Novel marine antifouling hydrogel coating material as well as preparation method and application thereof

Abstract

The invention discloses a novel marine antifouling gel coating material. The novel marine antifouling gel coating material comprises an antifouling gel monomer, a hardness modifier, an initiator and water, the antifouling gel monomer is an acrylamide series derivative compound or a polyethylene glycol derivative; the hardness modifier is a high polymer capable of providing a hydrogen bond donor or acceptor; the initiator is an organic initiator capable of initiating free radical polymerization of double bonds. The coating material provided by the invention is covalently bonded with an engineering bottom surface needing antifouling through a siloxane compound. A coating prepared from the marine antifouling hydrogel coating material provided by the invention has an excellent antifouling effect and also has excellent physical properties and adhesion strength, and the stability and durability of the antifouling coating can be ensured. In addition, due to the environmental friendliness of the material, the material has a wider application range, and powerful support is provided for the anti-fouling requirement of engineering in the ocean field.

Description

Technical Field

[0001] The invention relates to the field of marine antifouling applications, in particular to a hydrogel antifouling coating material and a preparation method and application thereof. Background Art

[0002] Biofouling, such as the adsorption of biomacromolecules such as polysaccharides and proteins, or the growth of microorganisms such as bacteria, is a long-standing problem in marine operations or engineering equipment applications. The attachment and growth of microorganisms in seawater on the equipment will cause continuous damage to the outer layer of the equipment. In addition, the long-term accumulation of biofouling will increase the ship's navigation resistance and increase fuel consumption. When large ships are in a static state, static biofouling will be more serious due to the lack of self-polishing relative to the seawater.

[0003] Spraying antifouling coating on the surface of ships is the most direct solution to the problem of marine biofouling. Hydrogel coating is a new type of antifouling coating with application prospects. Because of its excellent hydrophilicity and relatively low Young's modulus, this material not only exhibits excellent antifouling performance, but also can effectively remove the adsorption of marine organisms and show good drag reduction.

[0004] In recent years, research on hydrogel antifouling coatings has become increasingly in-depth. Among various hydrogel materials, polyethylene glycol (PEG) hydrogel has attracted widespread attention due to its high hydrophilicity and good compatibility with many components. A coatable strong hydrogel coating was developed based on polyacrylamide multi-arm PEG. Based on the antifouling effect of the strongly hydrophilic surface, the fouling release mechanism generated by the low Young's modulus and the slow self-polishing characteristics, this hydrogel coating exhibits significant inhibition of the attachment of proteins, polysaccharide molecules and microorganisms.

[0005] Although PEG hydrogels exhibit excellent antifouling properties, their easy oxidation and poor stability restrict their widespread application in marine environments. In addition, the weak bonding between the hydrophilic polymer chains of the hydrogels and the engineering surfaces and the low durability greatly limit the practical application of hydrogels. Summary of the invention

[0006] The problem to be solved by the present invention is to provide a new type of marine anti-sewage gel coating material with high stability and strong adhesion, as well as a preparation method and application thereof, in view of the shortcomings of the above-mentioned prior art.

[0007] To solve the above problems, the solution adopted by the present invention is as follows: a new type of marine anti-fouling gel coating material, characterized in that it includes an anti-fouling gel monomer, a hardness modifier, an initiator and water; the anti-fouling gel monomer is an acrylamide series derivative compound or a polyethylene glycol derivative; the hardness modifier is a polymer that can provide a hydrogen bond donor or acceptor; the initiator is an organic initiator that can initiate free radical polymerization of double bonds.

[0008] Furthermore, the novel marine anti-sewage gel coating material is characterized in that it also includes a surfactant, wherein the surfactant is sodium dodecylbenzene sulfonate (SDBS), and the mass fraction of SDBS is 0.1‰ to 0.5‰ of the total mass of the solution.

[0009] Furthermore, the novel marine anti-sewage gel coating material is characterized in that it also includes a surface modifier for pre-treating the target bottom surface, changing the affinity of the target bottom surface to the novel marine anti-sewage gel coating material, and enabling the target bottom surface to have functional groups that can be covalently cross-linked with the novel marine anti-sewage gel coating material.

[0010] Furthermore, the novel marine anti-fouling gel coating material is characterized in that the initiator is phenyl (2,4,6-trimethylbenzoyl) lithium phosphate (LAP), and the mass fraction of LAP is 1‰ to 10‰ of the anti-fouling gel monomer.

[0011] Furthermore, the novel marine anti-sewage gel coating material is characterized in that the acrylamide series derivative compound is one or more of acrylamide, dimethylacrylamide, N,N'-methylenebisacrylamide, hydroxyacrylamide, hydroxymethylacrylamide, and hydroxyethylpropionamide, and the mass ratio of the acrylamide series derivative compound to water is 1:1 to 1:10.

[0012] Furthermore, the novel marine antifouling gel coating material is characterized in that the mass ratio of the antifouling gel monomer to the hardness modifier is 1:1 to 1:9; the hardness modifier is polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP), and the degree of polymerization of PVA or PVP is between 2000 and 100000.

[0013] Furthermore, the novel marine anti-sewage gel coating material is characterized in that the surface modifier is composed of a siloxane compound and a diluent solvent, wherein the volume ratio of the siloxane compound to the diluent solvent is 1:4 to 1:9; the siloxane compound is one or more of glycidyloxypropyltrimethoxysilane (KH560), methacryloxypropyltrimethoxysilane (KH570), isocyanatepropyltriethoxysilane (TEPI), and 3-acrylamidopropyltri(trimethylsiloxy)silane (APMS); and the diluent solvent is a mixed solvent of methanol and / or ethanol and water.

[0014] Furthermore, the novel marine anti-sewage gel coating material is characterized in that the total volume fraction of alcohol in the dilution solvent is 90% to 100%.

[0015] Furthermore, the novel marine anti-sewage gel coating material is characterized in that the siloxane compound is a mixed solution of KH570 and TEPI in a volume ratio of 2:1 to 1:2.

[0016] A coating prepared using a new marine anti-sewage gel coating material, characterized in that the new marine anti-sewage gel coating material is coated on a target surface and then cured using ultraviolet light.

[0017] The invention discloses an application of a novel marine anti-sewage gel coating material in coating a substrate surface, characterized in that the novel marine anti-sewage gel coating material is coated on a substrate surface; the substrate surface includes a silicon-based surface, a high molecular polymer surface, and an epoxy resin polymer surface, including a glass substrate, various plastic substrates (polyethylene, polyvinyl chloride, polypropylene, etc.) and a high molecular polymer substrate (epoxy resin paint, etc.).

[0018] The novel anti-sewage gel coating material of the present invention has universal applicability. It can be covalently bonded to any silicon-based substrate by combining with the hydroxyl groups on the surface of the substrate through silicon-oxygen bonds, including various silicon-based surfaces such as glass, silicone sheets, and marble. It can also be combined with other substrate surfaces through hydrophobic effects or van der Waals forces, and can also be applied to different types of epoxy resin paint surfaces to meet the protection needs of different equipment interfaces.

[0019] The invention discloses a new type of marine antifouling gel coating material for use in ship antifouling, marine equipment antifouling and underwater equipment antifouling.

[0020] Based on the original design of anti-sewage gel coating, a hardness modifier is introduced to change the original polyacrylamide hydrogel polymer topology, enhance the cohesion between the gel polymer chains, improve the physical and chemical properties of the gel itself, and ensure the stability of the coating itself. At the same time, by applying a modifier to the target surface, the coating can be covalently bonded to a variety of modified surfaces, ensuring the firm bonding of the anti-sewage gel coating to the application surface, while further broadening the engineering application space of hydrogels, providing strong support for the prevention of underwater biological fouling.

[0021] The application method of the novel marine anti-fouling gel coating material comprises the following steps:

[0022] (1) coating the target surface to which the coating is to be applied using a surface modifier;

[0023] (2) evaporating the surface modifier solvent;

[0024] (3) applying a precursor solution of a sewage-proof gel coating material;

[0025] (4) ultraviolet light irradiation triggers a free radical polymerization reaction to form the anti-sewage gel coating on the target surface;

[0026] Preferably, the surface modifier coating amount in step (1) is about 50 mL / m2;

[0027] Preferably, the evaporation in step (2) is carried out naturally at room temperature in a ventilated and dark place for 2 to 24 hours;

[0028] Preferably, in step (3), the precursor solution coating is performed in an amount of about 1 L / m2 to obtain a coating material with a thickness of 1 mm;

[0029] Preferably, the free radical polymerization initiator in step (4) should be a UV lamp in the 200nm-450nm band, and the curing should be carried out for 15 to 120 minutes.

[0030] The technical effects of the present invention are as follows: First, the new anti-sewage gel coating material of the present invention has successfully completed the ocean hanging board test, and the formed coating has excellent performance. On the one hand, compared with traditional antifouling coatings, the material has a significant improvement in antifouling. Its uniqueness lies in that the hydrogel itself has a high water content, which can form a hydration layer around the polymer chain, effectively resist the attachment of proteins and polysaccharides, and thus prevent the colonization of bacteria, algae and plankton. And its bionic antifouling principle is environmentally friendly, avoiding the continuous pollution of the ocean by traditional antifouling coatings. On the other hand, compared with traditional hydrogels, the present invention has achieved significant improvements in the physical properties, chemical stability and adhesion strength of the hydrogel itself. It introduces polymers such as PVA as hardness modifiers for the gel, which increases the hydrogen bond cross-linking density inside the hydrogel, enhances the cohesion of the gel itself, and makes the hydrogel have higher toughness. At the same time, combined with surface modification methods, the antifouling coating is covalently linked to the modified surface, achieving ultra-high interfacial bonding strength, avoiding the coating from breaking or falling off when subjected to large tangential stress, ensuring that the antifouling coating has a long service life and can meet the antifouling needs of a variety of marine equipment and different types of underwater engineering surfaces.

[0031] The anti-sewage gel coating material of the present invention also has a wide range of applicability. The surface modifier involved in the present invention can be applied to a variety of surfaces, and can be combined with the hydroxyl groups on the surface of the substrate through silicon-oxygen bonds, and it can be covalently bonded to various silicon-based surfaces including glass, silica gel, etc. It is combined with other substrate surfaces through hydrophobic effects or van der Waals forces, making it widely applicable to different equipment or building surfaces to meet the needs of marine biological fouling prevention and control. Compared with traditional anti-fouling coatings, it has a longer service life, lower cost, and is environmentally friendly, providing a feasible way for large-scale application of hydrogel coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a schematic diagram of the appearance of the anti-sewage gel coating material provided by the present invention.

[0033] Figure 2 This is the one-dimensional tensile stress-strain curve of a preferred formulation of a part of the anti-sewage gel coating material of the present invention.

[0034] Figure 3 It is a schematic diagram and result of a 180 degree peeling test of the interfacial bonding strength of the anti-sewage gel coating material of the present invention.

[0035] Figure 4 This is a fluorescence microscope photograph of the anti-biological macromolecule adhesion test result of the anti-sewage gel coating material of the present invention.

[0036] Figure 5 This is a diagram showing the analysis results of the anti-adhesion performance of the anti-sewage gel coating material of the present invention against marine algae.

[0037] Figure 6 This is a diagram of the test results of the anti-sewage gel coating marine hanging board experiment. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below with reference to the accompanying drawings.

[0039] Example 1

[0040] This embodiment provides a novel anti-sewage gel coating material, and briefly introduces the preparation steps and physical property testing results of the anti-sewage gel material.

[0041] 1) Take 240 mg PVA and add it into 760 mg water, heat it to 95 degrees, and stir it continuously to completely dissolve the PVA; when the solution is cooled to about 50 degrees, add 120 mg acrylamide; repeat vortex oscillation and ultrasonication to completely dissolve the acrylamide; cool it to room temperature.

[0042] 2) Add 0.01 mL of 10 mg / mL LAP aqueous solution and vortex to make the solution evenly dispersed.

[0043] 3) Pour the solution into a mold and cure it under ultraviolet light for 2 hours; at this time, the precursor solution undergoes a phase change to form a hydrogel, and the hydrogel is taken out and placed in water to swell, thereby obtaining a sewage-proof gel material.

[0044] In order to verify the improvement of the physical properties of the hydrogel by the formula provided by the present invention, a series of hydrogels with different formulas prepared according to the above process were subjected to one-dimensional tensile tests. The hydrogel coating was stretched in one dimension using a tensile machine until the hydrogel broke. The experimental results are as follows: Figure 2 shown.

[0045] like Figure 2 As shown, hydrogels of various different formulations have a high modulus of rupture, a nominal stress exceeding 1 MPa, an actual stress exceeding 3 MPa, and have excellent mechanical properties.

[0046] Example 2

[0047] This embodiment provides an application method of the anti-sewage gel coating material, and briefly describes the process of applying the anti-sewage gel coating material of the present invention to the target surface that needs to be anti-fouling.

[0048] 1) KH570 and TEPI were mixed in a molar ratio of 2:1 to prepare solution A, 90% alcohol was used as a diluent, solution A and the diluent were mixed in a volume ratio of 1:4 to prepare solution B, and solution B was used as a surface modifier for epoxy primer and epoxy intermediate paint; due to the active chemical properties of TEPI, the solution should be used as soon as possible after mixing with the diluent to avoid long-term storage.

[0049] 2) Apply solution B evenly on the target epoxy resin paint surface by brushing, and dry the target surface naturally at room temperature under fume hood conditions for 2 hours.

[0050] 3) The anti-sewage gel coating precursor solution obtained in steps 1) to 2) of Example 1 is evenly applied on the above-mentioned dried target surface by brushing, and cured by ultraviolet light for 1 hour to form an anti-sewage gel coating on the target surface.

[0051] 4) Immersing the surface of the carrier carrying the cured hydrogel coating in water to swell the hydrogel, and finally obtaining Figure 3 Shown is a stain repellent gel coat applied to an epoxy painted surface.

[0052] In addition, in order to verify the superior performance of the surface modification scheme provided by the present invention on the adhesion of hydrogel to solid surface, a 180 degree peeling test was performed on the coating prepared according to the process described in Example 2 (as shown in FIG. Figure 3 a), a tensile machine was used to perform one-dimensional stretching on the carrier carrying the hydrogel coating until the coating was peeled off. The experimental results are shown in Figure 3 shown.

[0053] like Figure 3 As shown in Figure 2, during the measurement, the hydrogel broke at the weak bonding point, and the bonding surface was not completely peeled off from the epoxy resin paint. This embodiment also conducted a 180-degree peel test on a series of surface modifiers with different ratios. The results are shown in Figure 2. Figure 3 As shown in Figure c, when KH570:TEPI=2:1, the maximum adhesion strength of the coating can exceed 1000 J / m2, which is close to the bonding strength of common elastomers currently reported, providing a feasible way for the application of hydrogel coatings on various engineering surfaces.

[0054] Example 3

[0055] The novel anti-sewage gel coating of the present invention was used to test its anti-biological macromolecule adsorption effect. In terms of anti-adsorption, the adsorption capacity of bovine serum albumin (BSA), collagen, agarose and chitosan on the anti-sewage gel coating was measured and characterized, and the epoxy primer surface (Primer) and epoxy intermediate paint surface (Mid-coating) not coated with the anti-sewage gel coating were used as controls. Fluorescent markers were used in advance, and the three test surfaces were immersed in aqueous solutions of the above-mentioned biological macromolecules. An adsorption test was carried out for 14 days. After 14 days, the adsorption of various molecules on the coating was observed using a fluorescence microscope. The results are as follows. Figure 4 shown.

[0056] like Figure 4As shown in the figure, compared with the epoxy paint surface without anti-sewage gel coating, the coating showed excellent anti-biological macromolecule adsorption ability. Proteins and polysaccharides were hardly adsorbed on the coating, while the control group adsorbed a large number of biological macromolecules, especially chitosan.

[0057] Example 4

[0058] The anti-sewage gel coating material of Example 1 was used to conduct an anti-attachment test on marine algae. In terms of anti-marine algae adsorption, the adsorption capacity of Chlorella, Spirulina, Phaeodactylum and a mixed culture solution of the three algae on the anti-sewage gel coating was measured and characterized. The samples were immersed in a high concentration of the four algae culture solutions and cultured at 25 degrees, with a fixed light of 12 hours and a dark of 12 hours per day. After soaking for one week, they were taken out and the residual culture solution on the coating surface was rinsed with water. A confocal microscope was used to observe the adsorption of various algae on the coating. The control group was still an epoxy paint surface without an anti-sewage gel coating. The results are as follows: Figure 5 shown.

[0059] like Figure 5 As shown in the figure, compared with the control group, the coating showed a better ability to resist the adsorption of marine algae. The number of Spirulina, Triangle Finger Algae and Mixed Algae adsorbed on the coating was significantly less, and the number of Chlorella adsorbed was not significantly different from that of the control group, but the two control groups had no significant resistance to the adsorption of various algae.

[0060] Example 5

[0061] The anti-sewage gel coating material described in Examples 1 and 2 was coated on an epoxy intermediate paint iron plate to conduct an ocean hanging plate anti-fouling test to verify the durability and anti-fouling performance of the coating of the present invention. The test sea area is the Ligang sea area of ​​Zhoushan City, Zhejiang Province. The iron plate coated with the anti-sewage gel coating was hung in the shallow sea for 3 months to observe the fouling condition of the sample surface. The water quality of the test sea area selected in this embodiment is relatively turbid and has a high content of suspended solid particles. The control group is the epoxy intermediate paint surface. The experimental results are as follows Figure 6 shown.

[0062] like Figure 6As shown in the figure, after hanging in the Ligang sea area for 3 months, the edges of the experimental group and the control group both fell off due to electrochemical corrosion, which in turn caused the edges of the antifouling gel coating of the experimental group to lift up. It was observed that the epoxy intermediate paint on the surface of the control group in the middle area of ​​the hanging board had more wear, which was caused by the long-term wear of the epoxy intermediate paint hanging board surface by solid particulate matter in the ocean. The surface coating of the hanging board coated with the anti-sewage gel coating remained intact, indicating that the anti-sewage gel coating of the present invention can also reduce the physical wear caused by solid particulate matter on underwater equipment.

[0063] It can be seen from the above that the anti-sewage gel coating material of the present invention has excellent physical strength, coating performance, anti-fouling performance and wide application potential.

[0064] The polyacrylamide polymer part in the anti-fouling gel coating material of the present invention is used as an anti-fouling unit, and a polymer rich in hydrogen bonds such as PVA is introduced as a hardness modifier, so that the coating has excellent physical properties and anti-fouling effects at the same time. The siloxane group in the surface modifier used can form a covalent bond with the substrate surface, and the functional group at the other end of the siloxane can form a covalent connection with the anti-fouling unit, so that the coating is firmly bonded to the substrate, ensuring the binding stability of the anti-fouling gel coating material of the present invention on the substrate. For example, the siloxane group can be covalently bonded to the silicon-based substrate material, has excellent stability, will not be lost or fall off over time, and significantly improves the durability and reliability of the hydrogel coating; the siloxane group can also be combined with other substrate surfaces through hydrophobic effects and van der Waals forces, thereby providing flexibility and applicability for the wide application of the hydrogel coating. The material of the present invention can be applied to a variety of substrate surfaces, including glass substrates, various plastic substrates (polyethylene, polyvinyl chloride, polypropylene, etc.) and high molecular polymer substrates (epoxy resin paint, etc.), and has a wide range of applicability, especially for marine ships Provide stable and reliable anti-fouling effects.

Claims

1. A new type of marine anti-sewage gel coating material, characterized in that: The invention comprises an antifouling gel monomer, a hardness modifier, an initiator and water; the antifouling gel monomer is an acrylamide series derivative compound or a polyethylene glycol derivative; the hardness modifier is a polymer capable of providing a hydrogen bond donor or acceptor; and the initiator is an organic initiator capable of initiating free radical polymerization of double bonds.

2. The novel marine anti-sewage gel coating material according to claim 1, characterized in that: The invention also comprises a surfactant, which is sodium dodecylbenzene sulfonate (SDBS).

3. The novel marine anti-sewage gel coating material according to claim 1, characterized in that: It also includes a surface modifier for pre-treating the target bottom surface, changing the affinity of the target bottom surface to the new marine anti-fouling gel coating material, and enabling the target bottom surface to have functional groups that can be covalently cross-linked with the new marine anti-fouling gel coating material.

4. The novel marine anti-sewage gel coating material according to claim 1, characterized in that: The initiator is phenyl (2,4,6-trimethylbenzoyl) lithium phosphate (LAP), and the mass fraction of the LAP is 1‰ to 10‰ of the antifouling gel monomer.

5. The novel marine anti-sewage gel coating material according to claim 1, characterized in that: The acrylamide series derivative compounds are one or more of acrylamide, dimethyl acrylamide, N,N'-methylenebisacrylamide, hydroxy acrylamide, hydroxymethyl acrylamide, and hydroxyethyl propionamide, and the mass ratio of the acrylamide series derivative compounds to water is 1:1 to 1:

10.

6. The novel marine anti-sewage gel coating material according to claim 1, characterized in that: The mass ratio of the antifouling gel monomer to the hardness modifier is 1:1 to 1:9; The hardness modifier is polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP), and the polymerization degree of PVA or PVP is between 2000 and 100000.

7. The novel marine anti-sewage gel coating material according to claim 3 is characterized in that: The surface modifier is composed of a siloxane compound and a diluent solvent, wherein the volume ratio of the siloxane compound to the diluent solvent is 1:4 to 1:9; the siloxane compound is one or more of glycidyloxypropyltrimethoxysilane (KH560), methacryloxypropyltrimethoxysilane (KH570), isocyanatepropyltriethoxysilane (TEPI), and 3-acrylamidopropyltri(trimethylsiloxy)silane (APMS); and the diluent solvent is a mixed solvent of methanol and / or ethanol and water.

8. The novel marine anti-sewage gel coating material according to claim 7, characterized in that: The total volume fraction of alcohol in the dilution solvent is 90% to 100%.

9. The novel marine anti-sewage gel coating material according to claim 7, characterized in that: The siloxane compound is a mixed solution of KH570 and TEPI in a volume ratio of 2:1 to 1:

2.

10. A coating prepared using the novel marine anti-sewage gel coating material according to claim 1, characterized in that: The new marine anti-fouling gel coating material is coated on the target surface and then cured using ultraviolet light.

11. A use of the novel marine anti-sewage gel coating material as claimed in claim 1 in coating a substrate surface, characterized in that: A novel marine anti-sewage gel coating material is coated on a substrate surface; the substrate surface includes a silicon-based surface and a high molecular polymer surface.

12. An application of the novel marine antifouling gel coating material as claimed in claim 1 in antifouling of ships, marine equipment and underwater equipment.

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