CN113897117B

CN113897117B - Industrial coating capable of resisting marine organism fouling and preparation method thereof

Info

Publication number: CN113897117B
Application number: CN202111436253.XA
Authority: CN
Inventors: 周伟建; 张旭; 戴海雄; 黄理荣; 林蛟; 周波; 马庆磊
Original assignee: Guangdong Maydos Building Materials Co Ltd
Current assignee: Guangdong Maydos Building Materials Co Ltd
Priority date: 2021-11-29
Filing date: 2021-11-29
Publication date: 2022-05-13
Anticipated expiration: 2041-11-29
Also published as: CN113897117A

Abstract

The invention provides an industrial coating for resisting marine biofouling, which consists of a component A and a component B; the component A comprises 10 to 25 weight percent of organic fluorine modified epoxy resin, 15 to 25 weight percent of epoxy resin and 20 to 30 weight percent of Ag @ SiO₂15 to 25 percent of copper pyrithione and 1 to 2.5 percent of hollow mesoporous silica; the component B comprises 10 to 15 percent of curing agent and the balance of organic solvent; the marine biofouling resistant industrial coating provided by the invention has excellent marine biofouling resistance, can effectively release active silver ions and a copper pyrithione bacteriostatic agent for a long time, prolongs the effective service life of a coating, and keeps the marine biofouling resistance for a long time.

Description

Industrial coating capable of resisting marine organism fouling and preparation method thereof

Technical Field

The invention relates to the technical field of coatings, in particular to an industrial coating for resisting marine biofouling and a preparation method thereof.

Background

Hundreds of thousands of organisms grow in the ocean and when the artificial facility substrate comes into contact with the seawater, the artificial facility substrate is polluted by the marine organisms. In general, marine biofouling comprises four stages: in the first stage, organic matters such as protein, polysaccharide, lipid and the like and some inorganic matters are attached to the surface of a substrate to form a protein film; in the second stage, bacteria, diatom and other microorganisms are attached to the protein film to grow fast and secrete exophytic macromolecules such as protein, polysaccharide and the like to form a layer of biological film; in the third stage, the seaweed spores and protists are attached to a biological membrane to grow; in the fourth stage, a large amount of large fouling organisms continue to adhere and grow to form a serious biofouling layer. The ship running resistance and the ship surface resistance account for a large factor, and fouling organisms are attached to the surface of the ship body to roughen the surface of the ship body, so that the ship running resistance is greatly increased; on the other hand, the total amount of fouling organisms is huge, so that the weight of the ship body is greatly increased, and the oil consumption of the ship during running is increased.

In order to achieve the anti-biofouling effect of the marine coating, the antifouling agent particles are generally uniformly dispersed in the binder resin, and the antifouling agent in the coating is released into seawater by physical means of "dissolution" and "diffusion by seepage". The effective period of the antifouling agent is related to the dissolution and diffusion rate of the antifouling agent in a seawater environment, the antifouling agent has higher diffusion concentration at the initial use stage and can play a better antibacterial role, and the diffusion concentration of the antifouling agent is rapidly reduced along with the prolonging of the use time, so that the antifouling agent has short use period and can not resist long-acting biological fouling. Therefore, the development of the marine biofouling resistant industrial coating which can effectively resist marine biofouling and has long-acting effect has great economic benefit and application value.

Disclosure of Invention

The invention aims to provide an industrial coating for resisting marine biofouling, which is used for effectively preventing microorganisms from attaching to a substrate of artificial facilities and can play a role in resisting marine biofouling for a long time.

According to a first aspect of the present invention, there is provided an industrial coating for marine biofouling resistance, said coating being comprised of a component a and a component B; the component A comprises 10 to 25 weight percent of organic fluorine modified epoxy resin, 15 to 25 weight percent of epoxy resin and 20 to 30 weight percent of Ag @ SiO₂15 to 25 percent of copper pyrithione and 1 to 2.5 percent of hollow mesoporous silica; the component B comprises 10 to 15 percent of curing agent, and the balance is organic solvent.

Preferably, the weight ratio of the component A to the component B is 3.5-4.5: 1.

The fluorocarbon chain in the organic fluorine modified epoxy resin is a hydrophobic group, has extremely high surface activity, and can obviously reduce the surface tension of the material; and the C-F bond is long and short, the bond energy is high, and the surface energy is extremely low. The epoxy resin structure has aliphatic hydroxyl, ether bond, active epoxy group and other components, the hydroxyl and the ether bond have polarity, and molecules can react with free bonds between adjacent interfaces to form very firm chemical bonds, so that a coating film has relatively good physical and mechanical properties and relatively strong surface adhesion and hardness, and the integral adhesion is relatively strong on a metal surface, so that the epoxy resin structure can be used for preparing industrial coatings for ships. The silver used in the invention is nano silver, and the silver has a remarkable surface effect, a very strong sterilization effect, no toxicity and good stability due to the nano-scale size.

According to the marine organism fouling resistant coating provided by the invention, organic fluorine is added into matrix resin for modification, so that the hydrophobic property of the coating can be obviously improved, the surface energy of the coating is reduced, marine organisms are difficult to attach to the surface of the coating and are easy to fall off under the action of external force such as seawater scouring, and an excellent physical antifouling effect can be achieved. Ag @ SiO₂The nano silver coated by silicon dioxide is uniformly dispersed in a shell structure formed by silicon dioxide, so that the nano silver is uniformly dispersed in the coating, and silver ions can be slowly released to play a long-acting antibacterial role. Copper pyrithione is loaded on the hollow mesoporous silica material, so that the copper pyrithione can be uniformly dispersed on the pore canal and the surface of the hollow mesoporous silica material, and the drug agglomeration is avoided; the copper pyrithione is dispersed on the surface or in the pore canal of the hollow mesoporous silica, can be slowly released, and can play the role of bacteriostasis and sterilization for a long time. Hollow mesoporous silica-loaded copper pyrithione and Ag @ SiO₂The antibacterial agent can play a strong antibacterial effect after being compounded.

The organic fluorine modified epoxy resin as the matrix resin can obviously improve the hydrophobic property of the coating and reduce the surface energy of the coating, so that marine organisms are not easy to attach to the surface of the coating, and are easy to fall off under the action of external force such as seawater scouring and the like.

Preferably, the organic solvent in component B is selected from at least one of xylene and butanol.

The curing agent is dissolved in an organic solvent to prepare a component B which is matched with the component A for use, so that the coating can be rapidly cured to form a film.

Preferably, the component A also comprises 3-8% of pigment, 1-2% of dispersing agent, 0.5-2% of defoaming agent, 0.5-1% of flatting agent and 1.5-2.5% of anti-settling agent.

Preferably, the pigment is selected from at least one of titanium dioxide, cadmium red, cadmium yellow, chromium green, iron blue and carbon black.

Preferably, the dispersing agent is a BYK110 dispersing agent, the defoaming agent is a BYK-A530 defoaming agent, the leveling agent is a BYK306 leveling agent, and the anti-settling agent is a BYK410 anti-settling agent.

Preferably, the component A contains 20 percent of the organic fluorine modified epoxy resin, 20 percent of the epoxy resin and 20 percent of Ag @ SiO₂25% of copper pyrithione, 1% of hollow mesoporous silica, 4% of pigment and filler, 1% of dispersing agent, 1% of defoaming agent, 0.5% of flatting agent and 1.5% of anti-settling agent;

the component B contains 15 percent of curing agent;

the weight ratio of the component A to the component B is 4.5: 1.

Preferably, the organofluorine-modified epoxy resin is prepared by: adding organic fluorine powder and a catalyst into epoxy resin, and heating for reaction for 3-4 hours to obtain the organic fluorine modified epoxy resin.

Preferably, the organofluorine powder is N-ethyl, N-hydroxyethyl perfluorooctylsulfonamide.

Preferably, the epoxy resin is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin.

Preferably, the catalyst is selected from at least one of dibutyltin dilaurate, dibutyl diacetic acid and stannous octoate.

Preferably, Ag @ SiO₂Prepared by the following method: uniformly mixing a silver nitrate solution and an ethanol solution of 3-aminopropyltriethoxysilane to obtain a mixed solution, atomizing the mixed solution into aerosol droplets, dispersing the aerosol droplets in carrier gas, heating, and cooling to obtain Ag @ SiO₂。

Preferably, Ag @ SiO₂Has a particle diameter of 50 to 300 nm.

Selecting the particle size of 50-300 nmAg @ SiO₂The microspheres can play a role in coating the nano-silver, so that the nano-silver is slowly released, the release rate is moderate, the strong sterilization effect is achieved, and the time limit of the sterilization effect of the coating is prolonged.

According to another aspect of the invention, a preparation method of the industrial coating for resisting marine biofouling is provided, which is characterized by comprising the following steps:

s1, adding copper pyrithione into an organic solvent for dissolving, then adding hollow mesoporous silica, performing ultrasonic dispersion, and uniformly stirring to obtain a first solution;

s2, modifying organic fluorine into epoxy resin, epoxy resin and Ag @ SiO₂Uniformly mixing the pigment, the filler, the cosolvent and the first solution to obtain a second solution;

s3, adding a dispersing agent, a defoaming agent, a flatting agent and an anti-settling agent into the second solution, and uniformly stirring to obtain a component A;

and S4, dissolving the curing agent in the organic solvent, and uniformly mixing to obtain the component B.

Preferably, the component A and the component B are matched according to a specific proportion, so that the solidification rate of the coating can be improved, and the adhesion of the coating is enhanced.

Preferably, in S1, copper pyrithione is uniformly dispersed in the hollow mesoporous silica.

According to still another aspect of the present invention, the industrial coating for marine biofouling resistance described above is applied to marine biofouling resistance of ships.

Compared with the prior art, the invention has the following advantages:

1. using Ag @ SiO₂And the copper pyrithione loaded by the hollow mesoporous silica has stronger bacteriostatic and bactericidal effects and can prevent microorganisms from being attached to the ship body.

2. The anti-biofouling coating provided by the invention can effectively and long-term release active silver ions and copper pyrithione bacteriostat, prolong the effective service life of the coating and greatly save manpower and material resources.

3. The coating provided by the invention is simple in production process, easy to operate and suitable for large-scale industrial production and use.

Detailed Description

Example 1

(1) Preparation of organic fluorine modified epoxy resin

Adding 10-30 parts by weight of organic fluorine powder and 0.1-2 parts by weight of dibutyltin dilaurate catalyst into 100 parts by weight of epoxy resin, and heating to 90-95 ℃ for reaction for 3-4 hours to obtain the organic fluorine modified epoxy resin.

(2) Preparation of Ag @ SiO₂

Weighing AgNO₃Dissolving in deionized water, weighing 3-aminopropyltriethoxysilane, dissolving in anhydrous ethanol, and mixing with AgNO₃Uniformly mixing the solution and the alcoholic solution of the 3-aminopropyltriethoxysilane, adding nitric acid, performing ultrasonic oscillation, and stirring by using a magnetic stirrer to obtain a mixed solution. Wherein the weight ratio of the silver nitrate to the 3-aminopropyltriethoxysilane to the nitric acid is 1: 6-8: 0.03-0.05.

(3) Preparing industrial paint for resisting marine biofouling

S1, adding 25 parts of copper pyrithione into an organic solvent for dissolving, then adding 1 part of hollow mesoporous silica, and performing ultrasonic dispersion and uniform stirring to obtain a first solution;

s2, preparing 20 parts of organic fluorine modified epoxy resin, 20 parts of epoxy resin and 20 parts of Ag @ SiO₂(screening of Ag @ SiO particle size of 50nm₂) 4 parts of pigment and the first solution are uniformly mixed to obtain a second solution;

s3, adding 1 part of dispersing agent, 1 part of defoaming agent, 0.5 part of flatting agent and 1.5 parts of anti-settling agent into the second solution, and uniformly stirring to obtain a component A, wherein the total weight part of the component A is 100 parts, and the balance is xylene;

s4, dissolving the curing agent in a mixed solvent of xylene and butanol, and uniformly mixing to obtain a component B, wherein the content of the component B is 15%.

The weight ratio of the component A to the component B is 4.5:1

Example 2

Organic fluorine modified epoxy resin and Ag @ SiO of example 2₂The preparation steps are the same as example 1, and the steps for preparing the marine biofouling resistant industrial coating are as follows:

s1, adding 15 parts of copper pyrithione into an organic solvent for dissolving, then adding 1 part of hollow mesoporous silica, and performing ultrasonic dispersion and uniform stirring to obtain a first solution;

s2, mixing 25 parts of organic fluorine modified epoxy resin, 15 parts of epoxy resin and 30 parts of Ag @ SiO₂(screening particle diameter of 300 n)Ag @ SiO of m₂) 6 parts of pigment and the first solution are uniformly mixed to obtain a second solution;

s3, adding 1.5 parts of dispersing agent, 1 part of defoaming agent, 0.8 part of flatting agent and 2 parts of anti-settling agent into the second solution, and uniformly stirring to obtain a component A, wherein the total weight part of the component A is 100 parts, and the balance is xylene;

s4, dissolving the curing agent in a mixed solvent of xylene and butanol, and uniformly mixing to obtain a component B, wherein the content of the component B is 10%.

The weight ratio of the component A to the component B is 3.5:1

Example 3

Organic fluorine modified epoxy resin and Ag @ SiO of example 3₂The preparation steps are the same as example 1, and the steps for preparing the marine biofouling resistant industrial coating are as follows:

s1, adding 20 parts of copper pyrithione into an organic solvent to be dissolved, adding 1 part of hollow mesoporous silica, and performing ultrasonic dispersion and uniform stirring to obtain a first solution;

s2, mixing 10 parts of organic fluorine modified epoxy resin, 25 parts of epoxy resin and 25 parts of Ag @ SiO₂(screening of Ag @ SiO particle size of 100nm₂) 6 parts of pigment and the first solution are uniformly mixed to obtain a second solution;

s4, dissolving the curing agent in a mixed solvent of xylene and butanol, and uniformly mixing to obtain a component B, wherein the content of the component B is 12%.

The weight ratio of the component A to the component B is 4:1

Comparative example 1

Comparative example 1Ag @ SiO₂The procedure of preparation of the same as that of example 1 was carried out without the step of preparing the organic fluorine-modified epoxy resin, and at the following S2, the organic fluorine-modified epoxy resin was replaced with an epoxy resin, and the procedure of preparing the marine biofouling resistant industrial coating was as follows:

s2, mixing 40 parts of epoxy resin and 20 parts of Ag @ SiO₂(screening of Ag @ SiO particle size of 50nm₂) 4 parts of pigment and the first solution are uniformly mixed to obtain a second solution;

The weight ratio of the component A to the component B is 4.5:1

Comparative example 2

Comparative example 1 an organofluorine-modified epoxy resin was prepared in the same procedure as in example 1, and Ag @ SiO was not prepared₂The step of preparing the marine biofouling resistant industrial coating by using the nano silver in the following S2 is as follows:

s2, uniformly mixing 20 parts of organic fluorine modified epoxy resin, 20 parts of nano silver, 4 parts of pigment and the first solution to obtain a second solution;

s3, adding 1 part of dispersing agent, 1 part of defoaming agent, 0.5 part of flatting agent and 1.5 parts of anti-settling agent into the second solution, and uniformly stirring to obtain a component A, wherein the total weight part of the component A is 100 parts, and the balance is dimethylbenzene;

The weight ratio of the component A to the component B is 4.5:1

Comparative example 3

Organic fluorine modified epoxy resin and Ag @ SiO of comparative example 3₂The preparation procedure was the same as in example 1The difference is that the steps for preparing the marine biofouling resistant industrial coating without adding hollow mesoporous silica in the following S1 are as follows:

s1, adding 25 parts of copper pyrithione into an organic solvent for dissolving, and performing ultrasonic dispersion and uniform stirring to obtain a first solution;

The weight ratio of the component A to the component B is 4.5:1

Comparative example 4

Comparative example 4 differs from example 1 in the Ag @ SiO screened₂The particle size was 10nm, and the rest was the same as in example 1.

Comparative example 5

Comparative example 5 differs from example 1 in the Ag @ SiO screened₂The particle size was 400nm, and the rest was the same as in example 1.

Comparative example 6

Comparative example 6 is different from example 1 in that copper pyrithione is not added in the step of preparing the marine biofouling resistant industrial coating material, and the rest is the same as example 1.

Comparative example 7

Comparative example 7 is different from example 1 in that Ag @ SiO is not added in the step of preparing the marine biofouling resistant industrial coating₂The rest is the same as in example 1.

Comparative example 8

Comparative example 6 the procedure for preparing the marine biofouling resistant industrial coating was as follows:

s2, uniformly mixing 40 parts of epoxy resin, 20 parts of nano silver, 4 parts of pigment and the first solution to obtain a second solution;

The weight ratio of the component A to the component B is 4.5:1

Test example

Antifouling paint shallow sea hanging plate experiment

The experimental method refers to the national standard GB/T5370-2007 Experimental method for shallow sea immersion of antifouling paint sample plate. And fixing the prepared template in a wood frame, making a remarkable mark before sea immersion, and recording the original state. The depth of the sample plate immersed in the sea is 1 m. The sample plate immersed in the sea is vertically and firmly fixed on the frame, the surface of the sample plate is parallel to the main tide of the sea water, and the distance between the frames is more than or equal to 200 nm. After the panels were submerged, the area of mussels, mollusks and algae attached to the panels was observed periodically and the observation room was removed 20mm along the edges of the panels to eliminate edge effects. The observation time is shortened as much as possible, the surface of the sample plate is photographed, the antifouling performance of the experimental sample plate is evaluated, and the sample plate is immersed into the sea immediately after observation so as to avoid the death of attached organisms and influence on the observation result.

Calculation and evaluation of Experimental results

Measuring the coverage area of the fouling organisms by using a percent-grid plate with the same observation area as the sample plate; when the test sample plate or the control sample plate in the same frame is evaluated, the difference of the fouling organism coverage area is 5 percent, the average value is taken, otherwise, the average value is taken by two sample plates with larger fouling organism coverage areas, and the test result is calculated, wherein the test result is shown in table 1.

TABLE 1 antifouling Properties test of the coatings of examples 1 to 3 and comparative examples 1 to 5

The experimental results show that the coatings prepared in the embodiments 1 to 3 of the invention have excellent marine organism fouling resistance, and the fouling organism coverage area after 3 months of soaking is far lower than that of the comparative examples 1 to 6. Therefore, the coating provided by the invention can effectively and long-term release active silver ions and copper pyrithione bacteriostat, prolong the effective service life of the coating and keep the marine organism fouling resistance effect for a long term.

Finally, it should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the modifications and equivalents of the specific embodiments of the present invention can be made by those skilled in the art after reading the present specification, but these modifications and variations do not depart from the scope of the claims of the present application.

Claims

1. The marine biofouling-resistant industrial coating is characterized by consisting of a component A and a component B; the component A comprises 10 to 25 weight percent of organic fluorine modified epoxy resin, 15 to 25 weight percent of epoxy resin and 20 to 30 weight percent of Ag @ SiO₂15 to 25 percent of copper pyrithione and 1 to 2.5 percent of hollow mesoporous silica;

the organic fluorine modified epoxy resin is prepared by the following steps: adding organic fluorine powder and a catalyst into epoxy resin, and heating for reaction for 3-4 hours to obtain the organic fluorine modified epoxy resin;

the Ag @ SiO₂Prepared by the following method: uniformly mixing a silver nitrate solution and an ethanol solution of 3-aminopropyltriethoxysilane to obtain a mixed solution, atomizing the mixed solution into aerosol droplets, dispersing the aerosol droplets in carrier gas, heating, and cooling to obtain the Ag @ SiO₂；

The Ag @ SiO₂The particle size of (A) is 50-300 nm;

the component B comprises 10-15% of curing agent, and the balance of organic solvent.

2. The marine biofouling resistant industrial coating of claim 1, wherein the weight ratio of the a component to the B component is 3.5 to 4.5: 1.

3. The marine biofouling resistant industrial coating of claim 2, wherein the a component further comprises 3% to 8% of a pigment, 1% to 2% of a dispersant, 0.5% to 2% of a defoamer, 0.5% to 1% of a leveling agent, and 1.5% to 2.5% of an anti-settling agent.

4. The marine biofouling resistant industrial coating of claim 3, wherein the A component comprises 20% of the organofluorine modified epoxy resin, 20% of the Ag @ SiO₂25% of copper pyrithione, 1% of hollow mesoporous silica, 4% of pigment, 1% of dispersing agent, 1% of defoaming agent, 0.5% of flatting agent and 1.5% of anti-settling agent;

the component B contains 15 percent of the curing agent.

5. The industrial marine biofouling-resistant coating of claim 1 wherein the epoxy resin is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and novolac epoxy resin. .

6. A preparation method of the marine biofouling resistant industrial coating according to any one of claims 1 to 5, comprising the following steps:

s2, modifying organic fluorine into epoxy resin, epoxy resin and Ag @ SiO₂Uniformly mixing the pigment and the first solution to obtain a second solution;

7. The application of the marine biofouling resistant industrial coating according to any one of claims 1 to 5 in marine biofouling resistance of ships.