Environment-friendly antifouling paint with triple non-metal synergistic antifouling mechanism and preparation method of environment-friendly antifouling paint

Abstract

The invention belongs to the technical field of marine heavy anti-fouling materials, and particularly discloses an environment-friendly anti-fouling coating with a triple non-metal synergistic anti-fouling mechanism and a preparation method of the environment-friendly anti-fouling coating. 5 to 10 parts of polyaniline; 2-5 parts of an acidic solution with a pH value of 3; 3 to 6 parts of Fe3O4 (at) C nano enzyme; and 2-8 parts of a filler with a sharkskin-imitating structure. The environment-friendly anti-fouling paint with the triple non-metal synergistic anti-fouling mechanism has a triple-mechanism synergistic effect, and is suitable for anti-fouling protection of surfaces of underwater structures such as warships, polar ships, ocean platforms and the like with high requirements on environmental protection, long-term effectiveness and polar construction adaptability; no heavy metals such as copper and zinc are released; long-acting antifouling property: according to ASTM D5618 standard test, the barnacle adhesion rate within 24 months is lower than 5%; and the polar region construction adaptability is high, construction can be conducted in the low-temperature environment of-20 DEG C, and the polar region ship and platform construction requirements are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of marine antifouling materials, and particularly relates to an environmentally-friendly antifouling paint with a triple non-metal synergistic antifouling mechanism and a preparation method thereof. BACKGROUND

[0002] With the strict limitation of copper ion release amount in antifouling paint by IMO (International Maritime Organization), the traditional copper-containing antifouling paint gradually withdraws from the market. The current mainstream antifouling technologies on the market include:

[0003] Bio-inspired repellent: relying on specific chemicals to attract or repel attached organisms, but the cost is high and the mechanism is single.

[0004] Zinc pyrithione compound system: using metal zinc ions to inhibit biological attachment, but there is a strong metal dependence and environmental toxicity problem.

[0005] Conductive polymer / silicone composite coating: using dual mechanisms of electrophysiological interference and low surface energy, but lacking degradation ability and short antifouling life.

[0006] Graphene-based coating: mainly physical barrier, and the inhibition effect on hard shell organisms such as barnacles is limited.

[0007] Therefore, there is an urgent need for a new type of antifouling paint that is metal-free, integrates multiple antifouling mechanisms, is environmentally friendly, and is suitable for extreme environments. SUMMARY

[0008] In order to solve the above technical problems, the present application provides an environmentally-friendly antifouling paint with a triple non-metal synergistic antifouling mechanism and a preparation method thereof.

[0009] In order to achieve the above purpose, the present application is implemented according to the following technical solutions:

[0010] The first technical solution provided by the present application is an environmentally-friendly antifouling paint with a triple non-metal synergistic antifouling mechanism, which is prepared from the following components by weight:

[0011] 100 parts of fluorocarbon resin;

[0012] 5-10 parts of polyaniline;

[0013] 2-5 parts of an acidic solution with pH = 3;

[0014] 3-6 parts of Fe3O4@C nanoenzyme;

[0015] 2-8 parts of sharkskin structure filler.

[0016] Further, the acidic solution is hydrochloric acid or sulfuric acid.

[0017] Further, the sharkskin structure filler is polydimethylsiloxane modified silica gel particles, and the height of the sharkskin structure rib of the sharkskin structure filler is 20 μm.

[0018] The second technical solution provided by the application is a preparation method of the above-mentioned environmentally friendly antifouling paint with a triple non-metal synergistic antifouling mechanism, comprising the following steps:

[0019] S1, dissolving polyaniline in an acidic solution with pH=3, fully stirring until uniform to obtain a suspension;

[0020] S2, adding Fe3O4@C nano-enzyme to the suspension and ultrasonically dispersing for 20 minutes;

[0021] S3, adding sharkskin structure filler and fluorocarbon resin and stirring to mix;

[0022] S34, performing three-roll grinding treatment at a linear speed of 15 m / s to obtain a coating slurry with stable structure.

[0023] Specifically, the preparation process of the Fe3O4@C nano-enzyme is as follows:

[0024] (1) Preparation of precursor solution

[0025] In a 250 mL three-necked flask, 5 mmol of FeCl3·6H2O, 10 mmol of glucose, 10 mmol of urea and 50 mL of a mixed solvent composed of ethylene glycol and deionized water in a volume ratio of 4:1 were added, and ultrasonic treatment was performed for 10 minutes to form a transparent orange solution;

[0026] (2) Hydrothermal reaction

[0027] The transparent orange solution was transferred to a 100 mL polytetrafluoroethylene-lined reaction kettle, and after being closed, it was placed in a 180℃ reaction for 12 hours; after natural cooling to room temperature, a black precipitate was taken out;

[0028] (3) Washing and drying

[0029] The black precipitate was collected by a magnet, and then washed repeatedly with ethanol and deionized water for 3 times; and dried in a vacuum oven at 60℃ for 12 hours; to obtain Fe3O4@C nano-enzyme particles.

[0030] Further, in step S3, segmented stirring is adopted: first stirring at 500 rpm for 30 minutes; and then stirring at 1200 rpm for 15 minutes.

[0031] Compared with the prior art, the application has the following beneficial effects:

[0032] 1. Triple mechanism synergy: The conductive polymer polyaniline obtained by acid modification of polyaniline in the coating of the present application can form an electro-physiological interference layer, release a micro-current of 0.1-1 muA / cm 2 , interfere with the nerve signal conduction of marine organisms, and prevent their attachment behavior; Fe3O4@C nanozyme can form an enzyme-catalyzed degradation layer, in the presence of trace H2O2 or dissolved oxygen, catalyze the production of highly active ·OH free radicals, destroy the structure of biological adhesion proteins, and can exist stably for a long time, with biodegradability; The sharkskin-structured filler and fluorocarbon resin can form a biomimetic barrier layer with a surface energy of less than 20 mN / m, inhibiting the secretion of mucus by attached organisms; The sharkskin-structured filler forms a physical barrier to hinder biological attachment; It is suitable for the antifouling protection of underwater structure surfaces of military ships, polar ships, offshore platforms and the like with high requirements for environmental friendliness, long-term effectiveness and polar construction adaptability;

[0033] 2. Green and environmentally friendly: No release of heavy metals such as copper and zinc;

[0034] 3. Long-term antifouling: According to the ASTM D5618 standard test, the barnacle attachment rate is less than 5% within 24 months;

[0035] 4. Strong adaptability to polar construction: It can be constructed at a low temperature of-20℃, meeting the construction requirements of polar ships and platforms;

[0036] 5. Mature preparation process: The functional structure can be stably constructed through conventional processes such as three-roll grinding and multi-stage stirring. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 It is the catalytic activity stability experimental curve of Fe3O4@C nanozyme of the present application in seawater environment.

[0038] Figure 2 It is the SEM graph of the sharkskin-structured filler.

[0039] Figure 3 It is the SEM micrograph of the biomimetic sharkskin structure.

[0040] Figure 4 It is the cross-sectional structure diagram of the triple-function coating formed by the present application.

[0041] Figure 5 It is the comparison experiment graph of the triple-function coating formed by the present application and the steel plate in terms of barnacle attachment rate (24 months).

[0042] Figure 6 It is the adhesion test result of the triple-function coating formed by the present application at different temperatures. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0044] S1. Dissolve 7 g of polyaniline in 3 g of hydrochloric acid solution with a pH of 3, and stir thoroughly until uniform to obtain a suspension;

[0045] S2. Preparation of Fe3O4@C nanozyme:

[0046] (1) Precursor solution preparation

[0047] In a 250 mL three-necked flask, add 5 mmol of FeCl3·6H2O, 10 mmol of glucose, 10 mmol of urea, and 50 mL of a mixed solvent consisting of ethylene glycol and deionized water in a volume ratio of 4:1. Ultrasonicate for 10 minutes to completely dissolve the solution to form a transparent orange solution.

[0048] (2) Hydrothermal reaction

[0049] The transparent orange solution was transferred to a 100 mL polytetrafluoroethylene-lined reactor, sealed, and reacted at 180°C for 12 h. The black precipitate was removed after natural cooling to room temperature.

[0050] (3) Washing and drying

[0051] The black precipitate was collected by magnet and washed three times with ethanol and deionized water. It was then dried in a vacuum oven at 60°C for 12 h to obtain Fe3O4@C nanozyme particles. The catalytic activity stability of the nanozyme was tested as follows:

[0052] The Fe3O4@C nanozyme was placed in artificial seawater (pH = 8.2, 25 ° C) for 60 days, and its catalytic activity was detected (TMB colorimetric method). The experimental curve of the catalytic activity stability of Fe3O4@C nanozyme in seawater environment is shown in Figure 2. Figure 1 As shown by Figure 1 It can be seen that the activity retention rate of Fe3O4@C nanozyme is higher than 85%, indicating that the carbon coating structure significantly enhances the seawater stability of the nanozyme.

[0053] 5 g of Fe3O4@C nanozyme was added to the suspension and ultrasonically dispersed for 20 min;

[0054] S3, add 6g polydimethylsiloxane modified silica gel particles (commercially available) as shark skin structure filler (the height of the shark skin structure ribs is 20μm, and the SEM image of the bionic microstructure is as follows Figure 2 As shown, the SEM micrograph of the bionic shark skin structure is as follows Figure 3 As shown, from Figure 3The rib height can be about 20 microns) and fluorocarbon resin are stirred and mixed uniformly, and the stirring is performed in stages: stirring at 500 rpm for 30 minutes, and then stirring at 1200 rpm for 15 minutes.

[0055] S34, after three-roll grinding treatment, the line speed is controlled at 15 m / s, and a coating slurry with stable structure is obtained.

[0056] In use, the coating slurry is applied to the surface of a steel plate substrate or other substrate 1, dried and cured to form a triple-function coating layer, and the cross-sectional layered structure of the coating is as shown in Figure 4 The conductive polymer polyaniline obtained by acid modification of polyaniline in the coating can form an electro-physiological interference layer 2, release a micro-current of 0.1-1 muA / cm 2 , interfere with the neural signal conduction of marine organisms, and prevent their attachment behavior; the Fe3O4@C nano-enzyme can form an enzyme-catalytic degradation layer 2, catalyze the generation of highly active ·OH free radicals in the presence of trace amounts of H2O2 or dissolved oxygen, destroy the structure of biological adhesion proteins, and can exist stably for a long time and have biodegradation ability; the sharkskin-structured filler and fluorocarbon resin can form a biomimetic barrier layer 3 with a surface energy of less than 20 mN / m, which inhibits the secretion of mucus by attached organisms; the sharkskin-structured filler forms a physical barrier to hinder biological adhesion.

[0057] To further verify the antifouling performance and environmental adaptability of the coating of the present application, the following experiments were conducted:

[0058] 1. Barnacle attachment experiment:

[0059] Experimental object: triple-function coating layer of the present application vs. blank steel plate;

[0060] Experimental conditions: ASTM D3623 standard, seawater immersion time 24 months; barnacle attachment rate results are as shown in Figure 5 From Figure 5 it can be seen that the barnacle coverage rate of the triple-function coating layer of the present application is less than 5%, and the barnacle coverage rate of the blank steel plate is close to 80%, so the triple-function coating layer of the present application exhibits excellent barnacle attachment resistance performance under long-term immersion.

[0061] 2. Low-temperature construction performance test:

[0062] The coating was applied to a steel plate at -20℃, 0℃ and 25℃, respectively, and the adhesion was tested (ASTM D3359), and the adhesion test results at different temperatures are as shown in Figure 6 From Figure 6It can be known that the coating of the present application still shows good adhesion strength after construction in different polar low temperature environments (-20 DEG C, 0 DEG C, 25 DEG C). The pull-out method test shows that the average bonding strength is still 2.0 MPa at -20 DEG C, and the adhesion is further improved to 5.5 MPa as the temperature rises to 25 DEG C, which shows that the coating has construction adaptability and interface stability in the extreme cold environment. It can be seen that the coating of the present application has good polar low temperature construction adaptability.

[0063] 3. Surface energy test:

[0064] Method: The surface energy of the triple functional coating of the present application is measured by contact angle determination method (water drop angle), and the water contact angle of the triple functional coating of the present application is about 116 DEG, and the surface energy is less than 20 mN / m. Compared with the existing ordinary epoxy coating, the water contact angle is about 85 DEG, and the surface energy is about 35 mN / m, which has obvious advantages.

[0065] The technical scheme of the present application is not limited to the limitation of the above specific embodiments, and any technical deformation made according to the technical scheme of the present application falls within the protection scope of the present application.

Claims

1. An environmentally friendly antifouling coating with a triple non-metallic synergistic antifouling mechanism, characterized in that: The composition consists of the following components in parts by weight: 100 parts of fluorocarbon resin; 5-10 parts of polyaniline; 2-5 parts of acidic solution with pH=3; 3-6 parts of Fe3O4@C nanozyme; 2-8 parts of shark skin-like structural filler.

2. The environmentally friendly antifouling coating with triple non-metallic synergistic antifouling mechanism according to claim 1, characterized in that: The acidic solution is hydrochloric acid or sulfuric acid.

3. The environmentally friendly antifouling coating with triple non-metallic synergistic antifouling mechanism according to claim 1, characterized in that: The shark skin-like structural filler is polydimethylsiloxane-modified silica gel particles, and the height of the shark skin-like structural ribs of the shark skin-like structural filler is 20 μm.

4. A method for preparing an environmentally friendly antifouling coating having a triple non-metallic synergistic antifouling mechanism according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. dissolving polyaniline in an acidic solution with a pH of 3, stirring thoroughly until uniform, to obtain a suspension; S2, adding Fe3O4@C nanozyme to the suspension and dispersing it by ultrasonic wave for 20 min; S3, adding shark skin-like structural filler and fluorocarbon resin, stirring and mixing; S34, after three-roller grinding treatment, the line speed is controlled at 15m / s to obtain a coating slurry with a stable structure.

5. The method for preparing an environmentally friendly antifouling coating having a triple non-metallic synergistic antifouling mechanism according to claim 1, characterized in that: The preparation process of the Fe3O4@C nanozyme is as follows: (1) Precursor solution preparation In a 250 mL three-necked flask, add 5 mmol of FeCl3·6H2O, 10 mmol of glucose, 10 mmol of urea, and 50 mL of a mixed solvent consisting of ethylene glycol and deionized water in a volume ratio of 4:

1. Ultrasonicate for 10 minutes to completely dissolve the solution to form a transparent orange solution. (2) Hydrothermal reaction The transparent orange solution was transferred to a 100 mL polytetrafluoroethylene-lined reactor, sealed, and reacted at 180°C for 12 h. The black precipitate was removed after natural cooling to room temperature. (3) Washing and drying The black precipitate was collected by a magnet, washed repeatedly with ethanol and deionized water three times, and dried in a vacuum oven at 60°C for 12 h to obtain Fe3O4@C nanozyme particles.

6. The method for preparing an environmentally friendly antifouling coating having a triple non-metallic synergistic antifouling mechanism according to claim 1, characterized in that: In step S3, staged stirring is adopted: first stirring at 500 rpm for 30 minutes; then stirring at 1200 rpm for 15 minutes.

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