinc phosphate, and the mass ratio of the talc, the red iron oxide, the aluminum tripolyphosphate and the zinc phosphate is 1:1-5: 1-5.

5. A composite controlled release cuprous oxide antifouling paint according to claim 1 wherein said diluent is at least one of xylene, cyclohexanone, dimethyl phthalate, butyl acetate.

6. A composite controlled release cuprous oxide antifouling paint according to claim 1, wherein said filler is at least one of zinc oxide, zeolite, fumed silica, organobentonite, titanium dioxide, polydimethylsiloxane.

7. The preparation method of the composite antifouling paint capable of controllably releasing cuprous oxide is characterized by comprising the following steps:

(1) preparing boron nitride nanosheets: activating hexagonal boron nitride powder by hydrochloric acid with the pH value of 2-4 for 20-24h, then dispersing the activated hexagonal boron nitride powder in isopropanol solution after centrifugation, washing and drying, then stripping by ultrasonic waves, centrifuging for 70-90min at the rotating speed of 2000-4000r/min after stripping is finished, obtaining supernatant after centrifugation is finished, and washing and drying the supernatant to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding boron nitride nanosheets, polyethylene glycol diacrylate, trimethoxy silane and cuprous oxide into deionized water, then reacting in a sealed hydrothermal reactor, and after the reaction is finished, centrifuging and drying reaction products to obtain the composite nano-carrier coated cuprous oxide antifouling agent;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: uniformly dispersing the base material, the cuprous oxide-coated antifouling agent coated by the composite nano carrier, the antirust agent, the diluent and the filler on a high-speed dispersion machine, then grinding until the particle size is not less than 50 mu m to obtain a solid mixture, adding the solid mixture into deionized water, and uniformly stirring and mixing to obtain the cuprous oxide-releasing composite antifouling paint.

8. The preparation method of the cuprous oxide controlled-release composite antifouling paint as claimed in claim 7, wherein in the step (1), the ultrasonic power is 240-360w, and the ultrasonic time is 4-6 h.

9. The preparation method of the cuprous oxide controllable release composite antifouling paint, according to claim 7, is characterized in that in the step (2), the mass ratio of the boron nitride nanosheet, the polyethylene glycol diacrylate, the trimethoxysilane, the cuprous oxide and the deionized water is 4-6:7-9:1-3:2-4: 20.

10. The method for preparing the cuprous oxide controllable-release composite antifouling paint as claimed in claim 7, wherein in the step (2), the reaction temperature is 100-.

Background

The marine environment is a very complex corrosive fouling environment, equipment immersed in seawater is inevitably influenced by marine fouling organisms, and the marine fouling organisms are attached to the surface of a ship below a waterline, so that the performance of the ship is influenced, and huge economic loss and resource waste are caused.

Painting an antifouling paint is the most economical, simple and effective method in the marine antifouling technology, and currently 80% of marine antifouling paints adopt cuprous oxide as an antifouling agent. The antifouling mechanism of cuprous oxide is: the cuprous oxide is decomposed to generate bivalent copper ions which are continuously seeped out to the interface, and after the bivalent copper ions reach a certain concentration, main enzymes of some marine organisms are inactivated or cell proteins are precipitated, so that fouling organisms die, and the antifouling purpose is achieved.

Chinese patent CN201710032753 discloses modified silicon dioxide coated cuprous oxide with a novel core-shell structure and a preparation method thereof, wherein the cuprous oxide consists of a cuprous oxide core layer and a modified porous silicon dioxide shell layer, the particle size of the cuprous oxide is 0.02-20 mu m, the thickness of the modified porous silicon dioxide is 0.01-1 mu m, and the pore diameter is 5-60 nm. The preparation method is carried out in two parts, wherein in the first step, modified silicon dioxide coated cuprous oxide is formed, and in the second step, alkali is adopted to corrode the silicon dioxide layer to form a porous structure. The cuprous oxide coated by the modified porous silicon dioxide with the core-shell structure, which is prepared by the invention, has the advantages of simple preparation process, low cost, controllable release rate, easy dispersion in an organic solvent, certain hydrophilicity and the like, and can be used in the antifouling paint for marine facilities to prolong the service life and reduce the using amount. However, in the process of corroding the silicon dioxide with alkali, the pores of the silicon dioxide become larger and larger along with the prolonging of the time, so that the cuprous oxide released by the coating is more and more, the long-time stable release of the cuprous oxide cannot be realized, the cuprous oxide is wasted, and the protection of the marine environment is not facilitated.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a composite antifouling paint capable of controllably releasing cuprous oxide and a preparation method thereof, and solves the technical problem of unstable release rate of cuprous oxide in seawater.

In order to achieve the purpose, the invention adopts the following technical scheme:

a composite antifouling paint capable of controllably releasing cuprous oxide comprises the following components in parts by weight: 60-70 parts of base material, 5-10 parts of composite antifouling agent, 2-5 parts of antirust agent, 1-3 parts of diluent and 10-15 parts of filler.

Preferably, the base material is fluorosilicone resin.

Preferably, the composite antifouling agent is a cuprous oxide antifouling agent wrapped by a composite nano-carrier, wherein the composite nano-carrier is prepared from boron nitride nanosheets, trimethoxy silane and polyethylene glycol diacrylate.

Preferably, the antirust agent is a mixture of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate, and the mass ratio of the talcum powder to the iron oxide red to the aluminum tripolyphosphate to the zinc phosphate is 1:1-5: 1-5.

Preferably, the diluent is at least one of xylene, cyclohexanone, dimethyl phthalate and butyl acetate.

Preferably, the filler is at least one of zinc oxide, zeolite, gas-phase silica, organic bentonite, titanium dioxide and polydimethylsiloxane.

The invention also provides a preparation method of the composite antifouling paint capable of controllably releasing cuprous oxide, which comprises the following steps:

(1) preparing boron nitride nanosheets: activating hexagonal boron nitride powder by hydrochloric acid with the pH value of 2-4 for 20-24h, then dispersing the activated hexagonal boron nitride powder in isopropanol solution after centrifugation, washing and drying, then stripping by ultrasonic waves, centrifuging for 70-90min at the rotating speed of 2000-4000r/min after stripping is finished, obtaining supernatant after centrifugation is finished, and washing and drying the supernatant to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding boron nitride nanosheets, polyethylene glycol diacrylate, trimethoxy silane and cuprous oxide into deionized water, then reacting in a sealed hydrothermal reactor, and after the reaction is finished, centrifuging and drying reaction products to obtain the composite nano-carrier coated cuprous oxide antifouling agent;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: uniformly dispersing the base material, the cuprous oxide-coated antifouling agent coated by the composite nano carrier, the antirust agent, the diluent and the filler on a high-speed dispersion machine, then grinding until the particle size is not less than 50 mu m to obtain a solid mixture, adding the solid mixture into deionized water, and uniformly stirring and mixing to obtain the cuprous oxide-releasing composite antifouling paint.

Preferably, in the step (1), the ultrasonic power is 240- & ltwbr & gt 360 & lt w & gt, and the ultrasonic time is 4-6 h.

Preferably, in the step (2), the mass ratio of the boron nitride nanosheet, the polyethylene glycol diacrylate, the trimethoxy silane, the cuprous oxide and the deionized water is 4-6:7-9:1-3:2-4: 20.

Preferably, in the step (2), the reaction temperature is 100-.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention provides a composite antifouling paint capable of controllably releasing cuprous oxide and a preparation method thereof, the cuprous oxide is coated on a composite nano carrier, in alkaline environment, the ester group of the polyethylene glycol diacrylate ester of the composite nano-carrier can be hydrolyzed, so that the pores of the composite nano-carrier are enlarged, further releasing the coated cuprous oxide, wherein the pH value of the seawater is about 8, the pH value change of the seawater is about 0.5, this makes the gap size of the composite nano-carrier pores basically stable, controls the tightness of the composite nano-carrier by pH, so as to realize the uniform and quantitative release of cuprous oxide coated on the antifouling agent, and the cuprous oxide starts to be released only when the antifouling agent is contacted with seawater, namely, the cuprous oxide is released by the antifouling paint at the contact part of the ship body and the seawater for decontamination, so that the cost can be saved, and the service life of the paint is prolonged.

(2) The invention provides a composite antifouling paint capable of controllably releasing cuprous oxide and a preparation method thereof.

(3) The invention provides a composite antifouling paint capable of controllably releasing cuprous oxide and a preparation method thereof, wherein the composite nano carrier provided by the invention is prepared from a boron nitride nanosheet, trimethoxy silane and polyethylene glycol diacrylate, and the boron nitride nanosheet is conjugated with the trimethoxy silane and then condensed with the polyethylene glycol diacrylate through Michael addition reaction, so that the boron nitride nanosheet is functionalized, and the problem of uneven dispersion of cuprous oxide on the boron nitride nanosheet is solved.

Detailed Description

The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.

It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are commercially available.

Example 1

A preparation method of a composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps:

(1) preparing boron nitride nanosheets: activating 20g of hexagonal boron nitride powder by hydrochloric acid with the pH value of 3 for 24 hours, then centrifuging, washing and drying, dispersing the activated hexagonal boron nitride powder in isopropanol solution, then stripping by using ultrasonic waves with the power of 360w at room temperature for 6 hours, after the stripping is finished, centrifuging for 80 minutes at the rotating speed of 4000r/min, obtaining a supernatant after the centrifugation is finished, and washing and drying the supernatant by using absolute ethyl alcohol to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding 5g of boron nitride nanosheet, 8g of polyethylene glycol diacrylate, 2g of trimethoxy silane and 3g of cuprous oxide into 20g of deionized water, then reacting for 24 hours in a sealed hydrothermal reactor at 130 ℃, centrifuging the reaction product for 30 minutes at the rotating speed of 6000r/min after the reaction is finished, and drying the precipitate for 24 hours at 75 ℃ to obtain the cuprous oxide antifouling agent wrapped by the composite nano carrier;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: 70g of base fluorosilicone resin, 6g of antifouling agent with cuprous oxide coated by composite nano carrier, 4g of antirust agent (1 g of each of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate), 2g of diluent dimethylbenzene and 10g of filler fumed silica are uniformly dispersed on a high-speed dispersion machine, then the mixture is ground until the particle size is not less than 50 mu m to obtain a solid mixture, and then the solid mixture is added into deionized water and stirred and uniformly mixed to obtain the composite antifouling paint capable of controllably releasing cuprous oxide.

Example 2

A preparation method of a composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps:

(1) preparing boron nitride nanosheets: activating 20g of hexagonal boron nitride powder by hydrochloric acid with the pH value of 3 for 24 hours, then centrifuging, washing and drying, dispersing the activated hexagonal boron nitride powder in isopropanol solution, then stripping by using ultrasonic waves with the power of 300w at room temperature for 5 hours, after the stripping is finished, centrifuging for 80 minutes at the rotating speed of 4000r/min, obtaining a supernatant after the centrifugation is finished, and washing and drying the supernatant by using absolute ethyl alcohol to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding 6g of boron nitride nanosheet, 7g of polyethylene glycol diacrylate, 3g of trimethoxy silane and 3g of cuprous oxide into 20g of deionized water, then reacting for 22h at 120 ℃ in a sealed hydrothermal reactor, centrifuging the reaction product for 30min at the rotating speed of 5000r/min after the reaction is finished, and drying the precipitate for 24h at 75 ℃ to obtain the cuprous oxide antifouling agent wrapped by the composite nano carrier;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: 70g of base fluorosilicone resin, 7g of antifouling agent with cuprous oxide coated by composite nano carrier, 4g of antirust agent (1 g of each of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate), 2g of diluent dimethylbenzene and 10g of filler fumed silica are uniformly dispersed on a high-speed dispersion machine, then the mixture is ground until the particle size is not less than 50 mu m to obtain a solid mixture, and then the solid mixture is added into deionized water and stirred and uniformly mixed to obtain the composite antifouling paint capable of controllably releasing cuprous oxide.

Example 3

A preparation method of a composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps:

(1) preparing boron nitride nanosheets: activating 20g of hexagonal boron nitride powder by hydrochloric acid with the pH value of 3 for 24 hours, then centrifuging, washing and drying, dispersing the activated hexagonal boron nitride powder in isopropanol solution, then stripping for 6 hours at room temperature by using ultrasonic waves with the power of 280w, centrifuging for 80 minutes at the rotating speed of 4000r/min after stripping is finished, obtaining a supernatant after the centrifugation is finished, and washing and drying the supernatant by using absolute ethyl alcohol to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding 4g of boron nitride nanosheet, 9g of polyethylene glycol diacrylate, 2g of trimethoxy silane and 4g of cuprous oxide into 20g of deionized water, then reacting for 23 hours in a sealed hydrothermal reactor at 140 ℃, centrifuging the reaction product for 40 minutes at the rotating speed of 6000r/min after the reaction is finished, and drying the precipitate for 24 hours at 75 ℃ to obtain the cuprous oxide antifouling agent wrapped by the composite nano carrier;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: 70g of base fluorosilicone resin, 8g of antifouling agent with cuprous oxide coated by composite nano carrier, 4g of antirust agent (1 g of each of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate), 2g of diluent dimethylbenzene and 10g of filler fumed silica are uniformly dispersed on a high-speed dispersion machine, then the mixture is ground until the particle size is not less than 50 mu m to obtain a solid mixture, and then the solid mixture is added into deionized water and stirred and uniformly mixed to obtain the composite antifouling paint capable of controllably releasing cuprous oxide.

Example 4

A preparation method of a composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps:

(1) preparing boron nitride nanosheets: activating 20g of hexagonal boron nitride powder by hydrochloric acid with the pH value of 3 for 24 hours, then centrifuging, washing and drying, dispersing the activated hexagonal boron nitride powder in isopropanol solution, then stripping for 6 hours at room temperature by using ultrasonic waves with the power of 280w, centrifuging for 80 minutes at the rotating speed of 4000r/min after stripping is finished, obtaining a supernatant after the centrifugation is finished, and washing and drying the supernatant by using absolute ethyl alcohol to obtain boron nitride nanosheets;

(2) preparing the cuprous oxide antifouling agent wrapped by the composite nano carrier: adding 6g of boron nitride nanosheet, 7g of polyethylene glycol diacrylate, 1g of trimethoxy silane and 3g of cuprous oxide into 20g of deionized water, then reacting for 24 hours in a sealed hydrothermal reactor at 120 ℃, centrifuging the reaction product for 20 minutes at the rotating speed of 5000r/min after the reaction is finished, and drying the precipitate for 24 hours at 75 ℃ to obtain the composite nano carrier coated cuprous oxide antifouling agent;

(3) the preparation of the composite antifouling paint capable of controllably releasing cuprous oxide comprises the following steps: 70g of base fluorosilicone resin, 9g of antifouling agent with cuprous oxide coated by composite nano carrier, 4g of antirust agent (1 g of each of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate), 2g of diluent dimethylbenzene and 10g of filler fumed silica are uniformly dispersed on a high-speed dispersion machine, then the mixture is ground until the particle size is not less than 50 mu m to obtain a solid mixture, and then the solid mixture is added into deionized water and stirred and uniformly mixed to obtain the composite antifouling paint capable of controllably releasing cuprous oxide.

Comparative example 1

A preparation method of the composite antifouling paint comprises the following steps:

70g of base fluorosilicone resin, 8g of cuprous oxide, 4g of antirust agent (1 g of each of talcum powder, iron oxide red, aluminum tripolyphosphate and zinc phosphate), 2g of diluent dimethylbenzene and 10g of filler fumed silica are uniformly dispersed on a high-speed dispersion machine, then the mixture is ground until the particle size is not less than 50 mu m to obtain a solid mixture, and then the solid mixture is added into deionized water and stirred and uniformly mixed to obtain the composite antifouling paint.

The antifouling property test and the ultraviolet ray resistance test were performed on the composite antifouling paints prepared in examples 1 to 4 and comparative example 1.

And (3) antifouling performance detection: heating the antifouling material to 80 ℃ to generate melt viscosity, spraying the heated antifouling material on the surface of a metal plate, curing to form a film, wherein the film thickness is 1.2-1.5 mm, carrying out antifouling performance detection according to GB/T5370-one 2007 standard, taking a dark hard polyvinyl chloride plate with the surface sand-blasting thickness of 5mm as a blank sample, and detecting results of 30 days, 60 days and 90 days are as follows:

and (3) detecting the ultraviolet resistance: at an ultraviolet wavelength of 340nm and an intensity of 0.76W/m²The test specimens of examples 1 to 4 and comparative examples 1 to 2 were exposed to radiation at 60 ℃ for 4 hours in an exposure mode 1, and then subjected to an ultraviolet aging test under conditions in which exposure to non-radiation condensation at 50 ℃ for 4 hours was alternately carried out, the total aging exposure time being 500 hours. The results obtained are given in the following table:

item	Example 1	Example 2	Example 3	Example 4	Comparative example 1
						Percentage of cracks (%)	1.9	1.5	1.3	1.2	1.9
UPF value	44	46	47	50	40

The comparative examples and comparative examples show that the antifouling effect of the coating is obviously improved by wrapping cuprous oxide on the composite nano carrier, the ultraviolet resistance of the coating is enhanced, and the coating still maintains a good antifouling effect with the increase of time; in comparative example 1, the composite nano-carrier is not added, and the antifouling capability of the coating is obviously reduced, which shows that the composite nano-carrier not only can realize the stable release of cuprous oxide, but also can improve the ultraviolet resistance of the coating.

Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the present invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.