Biodegradable antifouling paint as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of antifouling paint, and relates to biodegradable antifouling paint as well as a preparation method and application thereof. The biodegradable antifouling paint is formed by compounding biodegradable resin, an antimicrobial agent, a filler, an auxiliary agent and a solvent according to the weight ratio of (30-40): (28-35): (20-24): (0.8-1.2): (10-13). The coating can continuously release an antimicrobial agent through a main chain degradation and side chain hydrolysis structure of biodegradable resin, so that the coating has double effects of self-cleaning and self-polishing, and in addition, the coating has antibacterial and antimicrobial effects due to introduction of the antimicrobial agent; and the final degradation products are micromolecules with good biocompatibility, do not generate secondary pollution to the ocean, and are green and environment-friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of antifouling coatings, and relates to a biodegradable antifouling coating, a preparation method thereof, and an application thereof. Background Art

[0002] At present, the surfaces of marine equipment such as ship hulls, docks, and drilling platforms will inevitably be eroded by marine fouling organisms. The attachment of marine organisms (such as algae, barnacles, and shellfish) will increase the roughness of the structure surface, thereby affecting the hydrodynamic characteristics and the durability of materials, resulting in serious economic costs and ecological environment problems. Using antifouling coatings is an economical and effective way to reduce the harm of marine organism attachment fouling or corrosion.

[0003] In the process of developing the ocean, it is expected to achieve the antifouling purpose in an eco-friendly way. Existing self-polishing resins are mainly composed of vinyl polymers. The antifouling effect depends on water flow scouring, resulting in poor static antifouling effect and inability to degrade, causing the problem of marine microplastic pollution. Therefore, developing an environmentally friendly and easily degradable antifouling coating is of great significance. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above-mentioned disadvantages of the prior art and propose a biodegradable antifouling coating and a preparation method thereof.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] A biodegradable antifouling coating is formed by compounding a biodegradable resin, an antimicrobial agent, a filler, an auxiliary agent, and a solvent in a weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13).

[0007] Specifically, the preparation method of the biodegradable coating provided by the present invention can continuously release the antimicrobial agent through the main chain degradation and side chain hydrolysis structure of the biodegradable resin, so that the coating has the dual effects of self-cleaning and self-polishing. In addition, the introduction of the antimicrobial agent makes the coating have the effect of antibacterial and antimicrobial; the final degradation products are all small molecules with good biocompatibility, which will not cause secondary pollution to the ocean and are green and environmentally friendly.

[0008] Further, the biodegradable resin is a biodegradable polyurethane resin.

[0009] Specifically, the present invention uses a green and environmentally friendly biodegradable polyurethane resin. This resin is a single-component resin and has unique main chain degradability, and can continuously update its surface by the degradation of the polymer main chain in seawater.

[0010] Further, the antimicrobial agent comprises the following raw material components in parts by weight: 3-5 parts by weight of copper pyrithione, 20-27 parts by weight of cuprous oxide, and 3-5 parts by weight of isothiazolinone.

[0011] Specifically, the copper pyrithione can be 3 parts by weight, 4 parts by weight, or 5 parts by weight, and can be adjusted according to actual requirements; the cuprous oxide can be 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, or 27 parts by weight, and can be adjusted according to actual requirements; the isothiazolinone can be 3 parts by weight, 4 parts by weight, or 5 parts by weight, and can be adjusted according to actual requirements.

[0012] It should be noted that copper pyrithione is an efficient, low-toxic, and environmentally friendly antifouling agent and bacteriostatic agent, and isothiazolinone is an efficient mildew and algae-proof agent. Copper pyrithione and isothiazolinone are effective against bacteria and algae, have low solubility in water, and can slow down the release rate; cuprous oxide enters organisms through the digestive and respiratory organs, coagulates the proteins in the organisms, and thus achieves the purpose of killing organisms.

[0013] In addition, in order to enhance the anti-biofouling effect of the coating, the present invention selects to use three antimicrobial agents, namely copper pyrithione, cuprous oxide, and isothiazolinone, in combination. These three antimicrobial agents are all low-toxic and are easily degradable in seawater, etc., and can achieve an efficient antifouling effect; among them, the main antimicrobial agent (cuprous oxide) has a scavenging effect on animals such as barnacles and mussels, and the auxiliary antimicrobial agents (copper pyrithione and isothiazolinone) have a scavenging effect on algae plants. The combination of the two achieves comprehensive protection to ensure the antifouling effect of the antifouling coating.

[0014] Further, the filler comprises the following raw material components in parts by weight: 4-8 parts by weight of zinc oxide, 4-8 parts by weight of iron oxide red, 2-3 parts by weight of bentonite, and 5-10 parts by weight of talc powder.

[0015] Specifically, the zinc oxide can be 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, or 8 parts by weight, the iron oxide red is 4-8 parts by weight, and can be adjusted according to actual requirements; the bentonite can be 2 parts by weight or 3 parts by weight, and can be adjusted according to actual requirements; the talc powder can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight, and can be adjusted according to actual requirements.

[0016] It should be noted that zinc oxide is slightly toxic, and at the same time can increase the copper ion leaching rate and enhance the antifouling performance; iron oxide red can improve the physical properties of the paint film, but also inhibits the copper ion leaching rate and balances the copper ion utilization rate; bentonite is used to improve the water resistance and adhesion of the coating, and talc powder is used to improve the sedimentation property of the coating.

[0017] Further, the auxiliary agent comprises the following raw material components in parts by weight: 0.7 - 0.9 part by weight of chlorinated paraffin and 0.1 - 0.3 part by weight of dispersant.

[0018] Specifically, the chlorinated paraffin can be 0.7, 0.8, or 0.9 part by weight, and can be adjusted according to actual requirements; the dispersant can be 0.1 part by weight, 0.2 part by weight, or 0.3 part by weight, and can be adjusted according to actual requirements.

[0019] It should be noted that the chlorinated paraffin is used to enhance the flexibility of the coating; the dispersant is used to uniformly disperse particles or powders in the coating.

[0020] Further, the solvent is one or two of toluene, xylene, and butyl ester.

[0021] In addition, the present invention also discloses a preparation method of a biodegradable antifouling coating. After weighing each raw material component according to the weight ratio, the degradation agent and auxiliary agent are first dispersed to obtain a resin mixture, and then an antimicrobial agent and filler are added to the resin mixture for a second dispersion to obtain the biodegradable antifouling coating.

[0022] Specifically, the degradation agent is a biodegradable resin, and the auxiliary agent is an auxiliary agent and a solvent.

[0023] Specifically, it includes the following steps:

[0024] Step 1: Weigh the biodegradable resin, antimicrobial agent, filler, auxiliary agent, and solvent according to the weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13).

[0025] Step 2: First disperse the biodegradable resin, auxiliary agent, and solvent to obtain a resin mixture.

[0026] Step 3: Sequentially add the antimicrobial agent and filler to the resin mixture for a second dispersion to obtain the biodegradable antifouling coating.

[0027] Further, the rotation speed of the first dispersion in Step 1 is 1500 r / min - 2500 r / min, and the high-speed dispersion time is 10 min - 20 min; in Step 2, the rotation speed of the second dispersion is 300 r / min - 500 r / min, and the high-speed dispersion time is 30 min - 50 min.

[0028] The present invention also provides the application of the biodegradable antifouling coating in antifouling treatment on the surface of marine equipment.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The present invention uses a green and environmentally friendly biodegradable polyurethane resin. This resin is a one-component resin and has unique main-chain degradability, and can continuously update its surface by the degradation of the polymer main chain in seawater.

[0031] 2. In order to enhance the anti-biofouling effect of the coating, the present invention selects and uses three kinds of antimicrobial agents, namely copper pyrithione, cuprous oxide, and isothiazolinone. These three antimicrobial agents all have low toxicity and are extremely easy to degrade in seawater and other characteristics, and can achieve a high-efficiency antifouling effect. Among them, the main antimicrobial agent (cuprous oxide) has a scavenging effect on animals such as barnacles and mussels, and the auxiliary antimicrobial agents (copper pyrithione and isothiazolinone) have a scavenging effect on algae plants. The combination of the two achieves comprehensive protection to ensure the antifouling effect of the antifouling coating.

[0032] 3. The coating of the present invention is a one-component self-curing coating, which can be used alone without the need to additionally add a curing agent, reducing the manufacturing and labor costs. And because this antifouling coating is a one-component coating, the construction process is simple and can adapt to various processes such as spraying, brushing, and scraping.

[0033] In summary, during the use of the biodegradable antifouling coating prepared by the present invention, through the main-chain degradation and side-chain hydrolysis structure of the resin, and continuously releasing antimicrobial agents, the coating simultaneously has the effects of self-cleaning and self-polishing. At the same time, the introduction of antimicrobial agents makes the coating have antibacterial and antimicrobial effects. In addition, the degradation products are all small molecules with good biocompatibility, will not cause secondary pollution to the ocean, are green and environmentally friendly, and the construction process is simple, reducing the manufacturing and labor costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings here are incorporated into the specification and form a part of this specification, and are used together with the specification to explain the principles of the present invention.

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0036] Figure 1 It is a schematic flow chart of the preparation method of the biodegradable antifouling coating in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] Here, the exemplary embodiments will be described in detail. The implementation manners described in the following exemplary embodiments do not represent all implementation manners consistent with the present invention. On the contrary, they are only examples consistent with some aspects of the present invention detailed in the appended claims.

[0038] The present invention provides a method for preparing a biodegradable antifouling coating, specifically as follows: After weighing each raw material component according to the weight ratio, the degradation agent and auxiliary agent are first dispersed to obtain a resin mixture, and then an antimicrobial agent and filler are added to the resin mixture for a second dispersion to obtain a biodegradable antifouling coating.

[0039] As Figure 1 shown, the preparation method specifically includes the following steps:

[0040] Step 1: Weigh the biodegradable resin, antimicrobial agent, filler, auxiliary agent, and solvent according to the weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13);

[0041] Step 2: First disperse the biodegradable resin, auxiliary agent, and solvent to obtain a resin mixture;

[0042] Step 3: Sequentially add the antimicrobial agent and filler to the resin mixture for a second dispersion to obtain a biodegradable antifouling coating.

[0043] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0044] It should be noted that, in order to comply with the single comparison principle, the weight portion of the auxiliary agent in the following three embodiments is 1.

[0045] Example 1 (Method for preparing a biodegradable antifouling coating)

[0046] A method for preparing a biodegradable antifouling coating specifically includes the following steps:

[0047] Step 1: Weigh the biodegradable resin, antimicrobial agent, filler, auxiliary agent, and solvent according to the weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13);

[0048] Specifically, in this embodiment, the biodegradable resin is 30 parts, the antimicrobial agent is 35 parts, the filler is 24 parts, the auxiliary agent is 1 part, and the solvent is 10 parts;

[0049] Among them:

[0050] The antimicrobial agent contains the following raw materials in parts by weight: 4 parts of copper pyrithione, 27 parts of cuprous oxide, and 4 parts of isothiazolinone;

[0051] The filler contains the following raw materials in parts by weight: 8 parts of zinc oxide, 8 parts of iron oxide red, 3 parts of bentonite, and 5 parts of talcum powder;

[0052] The auxiliary agent contains the following raw materials in parts by weight: 0.7 part of chlorinated paraffin and 0.3 part of dispersant;

[0053] The solvent contains the following raw materials in parts by weight: 8 parts of xylene and 2 parts of butyl ester.

[0054] Step 2: Perform the first dispersion on the biodegradable resin, auxiliary agent and solvent to obtain a resin mixture. Among them, the rotation speed of the first dispersion is 1500 r / min, and the time of the first dispersion is 20 min.

[0055] Step 3: Sequentially add the antimicrobial agent and filler into the resin mixture for the second dispersion to obtain a biodegradable antifouling coating. Among them, the rotation speed of the second dispersion is 300 r / min, and the time of the second dispersion is 50 min.

[0056] Example 2 (Preparation method of biodegradable antifouling coating)

[0057] A preparation method of a biodegradable antifouling coating specifically includes the following steps:

[0058] Step 1: Weigh the biodegradable resin, antimicrobial agent, filler, auxiliary agent and solvent according to the weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13);

[0059] Specifically, in this example, the biodegradable resin is 40 parts, the antimicrobial agent is 28 parts, the filler is 20 parts, the auxiliary agent is 1 part, and the solvent is 11 parts;

[0060] Among them:

[0061] The antimicrobial agent contains the following raw materials in parts by weight: 3 parts of copper pyrithione, 20 parts of cuprous oxide, and 5 parts of isothiazolinone;

[0062] The filler contains the following raw materials in parts by weight: 4 parts of zinc oxide, 4 parts of iron oxide red, 2 parts of bentonite, and 10 parts of talcum powder;

[0063] The auxiliary agent contains the following raw materials in parts by weight: 0.8 part of chlorinated paraffin and 0.2 part of dispersant;

[0064] The solvent contains the following raw materials in parts by weight: 8 parts of toluene and 3 parts of butyl ester.

[0065] Step 2: Perform the first dispersion on the biodegradable resin, auxiliary agent and solvent to obtain a resin mixture. Among them, the rotation speed of the first dispersion is 2000 r / min, and the time of the first dispersion is 15 min.

[0066] Step 3: Add the antimicrobial agent and filler into the resin mixture in sequence for the second dispersion to obtain the biodegradable antifouling coating. The rotation speed of the second dispersion is 400 r / min, and the time of the second dispersion is 40 min.

[0067] Example 3 (Preparation method of biodegradable antifouling coating)

[0068] A preparation method of a biodegradable antifouling coating specifically includes the following steps:

[0069] Step 1: Weigh the biodegradable resin, antimicrobial agent, filler, auxiliary agent, and solvent according to the weight ratio of (30 - 40):(28 - 35):(20 - 24):(0.8 - 1.2):(10 - 13).

[0070] Specifically, in this example, the biodegradable resin is 35 parts, the antimicrobial agent is 31 parts, the filler is 22 parts, the auxiliary agent is 1 part, and the solvent is 13 parts.

[0071] Among them:

[0072] The antimicrobial agent contains the following raw materials in parts by weight: 5 parts of copper pyrithione, 23 parts of cuprous oxide, and 3 parts of isothiazolinone.

[0073] The filler contains the following raw materials in parts by weight: 6 parts of zinc oxide, 6 parts of iron oxide red, 2 parts of bentonite, and 8 parts of talcum powder.

[0074] The auxiliary agent contains the following raw materials in parts by weight: 0.9 part of chlorinated paraffin and 0.1 part of dispersant.

[0075] The solvent contains the following raw materials in parts by weight: 13 parts of toluene.

[0076] Step 2: Disperse the biodegradable resin, auxiliary agent, and solvent for the first time to obtain a resin mixture. The rotation speed of the first dispersion is 2500 r / min, and the time of the first dispersion is 10 min.

[0077] Step 3: Add the antimicrobial agent and filler into the resin mixture in sequence for the second dispersion to obtain the biodegradable antifouling coating. The rotation speed of the second dispersion is 500 r / min, and the time of the second dispersion is 30 min.

[0078] In summary, Table 1 summarizes the various component ratios of the environmentally friendly biodegradable antifouling coatings in Examples 1 - 3, as shown specifically below:

[0079] Table 1 Component ratios of environmentally friendly biodegradable antifouling coatings

[0080]

[0081] Table 2 shows the process parameters of the environmentally friendly biodegradable antifouling coatings prepared in Examples 1 to 3, which are specifically as follows:

[0082] Process parameters of the environmentally friendly biodegradable antifouling coatings prepared in Examples 1 to 3

[0083]

[0084] Table 3 shows the test results of the environmentally friendly biodegradable antifouling coatings of Examples 1 to 3, which are specifically as follows:

[0085] Test results of the environmentally friendly biodegradable antifouling coatings of Examples 1 to 3

[0086]

[0087]

[0088] From the comparison of the above examples and the test results, it can be seen that the prepared environmentally friendly biodegradable antifouling coatings have excellent antifouling effects, surface energies and adhesion properties.

[0089] The above are only specific embodiments of the present invention, enabling those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention.

[0090] It should be understood that the present invention is not limited to the above-described content and can be modified and changed without departing from its scope. The scope of the present invention is only limited by the appended claims.

Claims

1. A biodegradable antifouling coating, characterized in that: The biodegradable resin, antimicrobial agent, filler, auxiliary agent and solvent are compounded in a weight ratio of (30-40): (28-35): (20-24): (0.8-1.2): (10-13).

2. A biodegradable antifouling coating according to claim 1, characterized in that: The biodegradable resin is a biodegradable polyurethane resin.

3. A biodegradable antifouling coating according to claim 1, characterized in that: The antimicrobial agent comprises the following raw materials in parts by weight: 3-5 parts by weight of copper pyrithione, 20-27 parts by weight of cuprous oxide, and 3-5 parts by weight of isothiazolinone.

4. A biodegradable antifouling coating according to claim 1, characterized in that: The filler comprises the following raw materials in parts by weight: 4-8 parts by weight of zinc oxide, 4-8 parts by weight of iron oxide red, 2-3 parts by weight of bentonite, and 5-10 parts by weight of talc.

5. The biodegradable antifouling coating according to claim 1, characterized in that: The auxiliary agent comprises the following raw materials in parts by weight: 0.7-0.9 parts by weight of chlorinated paraffin and 0.1-0.3 parts by weight of a dispersant.

6. The biodegradable antifouling coating according to claim 1, characterized in that: The solvent is one or two of toluene, xylene and butyl ester.

7. A method for preparing a biodegradable antifouling coating according to any one of claims 1 to 6, characterized in that: After weighing each raw material component according to the weight ratio, the degradation agent and the auxiliary agent are dispersed for the first time to obtain a resin mixture, and then the antimicrobial agent and the filler are added to the resin mixture for a second dispersion to obtain a biodegradable antifouling coating.

8. The method for preparing a biodegradable antifouling coating according to claim 7, characterized in that: The specific steps include: Step 1, weighing the biodegradable resin, antimicrobial agent, filler, additive, and solvent in a weight ratio of (30-40): (28-35): (20-24): (0.8-1.2): (10-13); Step 2: Dispersing the biodegradable resin, additives and solvent for the first time to obtain a resin mixture; Step 3: Add the antimicrobial agent and filler to the resin mixture in sequence for a second dispersion to obtain a biodegradable antifouling coating.

9. The method for preparing a biodegradable antifouling coating according to claim 8, characterized in that: In the step 1, the rotation speed of the first dispersion is 1500r / min-2500r / min, and the time of the first dispersion is 10min-20min; in the step 2, the rotation speed of the second dispersion is 300r / min-500r / min, and the time of the second dispersion is 30min-50min.

10. The biodegradable antifouling coating according to any one of claims 1 to 6, or the biodegradable antifouling coating prepared by the preparation method according to any one of claims 7 to 9, characterized in that: The biodegradable antifouling paint is used in antifouling treatment of the surface of marine equipment.

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