CN114181619B

CN114181619B - Water-based fluorine-silicon heavy-duty anticorrosive and antifouling paint and preparation method and application thereof

Info

Publication number: CN114181619B
Application number: CN202111439575.XA
Authority: CN
Inventors: 王敬伟; 郭占魁; 纪发达; 聂梓新
Original assignee: Shandong Longgang Silicon Technology Co ltd
Current assignee: Shandong Longgang Silicon Technology Co ltd
Priority date: 2021-11-30
Filing date: 2021-11-30
Publication date: 2022-09-16
Anticipated expiration: 2041-11-30
Also published as: CN114181619A

Abstract

The invention provides a water-based fluorosilicone heavy-duty anticorrosive antifouling paint, and a preparation method and application thereof. The invention provides a water-based fluorine-silicon heavy-duty anticorrosive antifouling paint which comprises the following raw materials in percentage by weight: 30-50% of fluorine-silicon emulsion, 10-15% of nano silicon dioxide, 1-3% of stabilizer, 0.5-1% of dispersant, 0.05-0.1% of defoamer, 0.15-0.35% of anti-settling agent, 0.5-1% of antimicrobial agent, 28.5-57.3% of zinc powder and 0.5-1% of graphene. The water-based fluorosilicone heavy-duty anti-corrosion and anti-fouling paint provided by the invention can realize a long-acting anti-corrosion effect on a ship steel structure and an anti-fouling effect on a ship body.

Description

Water-based fluorine-silicon heavy-duty anticorrosive and antifouling paint and preparation method and application thereof

Technical Field

The invention relates to preparation of a water-based fluorine-silicon heavy-duty anti-corrosion and anti-fouling paint, belonging to the field of anti-corrosion and anti-fouling and paint preparation.

Background

At present, most ships adopt metal shells. In the marine environment, metals are affected by seawater temperature, seawater salinity, marine atmospheric temperature, marine atmospheric humidity and marine organism adhesion, and are corroded to different degrees under the influence of the factors. The corrosion not only reduces the strength of the ship steel structure and shortens the service life of the ship, but also increases the resistance of the ship in the sailing process, reduces the sailing speed and increases the oil consumption due to the attachment of marine organisms. Compared with a clean ship body, the ship with marine organisms attached to the ship body has the oil consumption higher than 40 percent, and the CO is increased for every 1 ton of fuel oil ₂ The release amount of (A) is 2.97 ten thousand tons and SO ₂ The amount of released (A) was 0.01 ten thousand tons. This not only causes energy consumption, but also brings great harm to the environment. More seriously, once perforation or cracking occurs, sea damage accidents can also occur, and the personal safety of marine personnel and the biodiversity of marine organisms are affected. Survey statistics show that the total cost of corrosion in our country is about 4% of the GDP in the year, with marine corrosion accounting for about 1/3% of the total corrosion. This has led to the nationThe great attention of the experts of internal and external preservation.

Therefore, research and development of a safe, environment-friendly, anti-corrosive and anti-fouling material which has salt mist resistance, damp and heat resistance, corrosion resistance, marine organism adhesion resistance and the like and has long rust prevention time becomes a problem to be solved.

Disclosure of Invention

Aiming at the problems of corrosion of ships in marine environment and adhesion of marine organisms to ship bodies in the prior art, the invention provides a water-based fluorine-silicon heavy-duty anticorrosive antifouling paint.

The invention provides a water-based fluorine-silicon heavy-duty anticorrosive antifouling paint which comprises the following raw materials in percentage by weight: 30-50% of fluorine-silicon emulsion, 10-15% of nano silicon dioxide, 1-3% of stabilizer, 0.5-1% of dispersant, 0.05-0.1% of defoamer, 0.15-0.35% of anti-settling agent, 0.5-1% of antimicrobial agent, 28.5-57.3% of zinc powder and 0.5-1% of graphene.

Preferably, the feed comprises the following raw materials in percentage by weight: 30-40% of fluorine-silicon emulsion, 10-12% of nano silicon dioxide, 1-3% of stabilizer, 0.5-1% of dispersant, 0.05-0.1% of defoamer, 0.15-0.35% of anti-settling agent, 0.5-1% of antimicrobial agent, 45-55% of zinc powder and 0.5-0.8% of graphene.

Preferably, the preparation method of the fluorosilicone emulsion comprises the following steps:

1) heating the silicate solution to 50-80 ℃, preferably, heating the silicate, then preserving the heat for 1-3 hours,

2) adding a coupling agent for reaction, preferably, the reaction time is 2-3 hours;

3) adding fluorocarbon emulsion for reaction, preferably, the reaction time is 3-5 hours;

preferably, the silicate: coupling agent: the mass ratio of the fluorocarbon emulsion is 20-30: 1-1.5: 2-3;

preferably, the solid content of the fluorocarbon emulsion is 40-45%, and the balance is water.

Preferably, the silicate solution is one or the combination of more than two of potassium silicate solution, sodium silicate solution and lithium silicate solution;

preferably, the concentration of the silicate solution is 25wt% to 30 wt%.

Preferably, the coupling agent is one or the combination of more than two of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane, methyltriethoxysilane and aqueous titanate.

Preferably, the particle size of the nano silicon dioxide is 8-10 nm.

Preferably, the stabilizer is quaternary ammonium salt or quaternary ammonium base;

preferably, the stabilizer is

ST or STAB PV.

Preferably, the dispersant is quaternary ammonium salt or sodium polycarboxylate;

preferably, the dispersant is WY-001 or SPS.

Preferably, the defoaming agent is a silicone;

preferably, the defoamer is one of defoamer 240A, defoamer 740, or defoamer 1030.

Preferably, the anti-settling agent is cellulosic;

preferably, the anti-settling agent is HY-615 anti-settling agent or anti-settling agent XF-601.

Preferably, the antimicrobial agent is n-octyl isothiazolone or iodopropynyl n-butyl carbamate;

preferably, the antimicrobial agent is one of U-W194, U-W205, or U-W190.

The invention also provides a preparation method of the water-based fluorosilicone heavy-duty anti-corrosion and anti-fouling paint, which comprises the following steps:

1) adding the nano silicon dioxide and the stabilizing agent into the fluorine-silicon emulsion under the stirring state, and uniformly mixing;

2) respectively adding a dispersing agent, a defoaming agent, an anti-settling agent and an antimicrobial agent into the mixture obtained in the step 1), and uniformly mixing;

3) adding graphene into the mixture obtained in the step 2), and uniformly mixing;

4) adding zinc powder into the mixture obtained in the step 3), and uniformly mixing to obtain the final coating.

Preferably, in the step 1), stirring for 1-2 hours and uniformly mixing;

preferably, in the step 2), stirring for 0.5-1 hour and uniformly mixing;

preferably, in the step 3), 1400-1600rpm/min is used for stirring and mixing uniformly, and preferably, in the step 3), the stirring time is 1-2 hours;

preferably, in the step 4), the mixture is stirred for 0.5 to 1 hour and then uniformly mixed.

The invention also provides the application of the water-based fluorosilicone heavy-duty anti-corrosion and anti-fouling paint or the water-based fluorosilicone heavy-duty anti-corrosion and anti-fouling paint prepared by the preparation method in ship anti-corrosion and anti-fouling.

The raw materials of the water-based fluorine-silicon heavy-duty anticorrosive antifouling paint provided by the invention are all nontoxic and harmless substances, are green and environment-friendly, do not damage marine organisms and ecological systems, are free from heavy metal ion pollution, and can realize a long-acting anticorrosive effect on ship steel structures and an antifouling effect on ship hulls.

Detailed Description

The invention adopts the fluorine-silicon emulsion as the main film forming material, so that the coating forms the fluorine-containing microstructure nano coating on the surface of the steel, the coating has extremely low surface energy, the surface tension of the coating is greatly reduced, and the water contact angle is increased.

In a preferred embodiment, the preparation of the fluorosilicone emulsion of the present invention is prepared by a method comprising the following steps:

1) heating the silicate solution to 50-80 ℃,

2) adding a coupling agent for reaction;

3) adding fluorocarbon emulsion for reaction;

Wherein the coupling agent is preferably one or more than two of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane and methyltriethoxysilane. Among them, 3-glycidoxypropyltrimethoxysilane (type KH560), 3-aminopropyltriethoxysilane (type KH550), 3-aminopropyltrimethoxysilane (type KH540), 3- (methylpropyloxy) propyltrimethoxysilane (type Z-6030), 3-glycidoxypropyltriethoxysilane (type GLYMO), 1, 2-bis (triethoxysilyl) ethane (type SCA-K02X), and aqueous titanate (type TCA-T30) commercially available from Shanghai Needt New Material science and technology Co.

In one embodiment of the present invention, the stabilizer may be any stabilizer known in the art, such as quaternary ammonium salts or quaternary ammonium bases. Specifically, commercially available ones, for example, can be used in the present invention

ST (sold by Austhan chemical Co., Ltd., Beijing) or STAB PV (sold by Shikoku chemical Co., Ltd., Shanghai).

In one embodiment of the present invention, the dispersant is a quaternary ammonium salt or a polycarboxylate, and specifically, for example, commercially available WY-001 (sold by New materials, Inc. in Shanghai) or SPS (sold by New materials, Inc. in Shanghai) can be used in the present invention.

In one embodiment of the present invention, the defoaming agent is a silicone type, and specifically, for example, defoaming agent 240A, defoaming agent 740, or defoaming agent 1030 commercially available from new materials ltd, ten thousand, guangzhou, may be used in the present invention.

In one embodiment of the invention, the anti-settling agent is cellulose; specifically, for example, a commercially available HY-615 anti-settling agent (sold by Nelumbo leaves chemical Co., Ltd., Sundland, Fushan) or XF-601 (sold by Xiffi chemical Co., Ltd., Hangzhou) can be used in the present invention.

In one embodiment of the invention, the antimicrobial agent is n-octyl isothiazolone or iodopropynyl n-butyl carbamate; specifically, for example, U-W194, U-W205, or U-W190, which are commercially available from New materials, Inc., of Kwangsu, Guangzhou, may be used as the antimicrobial agent in the present invention.

According to the invention, the nano-silica is used as an auxiliary film forming substance, a large number of microscopic rough hydrophobic structures (hierarchical structures) such as microscopic nano mastoids, micro-nano channels, grooves, bulges and the like can be formed by the nano-silica and the pigment and filler, when water drops are contacted with the hydrophobic micro-nano hierarchical structures, part of the micro-nano channels and holes are sealed by the water drops to form a layer of air film, and the water drops shrink spontaneously under the action of surface tension, so that the water contact angle is increased.

The graphene has higher surface energy and stronger hydrophobic effect, and under the surface effect of the graphene, the contact angle of the coating and water is increased, so that the coating has excellent hydrophobic property, the adhesion of marine organisms on the surface of a ship body is reduced, and the biofouling problem is reduced.

The antimicrobial agent adopted by the invention has the characteristics of safety and environmental protection, meets the strictest European Union regulation requirements, and can effectively prevent the adhesion problem of marine microorganisms.

The invention adopts zinc powder and graphene as pigments and fillers. The zinc powder belongs to active metal, the iron belongs to inert metal, and the zinc powder and the iron are used for preparing the anticorrosive coating to play a role in electrochemical cathodic protection of steel, and simultaneously, a certain amount of graphene is added to increase the conductivity of the zinc and enhance the electrochemical protection effect; on the other hand, zinc powder and graphene can play a physical shielding role simultaneously, so that the penetration of corrosive media in the sea to the surface of steel through micropores of a paint film is shielded, and a double protection effect on steel is achieved.

In order to make those skilled in the art better understand the technical solution of the present invention, the following provides a detailed description of the present invention with reference to the embodiments.

The reagents and instrument sources used in the examples of the invention are shown in table 1 below.

EXAMPLE 1 preparation of Fluorosilicone emulsion

Taking 100g of 25% potassium silicate solution by mass, mechanically stirring in a three-neck flask, heating in water bath to 50 ℃ and keeping for 1 hour, then adding 1g of coupling agent 3-glycidyl propyl trimethoxy silane under stirring, keeping for 3 hours at the temperature, finally adding 5g of 42% fluorocarbon emulsion by mass with water as a solvent, continuing stirring for 5 hours at the temperature, and stopping the reaction to obtain the fluorosilicone emulsion.

Examples 2 to 6 and comparative examples 1 to 2

1kg of aqueous fluorosilicone heavy-duty anti-corrosion and anti-fouling paint is prepared according to the mass percentages of the components in the table 2, and the preparation method comprises the following steps:

1) adding the fluorosilicone emulsion prepared in the example 1 into a three-neck flask, and adding nano silicon dioxide with the particle size of 9nm and a stabilizer under the mechanical stirring state

ST, stirring for 1 hour;

2) adding a dispersing agent WY-001, a defoaming agent 740, an anti-settling agent XF-601 and an antimicrobial agent U-W194 into the mixture obtained in the step 1) respectively, and continuing stirring for 0.5 hour;

3) and (3) transferring the three-neck flask containing the mixture obtained in the step 2) into a high-speed dispersion machine with ultrasonic waves in an ultrasonic cleaning machine, arranging a mechanical stirring device on the three-neck flask, adding graphene, performing high-speed dispersion and ultrasonic dispersion for 2 hours, wherein the rotating speed of the mechanical stirring device is 1500rpm/min, the ultrasonic power is 400W, and the frequency is 33 kHz.

4) Adding zinc powder into the mixture obtained in the step 3), and stirring for 0.5 hour to obtain the final coating.

TABLE 2

The salt spray resistance test of the water-based fluorine-silicon heavy-duty anticorrosive and antifouling paint obtained in the above examples 2-6 and comparative examples 1 and 2 is detected according to GB1771-2007 determination of neutral salt spray resistance of colored paint and varnish, the flexibility test is detected according to GB/T1731-1993 paint film flexibility determination method, the impact resistance test is detected according to GB/T1732-1993 paint film impact resistance determination method, and the adhesion test is detected according to GB/T5210-2006 paint and varnish pull-open method adhesion test. The contact angle measurement adopts a JC2000C1 sessile drop contact angle measuring instrument of Shanghai morning digital technology equipment, Inc., and the specific steps are as follows, starting the machine and entering a measuring program; fixing the sample injector or the micro-injector on an objective table, and adjusting the focal length until the image is clear; and (3) dropping 0.6 mu L of sample on a stage, freezing the image, entering a main interface of a angulometry for measurement, and measuring twice to obtain an average value. The rolling angle measurement adopts JC2000F rolling angle measuring instrument of Beijing Zhongjieki science and technology, specifically comprises the following steps of placing a sample to be measured on an objective table and abutting against the edge of a baffle, slowly rotating a bolt above a needle tube to enable a drop of water to reach the surface of the object to be measured from the needle tube, slowly rotating the movable objective table to enable the objective table to slowly rise, stopping rotation when the drop of water on the sample to be measured just starts to roll, reading the angle on the instrument at the moment, and performing parallel measurement and taking an average value twice. The thickness of the coating was measured using a coating thickness gauge, the gauge was turned on and was directly put into the measurement mode, the base material Fe/NFe was displayed on the screen, and the data was measured and the values obtained are shown in Table 3.

The performance index is shown in Table 3.

TABLE 3

As shown in table 3, the water-based fluorosilicone heavy-duty anticorrosive and antifouling paint provided by the invention has excellent anticorrosive and antifouling performances when applied to ships. Particularly, the salt spray resistance of the aqueous fluorosilicone heavy-duty anticorrosive and antifouling paint provided in the embodiments 4 and 5 reaches 6000h and 5300h respectively, and the paint has excellent anticorrosive effect.

It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims

1. The water-based fluorine-silicon heavy-duty anticorrosive antifouling paint is characterized by comprising the following raw materials in percentage by weight: 30-50% of fluorine-silicon emulsion, 10-15% of nano silicon dioxide, 1-3% of stabilizer, 0.5-1% of dispersant, 0.05-0.1% of defoamer, 0.15-0.35% of anti-settling agent, 0.5-1% of antimicrobial agent, 28.5-57.3% of zinc powder and 0.5-1% of graphene;

the stabilizer is quaternary ammonium salt or quaternary ammonium alkali;

the dispersant is quaternary ammonium salt or sodium polycarboxylate;

the defoaming agent is organic silicon;

the anti-settling agent is cellulose;

the antimicrobial agent is n-octyl isothiazolone or iodopropynyl n-butyl carbamate;

the preparation method of the fluorosilicone emulsion comprises the following steps:

1) heating the silicate solution to 50-80 ℃,

2) adding a coupling agent for reaction, and adding a coupling agent for reaction,

3) adding the fluorocarbon emulsion to react with the mixture,

the silicate: coupling agent: the mass ratio of the fluorocarbon emulsion is 20-30: 1-1.5: 2 to 3.

2. The water-based fluorosilicone heavy-duty anticorrosive antifouling paint according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: 30-40% of fluorine-silicon emulsion, 10-12% of nano silicon dioxide, 1-3% of stabilizing agent, 0.5-1% of dispersing agent, 0.05-0.1% of defoaming agent, 0.15-0.35% of anti-settling agent, 0.5-1% of antimicrobial agent, 45-55% of zinc powder and 0.5-0.8% of graphene.

3. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 1, wherein the preparation method of the fluorosilicone emulsion comprises the following steps:

1) heating the silicate solution to 50-80 ℃, then preserving heat for 1-3 hours,

2) adding a coupling agent for reaction for 2-3 hours;

3) adding fluorocarbon emulsion to react for 3-5 hours;

the solid content of the fluorocarbon emulsion is 40-45%, and the balance is water.

4. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 2, wherein the preparation method of the fluorosilicone emulsion comprises the following steps:

2) adding a coupling agent for reaction for 2-3 hours;

3) adding fluorocarbon emulsion to react for 3-5 hours;

5. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 3, wherein the silicate solution is one or a combination of more than two of potassium silicate solution, sodium silicate solution and lithium silicate solution;

the concentration of the silicate solution is 25wt% -30 wt%.

6. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 4, wherein the silicate solution is one or a combination of more than two of potassium silicate solution, sodium silicate solution and lithium silicate solution;

the concentration of the silicate solution is 25wt% -30 wt%.

7. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 3, wherein the coupling agent is one or a combination of two or more of 3-glycidylpropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane, methyltriethoxysilane and water-based titanate.

8. The aqueous fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 4, wherein the coupling agent is one or a combination of two or more of 3-glycidylpropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane, methyltriethoxysilane and aqueous titanate.

9. The aqueous fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 5, wherein the coupling agent is one or a combination of two or more of 3-glycidylpropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane, methyltriethoxysilane and aqueous titanate.

10. The aqueous fluorosilicone heavy-duty anticorrosive and antifouling paint as claimed in claim 6, wherein the coupling agent is one or a combination of two or more of 3-glycidylpropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (methylpropyloxy) propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 1, 2-bis (triethoxysilyl) ethane, methyltriethoxysilane and aqueous titanate.

11. The water-based fluorosilicone heavy-duty anticorrosive antifouling paint as claimed in any one of claims 1 to 10, wherein the particle size of the nano-silica is 8-10 nm.

12. The water-based fluorosilicone heavy-duty anticorrosive antifouling paint as claimed in any one of claims 1 to 10, wherein the stabilizer is LOPON ST or STAB PV.

13. The aqueous fluorosilicone heavy duty anticorrosive and antifouling paint of any one of claims 1 to 10, wherein the dispersant is WY-001 or SPS.

14. The water-based fluorosilicone heavy-duty anticorrosive and antifouling paint of any one of claims 1 to 10, wherein the defoaming agent is one of a defoaming agent 740 or a defoaming agent 1030.

15. The preparation method of the water-based fluorosilicone heavy-duty anti-fouling paint of any one of claims 1 to 14, characterized by comprising the following steps:

16. The preparation method of claim 15, wherein in the step 1), the mixture is stirred for 1-2 hours and uniformly mixed;

in the step 2), stirring for 0.5-1 hour and uniformly mixing;

in the step 3), stirring and uniformly mixing at 1400-1600rpm/min for 1-2 hours;

and 4), stirring for 0.5-1 hour and uniformly mixing.

17. Use of the aqueous fluorosilicone heavy duty anti-corrosive and anti-fouling coating of any one of claims 1 to 14 for marine corrosion and fouling prevention.