Radiation-resistant antifouling paint and preparation method thereof

Abstract

The invention discloses a radiation-resistant antifouling paint and a preparation method thereof. The radiation-resistant antifouling paint comprises the following components in percentage by mass: 20-30% of radiation-resistant antifouling resin; 4-10% of a dissolution auxiliary agent; 10-20% of a radiation-resistant filler; 30-50% of an antifouling agent; 0.5%-2% of a surfactant; 0.5-2% of an anti-settling auxiliary agent; and 5-15% of a solvent. According to the radiation-resistant antifouling coating disclosed by the invention, through a benzene ring structure in a resin structure and a shielding effect of mica and flake graphite powder in the coating, the risk of paint film pulverization, cracking and failure caused by radiation can be effectively avoided, and under the stable hydrolysis effect of the main chain degradation type polysilane methacrylate self-polishing resin in seawater, the radiation-resistant antifouling coating has the advantages of good anti-fouling effect and good anti-fouling effect. The antifouling agent can be released continuously and stably, long-term antifouling performance is achieved, and normal operation of underwater equipment and ships is guaranteed.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine antifouling materials, in particular to a radiation-resistant antifouling coating and a preparation method thereof. BACKGROUND

[0002] Marine biofouling, also known as marine sessile organisms, is a general term for animals, plants and microorganisms that attach to and inhabit ships and various marine engineering equipment in the marine environment, causing economic losses and biological hazards. Antifouling paint is a coating used to prevent marine organisms from attaching, eroding and fouling, and to maintain the cleanliness of submerged structures such as ships, piers and sonars. It is applied on top of the rust-proof primer and uses the antifouling agent in the coating to slowly penetrate the surface of the coating film to form an antifouling surface layer, and uses the low surface energy of the coating to kill or disperse marine organisms (such as barnacles and oysters) attached to the coating film. Antifouling paint can be divided into contact type, dissolution type, diffusion type and self-polishing type, and is mainly used in antifouling engineering of ships, marine structures and pipelines in seawater and freshwater. So far, applying antifouling paint is still the most economical and effective measure to prevent marine organisms from attaching.

[0003] With the emergence of various emerging marine equipment, such as offshore floating nuclear power plants, the antifouling paint used may be exposed to gamma radiation. Generally, coatings will produce adverse reactions such as blistering, peeling, discoloration, chalking and cracking under radiation, which will damage the protected structure and affect its service life. The existing antifouling paint does not have radiation resistance, and the antifouling function may quickly fail under radiation conditions, resulting in the attachment of a large number of fouling organisms on the surface of the equipment and facilities, affecting normal service. Traditional nuclear radiation-resistant coatings are commonly used in strong radiation environments such as nuclear power plants, reactors and nuclear fuel reprocessing plants as protective coatings to prevent substrate materials from being damaged by radiation. The current research focus of radiation-resistant coatings is on radiation-resistant anticorrosion coatings, such as the high-solid-content bottom-surface-integrated coating resistant to radiation and corrosion and its preparation method disclosed in Chinese Patent Publication No. CN103351788A, the radiation-resistant polyamide decentralized epoxy paint and its preparation method disclosed in Chinese Patent Publication No. CN114773964A, and the two-component waterborne epoxy radiation-resistant coating for nuclear power plants disclosed in Chinese Patent Publication No. CN101781509A. The implementation of the above technologies is based on epoxy polymer resins, which have good effects on radiation resistance and corrosion resistance, but epoxy resins do not have self-polishing function and cannot achieve long-term stable release of antifouling agents, making it difficult to solve the problem of underwater marine biofouling. At present, there is no related report on radiation-resistant antifouling coatings. Therefore, it is urgent to modify the antifouling coating with radiation resistance to make it have both antifouling and radiation resistance, and to achieve efficient protection of marine engineering equipment. SUMMARY

[0004] The present application provides a kind of radiation resistant antifouling paint and preparation method to solve the above technical problems.The radiation resistant antifouling paint of the present application can not only meet the requirements of radiation resistance, but also solve the problem of fouling in marine environment.

[0005] In the first aspect, the present application provides a kind of radiation resistant antifouling paint, which is realized by the following technical scheme.

[0006] A kind of radiation resistant antifouling paint, including the following mass percentage of components:

[0007]

[0008] Further, the radiation resistant antifouling resin is selected from a degradation type polymethylsilane ester self-polishing resin (Guangdong Haiwei, radiation resistant silane ester self-polishing resin). The resin has a radiation resistant benzene ring structure, a molecular weight of not less than 10000 g / mol, and a viscosity of 400-1000 mPa·s.

[0009] Further, the dissolution aid is selected from one or a mixture of both of a primary rosin and a hydrogenated rosin. Specifically, the primary rosin is Yoshida Chemical AT01 primary rosin, and the hydrogenated rosin is Yoshida SZ8104 hydrogenated rosin. Preferably, the dissolution aid is selected from the hydrogenated rosin.

[0010] Further, the radiation resistant filler is selected from a mixture of at least three materials of iron oxide red, carbon black, flaky graphite, mica powder, precipitated barium sulfate, and heavy calcium carbonate. Preferably, the radiation resistant filler is composed of iron oxide red, mica powder, and flaky graphite powder, and the mass ratio of the iron oxide red, mica powder, and flaky graphite powder is (2-4):(4-8):(5-8).

[0011] Further, the antifouling agent is selected from a mixture of at least three materials of cuprous oxide, bromopyrrole nitrile, copper pyrithione, zineb, diuron, and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone (DCOIT). Preferably, the antifouling agent is composed of cuprous oxide, copper pyrithione, zineb, and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone, and the mass ratio of the cuprous oxide, copper pyrithione, zineb, and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone is (30-40):(3-8):(3-5):(1-2).

[0012] Further, the surface active agent includes a dispersant and a defoaming agent, and the mass ratio of the dispersant and the defoaming agent is (0.5-2):1. The dispersant is selected from a high molecular weight block copolymer solution containing a pigment affinity group (BYK-163), and the defoaming agent is selected from a bubble-breaking polymer and a polysiloxane solution (BYK-066N).

[0013] Further, the anti-settling aid is one or a mixture of two of polyamide wax and organic bentonite. Preferably, the anti-settling aid is composed of polyamide wax and organic bentonite, and the mass ratio of polyamide wax to organic bentonite is (0.5-2):1. Specifically, the polyamide wax is Itoh polyamide wax T-550F, and the organic bentonite is Chang'an Renheng easily dispersible organic bentonite CLAYMINTON 70.

[0014] Further, the solvent is one or a mixture of two or more of xylene, trimethylbenzene and n-butanol.

[0015] In a second aspect, the present application provides a preparation method of the radiation-resistant antifouling coating.

[0016] The preparation method of the radiation-resistant antifouling coating comprises the following steps:

[0017] S1. A specified amount of a dissolution aid is added to a part of the solvent to prepare a dissolution aid solution by high-speed stirring; and flaky graphite in the radiation-resistant filler is added to the dissolution aid solution to prepare a dissolution aid-radiation-resistant filler mixture by high-speed stirring;

[0018] S2. The radiation-resistant antifouling resin, the dispersant, the defoaming agent and the anti-settling aid are added to the dissolution aid-radiation-resistant filler mixture, and the mixture is stirred and dispersed at a rotation speed of 600-800 r / min for 25-30 min to obtain a mixed material;

[0019] S3. Another part of the solvent is added to the mixed material obtained in step S2, and the remaining radiation-resistant filler and the antifouling agent are added, and the fineness is controlled to be ≤80 μm by high-speed dispersion, and then the remaining solvent is added, and the mixture is stirred uniformly to obtain the radiation-resistant antifouling coating.

[0020] Further, in step S3, the high-speed dispersion condition is that the mixture is stirred and dispersed at a rotation speed of 1000-1200 r / min for 30-40 min.

[0021] The present application has the following beneficial effects.

[0022] The radiation-resistant antifouling resin used in the present application is a silane ester methacrylic resin series (hereinafter referred to as the radiation-resistant antifouling resin). Compared with the traditional antifouling resin, the radiation-resistant antifouling resin can effectively coordinate the hydrolysis of silane ester and the solubility of polymer in the self-polishing resin through chain breaking by degradation while maintaining the side chain silane ester hydrolysis characteristics. The unique methyl silane ester structure can slowly hydrolyze in seawater to achieve a long-term stable low polishing rate and realize long-term marine biofouling protection. The radiation-resistant benzene ring in the resin structure and the radiation-resistant powder mica powder and flaky graphite powder materials in the coating can improve the radiation resistance. However, the flaky graphite powder has poor wettability, which affects the dispersibility and the overall storage stability of the coating. During the preparation of the test sample in the laboratory, it was accidentally found that a stable hydrogenated rosin-flaky graphite mixed liquid can be prepared by melting the hydrogenated rosin with xylene and then adding flaky graphite powder for high-speed dispersion, and then the radiation-resistant antifouling coating can be prepared. DETAILED DESCRIPTION

[0023] The present patent application is further illustrated below in conjunction with examples.

[0024] The specific formulations of the radiation-resistant antifouling coatings of Examples 1-3 are shown in Table 1.

[0025] Table 1 Formulation Table of Examples

[0026]

[0027] Example 1

[0028] A method for preparing a radiation-resistant antifouling coating, the steps are as follows:

[0029] (1) Preparation of rosin-flaky graphite mixed liquid:

[0030] 50g of xylene was used as a dispersion medium, 80g of hydrogenated rosin was added to the solvent, and a hydrogenated rosin solution without hard lumps was prepared by high-speed stirring;

[0031] 60g of flaky graphite powder was added to the rosin solution, and a rosin-flaky graphite mixed liquid was prepared by high-speed stirring.

[0032] (2) Preparation of radiation-resistant antifouling coating dispersion liquid:

[0033] 200g of radiation-resistant antifouling resin, 5g of dispersant, 3g of defoaming agent, 5g of T-550F, and 5g of CLAYMINTON 70 were added to the prepared rosin-flaky graphite liquid dispersion kettle, and the mixture was stirred and dispersed at a speed of 600r / min for 30min to ensure stable dispersion of the anti-settling aids;

[0034] (3) Preparation of radiation-resistant antifouling coating:

[0035] To the mixture obtained in step (2), 50 g of xylene, the remaining 70 g of radiation resistant filler (precipitated barium sulfate 50 g, red iron oxide 20 g), 440 g of antifouling agent (cuprous oxide 350 g, copper pyrithione 50 g, Zineb 30 g, DCOIT 10 g) are added, and high-speed stirring dispersion is carried out at a speed of 1200 r / min for 30 min. The fineness of the material is controlled to be ≤80 μm by high-speed dispersion, and then 32 g of xylene is added and stirred uniformly. After filtration and packaging, a radiation resistant antifouling coating is obtained.

[0036] Example 2

[0037] A method for preparing a radiation resistant antifouling coating, the steps are as follows:

[0038] (1) Preparation of a rosin-plate-shaped graphite mixed liquid:

[0039] 50 g of xylene is used as a dispersion medium, and 60 g of hydrogenated rosin is added to the solvent to prepare a hard block-free hydrogenated rosin solution by high-speed stirring.

[0040] 60 g of plate-shaped graphite powder is added to the rosin solution to prepare a rosin-plate-shaped graphite mixed liquid by high-speed stirring.

[0041] (2) Preparation of a radiation resistant antifouling coating dispersion liquid:

[0042] To the prepared rosin-plate-shaped graphite liquid dispersion kettle, 240 g of radiation resistant antifouling resin, 5 g of dispersant, 3 g of defoaming agent, 5 g of T-550F and 5 g of CLAYMINTON 70 are added, and stirring dispersion is carried out at a speed of 600 r / min for 25 min to ensure stable dispersion of the anti-settling aids, and a mixture is obtained.

[0043] (3) Preparation of a radiation resistant antifouling coating:

[0044] To the mixture obtained in step (2), 50 g of xylene, the remaining 70 g of radiation resistant filler (precipitated barium sulfate 50 g, red iron oxide 20 g), 440 g of antifouling agent (cuprous oxide 350 g, copper pyrithione 50 g, Zineb 30 g, DCOIT 10 g) are added, and high-speed stirring dispersion is carried out at a speed of 1200 r / min for 30 min. The fineness of the material is controlled to be ≤80 μm by high-speed dispersion, and then 32 g of xylene is added and stirred uniformly. After filtration and packaging, a radiation resistant antifouling coating is obtained.

[0045] Example 3

[0046] A method for preparing a radiation resistant antifouling coating, the steps are as follows:

[0047] (1) Preparation of a rosin-plate-shaped graphite mixed liquid:

[0048] 60g of xylene as a dispersion medium, 40g of hydrogenated rosin was added into the solvent, and a non-hardened hydrogenated rosin solution was prepared by high-speed stirring;

[0049] 60g of flaky graphite powder was added into the rosin solution, and a rosin-flaky graphite mixture was prepared by high-speed stirring.

[0050] (2) Preparation of radiation-resistant antifouling coating dispersion:

[0051] 280g of radiation-resistant antifouling resin, 5g of dispersant, 3g of defoaming agent, 5g of T-550F and 5g of CLAYMINTON 70 were added into the prepared rosin-flaky graphite liquid dispersion kettle, and the mixture was dispersed at a stirring speed of 600r / min for 25min to ensure stable dispersion of the anti-settling aids, and the mixture was obtained;

[0052] (3) Preparation of radiation-resistant antifouling coating:

[0053] 10g of xylene, the remaining 70g of radiation-resistant fillers (50g of precipitated barium sulfate and 20g of red iron oxide), 440g of antifouling agents (350g of cuprous oxide, 50g of copper pyrithione, 30g of zineb and 10g of DCOIT) were added into the mixture obtained in step (2), and the mixture was dispersed at a stirring speed of 1200r / min for 40min to control the fineness of the mixture to ≤80μm. Then 22g of xylene was added and stirred uniformly, and the radiation-resistant antifouling coating was obtained by filtration and packaging.

[0054] Detection of coating performance

[0055] The radiation-resistant antifouling coating of the present application belongs to a topcoat product, which needs to be used in combination with an epoxy primer (CNO Changzhou Environmental Protection Coating Co., Ltd., high solid epoxy coating) and a modified epoxy intermediate coating (CNO Changzhou Environmental Protection Coating Co., Ltd., epoxy intermediate coating).

[0056] Physical performance test: the size of the tinplate board is 140*70*0.3mm, and the film thickness of the radiation-resistant antifouling coating is 25±2μm.

[0057] Composite coating performance: the size of the hot-rolled steel plate is 140*70*3mm, and the surface is treated by sandblasting at Sa2.5 level. The epoxy primer, modified epoxy intermediate coating and radiation-resistant antifouling coating are sprayed in a dry and ventilated environment. The film thickness of the primer is 200-250μm, the film thickness of the modified epoxy intermediate coating is controlled at 50-70μm, the film thickness of the radiation-resistant antifouling coating is 200-250μm, and the total film thickness is controlled at 500-550μm.

[0058] Maintenance conditions: 5-40℃, relative humidity 50-80%, and maintenance for 7 days.

[0059] The test results are shown in Table 2.

[0060] Table 2 Test Results Table

[0061]

[0062]

[0063] From the test results in Table 2, it can be seen that the radiation resistant antifouling coating of the present application has excellent radiation resistance, high solid content in the formula design, low VOC content, environmental protection and green. After one sea biological season of shallow sea immersion, the effect of Example 2 is the best, the sample board has no marine growth, and the antifouling performance is excellent.

[0064] The embodiments of the specific embodiment are the preferred embodiments of the present application, but do not limit the protection scope of the present application, so: any equivalent changes made according to the structure, shape, principle of the present application should be covered within the protection scope of the present application.

Claims

1. A radiation resistant antifouling coating, characterized by: The components include the following mass percentages:

2. The radiation resistant antifouling paint according to claim 1, characterized in that: The radiation-resistant antifouling resin is a degradable polymethylsilane ester self-polishing resin with a molecular weight of not less than 10,000 g / mol and a viscosity of 400-1,000 mPa·s.

3. The radiation resistant antifouling paint according to claim 1, characterized in that: The dissolution aid is selected from one or a mixture of the other of primary rosin and hydrogenated rosin.

4. The radiation resistant antifouling paint according to claim 1, characterized in that: The radiation-resistant filler is a mixture of at least three materials selected from iron oxide red, carbon black, flaky graphite, mica powder, precipitated barium sulfate, and heavy calcium carbonate.

5. The radiation resistant antifouling paint according to claim 1, characterized in that: The antifouling agent is a mixture of at least three materials selected from cuprous oxide, bromopyrrole nitrile, copper pyrithione, zineb, diuron, and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone.

6. The radiation resistant antifouling paint according to claim 1, characterized in that: The surfactant includes a dispersant and a defoaming agent, and the mass ratio of the dispersant to the defoaming agent is (0.5-2):1; the dispersant is a high-molecular-weight block copolymer solution containing a pigment affinity group, and the defoaming agent is a bubble-breaking polymer and a polysiloxane solution.

7. The radiation resistant antifouling paint according to claim 1, characterized in that: The anti-settling aid is a mixture of one or both of polyamide wax and organic bentonite.

8. The radiation resistant antifouling paint according to claim 1, characterized in that: The solvent is a mixture of one or more of xylene, trimethylbenzene, and n-butanol.

9. A process for the preparation of the radiation resistant antifouling coating according to any one of claims 1 to 8, characterized in that: The method includes the following steps: S1. A specified amount of dissolution aid is added to a portion of the solvent to prepare a dissolution aid solution by high-speed stirring; flaky graphite in the radiation-resistant filler is added to the dissolution aid solution to prepare a dissolution aid-radiation-resistant filler mixture by high-speed stirring; S2. The radiation-resistant antifouling resin, the dispersant, the defoaming agent, and the anti-settling aid are added to the dissolution aid-radiation-resistant filler mixture, which is stirred and dispersed at a speed of 600-800 r / min for 25-30 min to obtain a mixture; S3. Another portion of the solvent is added to the mixture obtained in step S2, and the remaining radiation-resistant filler and the antifouling agent are added, the fineness is controlled to be ≤80 μm by high-speed dispersion, and the remaining solvent is added, which is stirred and filtered to obtain the radiation-resistant antifouling coating.

10. The method for preparing a radiation-resistant and antifouling coating according to claim 9, characterized in that: In step S3, the high-speed dispersion conditions are a stirring speed of 1,000-1,200 r / min and a stirring and dispersion time of 30-40 min.

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