CN109266172B - Marine antifouling paint and preparation method and application thereof - Google Patents
Marine antifouling paint and preparation method and application thereof Download PDFInfo
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- CN109266172B CN109266172B CN201811062467.3A CN201811062467A CN109266172B CN 109266172 B CN109266172 B CN 109266172B CN 201811062467 A CN201811062467 A CN 201811062467A CN 109266172 B CN109266172 B CN 109266172B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention provides a marine antifouling paint, which comprises a component A and a component B; the component A comprises the following components in parts by weight: 15-30 parts of epoxy resin, 1-5 parts of pigment, 5-8 parts of silane coupling agent, 2-5 parts of auxiliary agent, 3-6 parts of filler and 15-25 parts of solvent; the component B comprises the following components in parts by weight: 20-40 parts of epoxy resin curing agent, 5-10 parts of antifouling agent and 10-20 parts of solvent; the mass ratio of the component A to the component B is (2.5-4) 1, and the antifouling agent is a combination of a compound I and a compound II; the marine antifouling paint provided by the invention has strong marine organism erosion resistance and higher storage stability, is stored for 12 months, is uniform after being stirred, has no phenomena of coarse particles, hard or colloid precipitates, crusting, hard pigment sinking and the like, and has excellent performance.
Description
Technical Field
The invention belongs to the field of coatings, and relates to a marine antifouling coating, and a preparation method and application thereof.
Background
The shells below the waterline of ships, wharfs and the like are contacted with seawater for a long time and are corroded by the seawater; the attachment of marine organisms causes the ship speed to be reduced, the corrosion speed of the ship hull to be accelerated, the underwater platform facilities to be damaged, and the cooling water pipeline of the power plant to be blocked. The above problems can be prevented by applying various marine antifouling paints thereto.
The marine antifouling paint is a special paint and mainly has the function of preventing fouling of marine organisms through gradual seepage of antifouling agents (poison materials) in a paint film. However, the prior antifouling paint inhibits the adhesion of marine organisms and causes secondary pollution to the marine environment.
CN102807796A discloses a novel marine environment-friendly antifouling paint, which aims to solve the problem that the current marine antifouling paint has great harm to marine pollution, and comprises the following components in parts by weight: 10-20 parts of organic silicon modified acrylic resin, 10-20 parts of water-based acrylic modified epoxy resin, 5-9 parts of hydroxyl-terminated polydimethylsiloxane, 0.5-3 parts of silane coupling agent, 17-24 parts of organic solvent, 22-30 parts of environment-friendly antifouling agent, 6-10 parts of zinc oxide, 2-5 parts of talcum powder, 1-3 parts of bentonite, 3-5 parts of ferric oxide, 2-5 parts of nano silicon dioxide and 1-3 parts of polytetrafluoroethylene. The marine environment-friendly antifouling paint does not contain harmful substances such as organic tin, cuprous oxide and the like which seriously harm the marine ecological environment, avoids pollution damage to the environment, achieves high-efficiency antifouling performance by reducing the surface energy of the paint and matching with an environment-friendly organic antifouling agent, but neglects the problems of serious corrosion, fouling and the like of marine organisms on the paint while ensuring the marine environment protection, and has certain defects.
The CN106065232A nontoxic environment-friendly antifouling paint comprises fluororesin, modified fluorine-containing resin, rosin, pigment, antifouling agent, auxiliary agent and mixed solvent, and the specific formula by weight ratio is as follows: 25-30 parts of fluororesin, 15-20 parts of modified fluorine-containing resin, 10-20 parts of rosin, 20-26 parts of antifouling agent, 8-12 parts of pigment, 10-20 parts of mixed solvent, 2-4 parts of organic bentonite and 5-20 parts of auxiliary agent. The nontoxic environment-friendly antifouling paint provided by the method has excellent physical and mechanical properties, is convenient to paint and construct, can achieve an effective antifouling effect, and simultaneously avoids marine pollution and harm to human beings due to accumulation of toxic substances caused by using the toxic antifouling paint, but the paint ignores the corrosion of marine organisms on a paint coating, and reduces the service life of the paint.
CN104177968A discloses an ocean antifouling paint which is prepared from the following raw materials in parts by weight: 10 to 20 portions of antifouling film forming material, 10 to 20 portions of filler, 10 to 20 portions of pigment, 10 to 20 portions of silane coupling agent, 2 to 8 portions of zinc oxide, 0.1 to 2 portions of lubricant, 0.1 to 2 portions of plasticizing accelerant, 10 to 20 portions of flatting agent and 10 to 20 portions of solvent. The antifouling film-forming substance provided by the method contains two bactericidal and antibacterial substances with different mechanisms, has a bactericidal and antibacterial synergistic effect, and can effectively reduce the drug resistance of bacterial microorganisms.
Therefore, the development of the environment-friendly marine antifouling paint which is efficient and durable in marine organism corrosion prevention has important significance for the protection of marine environment and the surface protection of marine machinery, ships and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a marine antifouling paint and a preparation method and application thereof, and aims to solve the problems of poor marine organism corrosion resistance and short storage time of the conventional paint.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a marine antifouling paint, which comprises a component A and a component B; the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
20-40 parts of epoxy resin curing agent
5-10 parts of antifouling agent
10-20 parts of a solvent;
the mass ratio of the component A to the component B is (2.5-4): 1, for example, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1 or 4:1, the antifouling agent is a combination of a compound I and a compound II, the structure of the compound I is
The structure of the compound II is
The marine antifouling paint provided by the invention is unexpectedly found to have good marine organism erosion resistance by combined use of the compound I and the compound II, and through 3 months of testing in a busy marine organism growing season, the sample plate coated with the marine antifouling paint has a minimum fouling area of about 2 percent, high storage stability, and even stirring after 12 months of storage, and has no phenomena of coarse particles, hard or colloid precipitates, crusting, hard pigment sinking and the like. Compared with the coating in the prior art, the marine antifouling coating provided by the invention only focuses on environmental protection but neglects the problem of marine organism corrosion resistance, has the environmental protection and marine organism corrosion resistance capabilities, and has excellent performance.
Preferably, the mass ratio of the compound I to the compound II is (3-5): 1, and may be, for example, 3:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1 or 5: 1.
According to the invention, the anti-erosion capability of the coating can be optimized by reasonably matching the mass ratio of the compound I to the compound II. If one of the compound I or the compound II is lacked, the antifouling and anticorrosion effects are greatly influenced, and the performance is greatly reduced.
In the present invention, the epoxy resin is 15 to 30 parts by weight, for example, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 30 parts, or the like.
In the present invention, the epoxy resin may be selected from epoxy resins commonly used in the art, such as bisphenol a type epoxy resin, bisphenol S type epoxy resin, amine based epoxy resin, and the like.
In the present invention, the pigment is 1 to 5 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.
Preferably, the pigment comprises any one of or a combination of at least two of black iron oxide, red iron oxide or yellow iron oxide.
In the present invention, the silane coupling agent is 5 to 8 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, or the like.
Preferably, the silane coupling agent comprises any one of or a combination of at least two of a silane coupling agent KH-550, a silane coupling agent KH-560 or a silane coupling agent KH-570.
In the present invention, the amount of the auxiliary is 2 to 5 parts by weight, and may be, for example, 2 parts, 3 parts, 4 parts, or 5 parts.
Preferably, the adjuvant comprises any one or a combination of at least two of talc, glyceryl monostearate, ethylene bis stearamide, BYK-P104 or BYK-306, wherein typical but non-limiting combinations include: talc and stearic acid monoglyceride; stearic acid monoglyceride, ethylene bis stearamide and BYK-P104; talc, stearic acid monoglyceride, ethylene bis stearamide, and the like.
In the present invention, BYK-P104 and BYK-306 are both existing products of Pico chemistry.
In the present invention, the filler is 3 to 6 parts by weight, and may be, for example, 3 parts, 4 parts, 5 parts, or 6 parts.
Preferably, the filler comprises any one of bentonite, zinc powder, titanium dioxide or mica powder, or a combination of at least two thereof, wherein typical but non-limiting combinations include: bentonite, zinc powder and titanium dioxide; titanium dioxide and mica powder; bentonite and zinc powder.
In the present invention, the amount of the solvent in the component a is 15 to 25 parts by weight, and may be, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, or the like.
The amount of the solvent in the component B is 10 to 20 parts by weight, and may be, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like.
Preferably, the solvent in both the a and B components is any one or a combination of at least two of benzene, xylene, n-butanol, petroleum ether, dimethyl phthalate, butyl acetate, ethyl acetate, acetone, cyclohexanone, diethyl ether or ethylene glycol ethyl ether, wherein typical but non-limiting combinations include: benzene and xylene; butyl acetate and ethyl acetate; xylene and n-butanol. Preferably a combination of n-butanol and xylene.
In the present invention, the epoxy resin curing agent is 20 to 40 parts by weight, and may be, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or the like.
In the present invention, the curing agent for epoxy resin may be selected from those commonly used in the art, and may be, for example, aliphatic amine, aromatic amine, imidazole, etc.
In the present invention, the antifouling agent is 5 to 10 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
In a second aspect, the present invention provides a method for preparing a marine antifouling paint as described in the first aspect, wherein the method comprises the following steps:
(1) firstly mixing the pigment and the filler for the first time, uniformly dispersing to obtain a solid mixture, and then adding the epoxy resin, the silane coupling agent, the auxiliary agent and the solvent into the solid mixture for the second time to mix to form a liquid mixture of the component A;
(2) and mixing an epoxy resin curing agent, an antifouling agent and a solvent to obtain a mixture of the component B, and then adding the component B into the component A under a high-speed shearing and stirring state to obtain the marine antifouling paint.
The preparation method provided by the invention is simple and feasible, and is suitable for industrial large-scale production.
Preferably, the dispersing time in the step (1) is 20-40 min, such as 20min, 25min, 30min, 35min or 40 min.
Preferably, the temperature of the second mixing in step (1) is 40 to 60 ℃, and may be, for example, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 53 ℃, 55 ℃, 58 ℃ or 60 ℃.
Preferably, the time for the second mixing in step (1) is 1 to 4 hours, and may be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, or 4 hours, for example.
Preferably, the rotation speed of the stirring in the step (2) is 1000-3000 r/min, such as 1000r/min, 1200r/min, 1500r/min, 1800r/min, 2000r/min, 2500r/min, 2800r/min or 3000 r/min.
In a third aspect, the invention provides a use of the marine antifouling paint as described in the first aspect in marine engineering and marine machinery.
The marine antifouling paint provided by the invention is widely applied. The coating can be used on the surface of a ship, a primer, a wharf and other waterline shells, which is in contact with seawater for a long time, and the formed coating has excellent protection effect on the shells.
Compared with the prior art, the invention has the following beneficial effects:
the marine antifouling paint provided by the invention has good marine organism erosion resistance, the sample plate coated with the marine antifouling paint has a minimum fouling area of about 2% through a test in 3 months of marine organism growth season, the storage stability is high, the sample plate is still uniform after being stirred after being stored for 12 months, and the phenomena of coarse particles, hard or colloidal precipitates, crusting, hard pigment bottom sinking and the like do not exist. Compared with the coating in the prior art, the marine antifouling coating provided by the invention only focuses on environmental protection but neglects the problem of marine organism corrosion resistance, has the environmental protection and marine organism corrosion resistance, has excellent performance, and can be widely applied to the fields of marine engineering, shore-based construction, marine machinery and the like.
Drawings
FIG. 1 is a topography of a coating formed by the marine antifouling paint provided by example 1 of the invention after a marine soaking test.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. The examples are given solely to assist in understanding the invention and are not to be construed as limiting the invention in any way.
Example 1
The embodiment provides a marine antifouling paint, which specifically comprises the following components:
the component B comprises the following components in parts by weight:
is prepared by the following steps:
(1) firstly mixing iron oxide red and bentonite for the first time, uniformly dispersing for 30min to obtain a solid mixture, then adding epoxy resin, a silane coupling agent KH-550, talcum powder, BYK-P104 and xylene into the solid mixture, and mixing for the second time for 2h at 50 ℃ to form a liquid mixture of the component A;
(2) and mixing the epoxy resin curing agent, the compound I, the compound II and xylene to obtain a mixture of the component B, and then adding the component B into the component A under a high-speed shearing and stirring state, wherein the stirring speed is 2000r/min, so as to obtain the marine antifouling paint.
The topography of the coating obtained from the marine antifouling paint obtained in example 1 after the marine immersion test is shown in fig. 1.
Example 2
The embodiment provides a marine antifouling paint, which specifically comprises the following components:
the component B comprises the following components in parts by weight:
is prepared by the following steps:
(1) firstly mixing iron oxide black, bentonite and mica powder for the first time, uniformly dispersing for 40min to obtain a solid mixture, then adding epoxy resin, a silane coupling agent KH-560, ethylene bis stearamide, BYK-306 and xylene into the solid mixture, and mixing for the second time at 60 ℃ for 4h to form a liquid mixture of the component A;
(2) and mixing an epoxy resin curing agent, a compound I, a compound II and xylene to obtain a mixture of the component B, and then adding the component B into the component A under a high-speed shearing stirring state, wherein the stirring speed is 3000r/min, so as to obtain the marine antifouling paint.
Example 3
The embodiment provides a marine antifouling paint, which specifically comprises the following components:
the component B comprises the following components in parts by weight:
is prepared by the following steps:
(1) firstly, mixing iron oxide yellow and bentonite for the first time, uniformly dispersing for 20min to obtain a solid mixture, then adding epoxy resin, a coupling agent KH-550, talcum powder and xylene into the solid mixture, and mixing for the second time for 1h at 40 ℃ to form a liquid mixture of the component A;
(2) and mixing the epoxy resin curing agent, the compound I, the compound II and xylene to obtain a mixture of the component B, and then adding the component B into the component A under a high-speed shearing and stirring state, wherein the stirring speed is 1000r/min, so as to obtain the marine antifouling paint.
Example 4
This example is different from example 1 only in that 7 parts by weight of compound I and 1 part by weight of compound II are used, and a marine antifouling paint is prepared in the same manner as in example 1.
Comparative example 1
The comparative example is different from example 1 only in that the comparative example does not include the compound I, and the compound II is 8 parts by weight, and the marine antifouling paint is prepared in the same manner as in example 1.
Comparative example 2
The comparative example is different from example 1 only in that the comparative example does not include the compound II, and the compound I is 8 parts by weight, and the marine antifouling paint is prepared in the same manner as in example 1.
Comparative example 3
The comparative example is different from example 1 only in that the comparative example does not include compound I and compound II, and the marine antifouling paint is prepared in the same manner as in example 1.
Comparative example 4
This comparative example differs from example 1 only in that it replaces both compound I and compound II with
Held by
8 parts by weight of a marine antifouling paint, and the balance of the paint was the same as in example 1.
Performance testing
The marine antifouling paints prepared in examples 1-4 and comparative examples 1-4 are subjected to performance tests (wherein the effect of the coating formed by the marine anticorrosive paint prepared in example 1 is shown in FIG. 1 after the tests), including marine soaking (according to GB/T5370-2007) and storage stability (according to GB/T6753.3-1986), and specific results are shown in the following table 1:
TABLE 1
As can be seen from the comparison of examples 1-2 with examples 3-4, when the mass ratio of compound I to compound II is outside the range defined in the present invention, the corrosion resistance and stability of the coating material are slightly lowered; it is clear from the comparison of comparative examples 1 to 4 that, in the absence of any one of compound I or compound II or replacement with another type of compound, the corrosion resistance of the coating is greatly reduced, the stability is also greatly reduced, and the performance is reduced.
As can be seen from fig. 1, the anticorrosive coating formed by the marine antifouling paint provided by the invention can still maintain good stability after being soaked in seawater, and has no corrosion trace, which indicates that the marine antifouling paint has excellent performance and can be widely applied in the fields of marine engineering and the like.
The applicant states that the present invention is illustrated by the above examples to the marine antifouling paint of the present invention and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (13)
1. A marine antifouling paint, which is characterized by comprising a component A and a component B; the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
20-40 parts of epoxy resin curing agent
5-10 parts of antifouling agent
10-20 parts of a solvent;
the mass ratio of the component A to the component B is (2.5-4): 1, the antifouling agent is a combination of a compound I and a compound II, and the structure of the compound I is
The structure of the compound II is
The mass ratio of the compound I to the compound II is (3-5) to 1.
2. A marine antifouling paint according to claim 1, wherein the pigment comprises any one of or a combination of at least two of black iron oxide, red iron oxide or yellow iron oxide.
3. A marine antifouling paint according to claim 1, wherein the silane coupling agent comprises any one of or a combination of at least two of a silane coupling agent KH-550, a silane coupling agent KH-560, or a silane coupling agent KH-570.
4. A marine antifouling paint according to claim 1, wherein the auxiliary agent comprises any one or a combination of at least two of talc, glyceryl monostearate, ethylene bis stearamide, BYK-P104 or BYK-306.
5. A marine antifouling paint according to claim 1, wherein the filler comprises any one or a combination of at least two of bentonite, zinc powder, titanium dioxide or mica powder.
6. The marine antifouling paint as claimed in claim 1, wherein the solvent of the A and B components is any one or a combination of at least two of benzene, xylene, n-butanol, petroleum ether, dimethyl phthalate, butyl acetate, ethyl acetate, acetone, cyclohexanone, diethyl ether and ethylene glycol ethyl ether.
7. A marine antifouling paint according to claim 6, wherein the solvents in the A and B components are a combination of n-butanol and xylene.
8. A process for the preparation of a marine antifouling paint according to any of claims 1 to 7, characterised in that the process comprises the steps of:
(1) firstly mixing the pigment and the filler for the first time, uniformly dispersing to obtain a solid mixture, and then adding the epoxy resin, the silane coupling agent, the auxiliary agent and the solvent into the solid mixture for the second time to mix to form a liquid mixture of the component A;
(2) and mixing an epoxy resin curing agent, an antifouling agent and a solvent to obtain a mixture of the component B, and then adding the component B into the component A under a high-speed shearing and stirring state to obtain the marine antifouling paint.
9. The method according to claim 8, wherein the dispersing time in the step (1) is 20 to 40 min.
10. The method according to claim 8, wherein the temperature of the second mixing in the step (1) is 40 to 60 ℃.
11. The preparation method according to claim 8, wherein the time of the second mixing in the step (1) is 1 to 4 hours.
12. The method according to claim 8, wherein the stirring speed in the step (2) is 1000 to 3000 r/min.
13. Use of a marine antifouling paint according to any of claims 1-7 in marine engineering, marine machinery.
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| CN201811062467.3A CN109266172B (en) | 2018-09-12 | 2018-09-12 | Marine antifouling paint and preparation method and application thereof |
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| CN201811062467.3A CN109266172B (en) | 2018-09-12 | 2018-09-12 | Marine antifouling paint and preparation method and application thereof |
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| CN109266172B true CN109266172B (en) | 2021-02-09 |
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| CN116041908B (en) * | 2023-02-02 | 2023-09-05 | 南雄市星隆化工有限公司 | Modified epoxy resin with antifouling effect and preparation method thereof |
| CN116656213A (en) * | 2023-06-27 | 2023-08-29 | 厦门双瑞船舶涂料有限公司 | Self-lubricating fouling self-stripping type anti-fouling paint and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156471A (en) * | 1994-07-06 | 1997-08-06 | 单一检索有限公司 | Anti-fouling compositions |
| CN103289531A (en) * | 2013-07-02 | 2013-09-11 | 长沙盛康高分子材料科技有限公司 | Underwater coating anti-pollution and anti-corrosion epoxy coating and preparation method thereof |
-
2018
- 2018-09-12 CN CN201811062467.3A patent/CN109266172B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156471A (en) * | 1994-07-06 | 1997-08-06 | 单一检索有限公司 | Anti-fouling compositions |
| CN103289531A (en) * | 2013-07-02 | 2013-09-11 | 长沙盛康高分子材料科技有限公司 | Underwater coating anti-pollution and anti-corrosion epoxy coating and preparation method thereof |
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