Thin film material with anti-fouling function as well as preparation method and application of thin film material

Abstract

The invention relates to a thin film material with an anti-fouling function and a preparation method and application thereof.The thin film material with the anti-fouling function comprises a base material layer and an anti-fouling coating which are sequentially arranged in a stacked mode, the base material layer comprises resin and an anti-fouling auxiliary, and the anti-fouling coating comprises a polymer anti-fouling material. The thin film material with the anti-pollution function has excellent anti-pollution performance and long anti-pollution lasting period.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-fouling functional materials, and particularly relates to a thin film material with anti-fouling function, a preparation method thereof, and an application thereof. Background Art

[0002] Soft thin film materials have extensive applications in microalgae culture, aquaculture, and marine industries. However, during the application process, the problem of biofouling is widespread. Biofouling refers to the biological fouling formed by the massive attachment, aggregation, growth, and reproduction of attached organisms on the surface of underwater facilities. The types of attached organisms are diverse, including bacteria, algae (diatoms and algal spores), barnacles, mussels, etc. Biofouling seriously affects the surface and interfacial properties of materials, causing serious economic losses to industries such as microalgae culture, aquaculture, and marine industries; in the fields of medical and health and food safety, biofouling may pose a serious threat to human health; in the prior art, anti-fouling coatings are often set on the material surface to inhibit biofouling, but there are problems of limited effect and short effective period, and further improvement is needed.

[0003] Therefore, it is necessary to develop a thin film material with anti-fouling function to improve the anti-fouling effect and the effective period. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a thin film material with anti-fouling function, a preparation method thereof, and an application thereof. In the thin film material with anti-fouling function, the anti-fouling additive and the polymer anti-fouling material jointly play an anti-fouling role, with good anti-fouling effect. At the same time, the polymer anti-fouling material and the substrate form a chemical bond, which can greatly improve the effective period of the anti-fouling function.

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

[0006] In the first aspect, the present invention provides a thin film material with anti-fouling function, which includes a substrate layer and an anti-fouling coating arranged in a stacked manner in sequence. The substrate layer includes a resin and an anti-fouling additive, and the anti-fouling coating includes a polymer anti-fouling material.

[0007] In the present invention, the polymer anti-fouling material in the anti-fouling coating can reduce the attachment of biofouling and promote the release of fouling. At the same time, by adding an anti-fouling additive to the substrate layer, the substrate layer can fix the anti-fouling additive, making it stably exist and slowly release. Among them, the anti-fouling additive can produce an avoidance effect or an inhibitory effect on proteins, bacteria, algal cells, etc., and can damage or kill the fouling organisms attached to the surface, so that the fouling organisms attached to the surface fall off from the surface. The two work together to greatly improve the anti-fouling effect. At the same time, the anti-fouling material in the anti-fouling coating is combined with the substrate layer through a chemical bond, which has higher stability than the traditional physical coating and can greatly improve the effective period of the anti-fouling function.

[0008] In the present invention, the substrate layer may be composed of a single layer or a multi-layer structure.

[0009] Preferably, the substrate layer includes an inner layer, an intermediate layer, and a surface layer.

[0010] Preferably, the surface layer and the inner layer include an anti-fouling additive, and the intermediate layer does not include an anti-fouling additive.

[0011] Preferably, the surface layer, the inner layer, and the intermediate layer all include an anti-fouling additive.

[0012] Preferably, the anti-fouling additive includes any one or a combination of at least two of metal-organic complexes, organosilicon compounds, metal chlorides, metal oxides, quaternary ammonium salt compounds, or chlorophenol compounds, and is further preferably a metal-organic complex.

[0013] In the present invention, the anti-fouling additive is preferably a metal-organic complex. Adding a metal-organic complex to the substrate layer can enable partial embedding of the metal-organic complex on the surface of the substrate layer, and graft a polymer anti-fouling material on the surface of the substrate layer to form an anti-fouling coating. The slow release of the metal-organic complex can improve the synergistic anti-fouling effect of metal ions and the polymer anti-fouling material. The relative concentration of surface metal ions in the thin film material with anti-fouling function is relatively high, which will produce an avoidance effect or an inhibitory effect on proteins, bacteria, and algal cells, etc. The polymer anti-fouling material will reduce the attachment of biological fouling and promote fouling release, making the anti-fouling effect better. It can achieve metal ion release and exert a good anti-fouling effect without hydrolysis of the organic film-forming agent.

[0014] Preferably, the metal element in the metal-organic complex is selected from any one or a combination of at least two of titanium, silver, copper, zinc, aluminum, molybdenum, germanium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, or scandium.

[0015] Preferably, the organic ligand in the metal-organic complex is selected from any one or a combination of at least two of tannic acid, 8-hydroxyquinoline, sorbic acid, 3-methyl-4-isopropylphenol, hydroxybenzoic acid, pyrithione, hexahydro-1,3,5-tris(hydroxyethyl)melamine, 1,2-benzisothiazol-3-one, 2-hydroxypyridine-N-oxide, 2-1 six-level must-N-oxide, gallate, or catechin.

[0016] In the present invention, the metal-organic complex can be a commercially available product or synthesized by existing technologies. It can be formed by mixing a metal ion-containing compound with a corresponding organic ligand under appropriate conditions to cause a coordination reaction between them to form a metal-organic complex, or by reducing the metal ion to a lower oxidation state and then reacting it with the organic ligand to form a metal-organic complex, or by reacting the metal ion-containing compound with an excess of the organic ligand so that the complex precipitates out, followed by filtration, washing, and drying to obtain a pure metal-organic complex, or by reacting the metal ion-containing compound with the organic ligand under high-temperature and high-pressure solvent conditions to accelerate the coordination reaction and form a metal-organic complex.

[0017] Preferably, the organosilicon compound includes any one or a combination of at least two of methylsilane, ethylsilane, propenylsilane, aminosilane, or epoxy silane.

[0018] Preferably, the metal chloride includes any one or a combination of at least two of silver chloride, copper chloride, zinc chloride, rare earth chloride, or aluminum chloride.

[0019] Preferably, the metal oxide includes any one or a combination of at least two of zinc oxide, aluminum oxide, titanium dioxide, rare earth oxide, or zirconium oxide.

[0020] Preferably, the quaternary ammonium salt compound includes any one or a combination of at least two of cetyltrimethylammonium chloride, cetyl dimethylbenzylammonium chloride, hexadecanamidopropyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, dicocodimethylammonium chloride, trioctylmethylammonium chloride, cocamidopropyltrimethylammonium chloride, tallow bis(hydroxyethyl)methylammonium chloride, dodecyl bis(hydroxyethyl)methylammonium chloride, dodecyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium chloride, distearyldimethylbenzylammonium chloride, lauryltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide, lauramidopropyltrimethylammonium chloride, cocoyl bis(hydroxyethyl)methylammonium chloride, dodecyltrimethylammonium chloride, or docosyltrimethylammonium chloride.

[0021] Preferably, the chlorophenol compound includes any one or a combination of at least two of tribrominated trichlorobenzene, dichlorophenol, or p-dichlorophenol.

[0022] Preferably, the resin includes any one or a combination of at least two of polyethylene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate, polyethylene terephthalate, polycarbonate, polyamide, polyethersulfone, polytetrafluoroethylene, polystyrene, polyurethane, polymethyl methacrylate, or polylactic acid.

[0023] Preferably, based on the total mass of the substrate layer being 100%, the mass percentage of the anti-fouling aid in the substrate layer is 0.01% to 10%, such as 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0024] Preferably, the substrate layer further comprises other aids.

[0025] Preferably, the other aids include any one or a combination of at least two of antioxidants, ultraviolet absorbers, nucleating agents, plasticizers, toughening agents, stabilizers, dispersants, lubricants, colorants, light stabilizers or antistatic agents.

[0026] Preferably, the polymer anti-fouling material comprises an anti-fouling functional group and a photoreactive group, and the polymer anti-fouling material has any one of the structures shown in Formula I, Formula II or Formula III:

[0027]

[0028]

[0029] Wherein, R1, R2 and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (such as 2, 3, 4 or 5, etc.).

[0030] X, Y and Z are each independently selected from an ester group, an amide group, an ether group, an aromatic group having 6 to 12 carbon atoms (such as 7, 8, 9, 10 or 11, etc.), an alkyleneoxy group having 1 to 6 carbon atoms (such as 2, 3, 4 or 5, etc.) and an alkyl group having 1 to 6 carbon atoms (such as 2, 3, 4 or 5, etc.).

[0031] R4 is selected from hydrophilic groups.

[0032] R5 is selected from hydrophobic groups.

[0033] R6 is selected from photoreactive groups.

[0034] Wherein a is an integer from 1 to 200 (such as 20, 40, 60, 80, 100, 120, 140, 160 or 180, etc.), b is an integer from 1 to 200 (such as 20, 40, 60, 80, 100, 120, 140, 160 or 180, etc.), and c is an integer from 1 to 200 (such as 20, 40, 60, 80, 100, 120, 140, 160 or 180, etc.).

[0035] In the present invention, the ester group is -COO-, the amide group is -CO-NH-, and the ether group is -O-.

[0036] In the present invention, when the polymer antifouling material has the structure shown in Formula II, it can form a hydrophobic surface on the substrate layer, thereby reducing the binding force between fouling organisms and the surface, and achieving an antifouling effect by the scouring action of water flow; when the polymer antifouling material has the structure shown in Formula III, it can form a hydrophilic surface on the substrate layer, so that water forms a water film on the hydrophilic surface, thereby reducing the contact between fouling organisms and the surface to achieve an antifouling effect; when the polymer antifouling material has the structure shown in Formula I, it contains both hydrophilic groups and hydrophobic groups, forming an amphiphilic polymer, which can be effectively used for surface antifouling. The amphiphilic polymer can provide a heterogeneous nanoscale mosaic chemical surface, where the coexistence of hydrophobic and hydrophilic regions can confuse organisms during the sedimentation and adhesion processes. Once the area available for microbial settlement is below the critical size, organisms that tend to settle on hydrophobic or hydrophilic surfaces will be repelled, thus achieving an antifouling effect, with broad-spectrum and structural stability.

[0037] Preferably, the hydrophilic group contains any one or a combination of at least two of carboxyl, amino, hydroxyl, phosphate or sulfonic acid groups.

[0038] Preferably, the hydrophilic group is selected from any one of the following groups:

[0039]

[0040] Preferably, the hydrophobic group is selected from any one of an alkyl group having 1 to 20 carbon atoms (such as 2, 4, 6, 8, 10, 12, 14, 16 or 18, etc.), an alkoxy group having 1 to 20 carbon atoms (such as 2, 4, 6, 8, 10, 12, 14, 16 or 18, etc.), an aryl group having 6 to 12 carbon atoms (such as 7, 8, 9, 10 or 11, etc.), a siloxane group having 1 to 20 carbon atoms (such as 2, 4, 6, 8, 10, 12, 14, 16 or 18, etc.) or a fluorine-substituted alkyl group having 1 to 20 carbon atoms (such as 2, 4, 6, 8, 10, 12, 14, 16 or 18, etc.).

[0041] Preferably, the hydrophobic group is selected from any one of the following groups:

[0042]

[0043]

[0044] Among them, n is 1 to 20, such as 2, 4, 6, 8, 10, 12, 14, 16 or 18, etc. Preferably, the photo-reactive group is selected from any one of the following groups:

[0045]

[0046] Preferably, the polymer anti-fouling material is selected from any one of the following structures:

[0047]

[0048]

[0049]

[0050] Preferably, the anti-fouling coating further comprises coating additives.

[0051] Preferably, the coating additives include any one or a combination of at least two of a leveling agent, a dispersant, an antifoaming agent, an emulsifier, a diluent, a drier, a preservative, a pigment or a filler.

[0052] In a second aspect, the present invention provides a method for preparing a thin film material having an anti-fouling function as described in the first aspect, and the preparation method comprises the following steps:

[0053] (1) Mix an anti-fouling aid, a resin and optionally other aids to prepare a substrate layer.

[0054] (2) Mix a polymer anti-fouling material, a solvent and optionally coating additives to form an anti-fouling coating solution, then place it on the substrate layer prepared in step (1), dry it, and irradiate it with ultraviolet light to obtain the thin film material having an anti-fouling function.

[0055] Preferably, the preparation method comprises the following steps:

[0056] (a) Mix an optional anti-fouling aid, a resin and optionally other aids to prepare an inner layer raw material.

[0057] (b) Mix an optional anti-fouling aid, a resin and optionally other aids to prepare an intermediate layer raw material.

[0058] (c) Mix an optional anti-fouling aid, a resin and optionally other aids to prepare a surface layer raw material.

[0059] (d) Make the inner layer raw material prepared in step (a), the intermediate layer raw material prepared in step (b) and the surface layer raw material prepared in step (c) into an inner layer, an intermediate layer and a surface layer which are sequentially stacked.

[0060] (e) Mix a polymer anti-fouling material, a solvent and optionally coating additives to form an anti-fouling coating solution, then place it on the surface layer and / or the inner layer prepared in step (d), dry it, and irradiate it with ultraviolet light to obtain the thin film material having an anti-fouling function.

[0061] At least one of the inner layer raw material in step (a) and the surface layer raw material in step (c) contains an anti-fouling aid.

[0062] Steps (a), (b) and (c) are carried out step by step without considering the order, or simultaneously.

[0063] Preferably, the preparation method of forming the inner layer, the intermediate layer and the surface layer which are sequentially stacked in step (d) is selected from any one of the following methods 1 to 3.

[0064] Method 1: The inner layer raw material, the intermediate layer raw material and the surface layer raw material are melt co-extruded through three layers to obtain the inner layer, the intermediate layer and the surface layer which are sequentially stacked.

[0065] Method 2: The inner layer raw material, the intermediate layer raw material and the surface layer raw material are respectively melt extruded to obtain the inner layer film, the intermediate layer film and the surface layer film, which are stacked and hot pressed to obtain the inner layer, the intermediate layer and the surface layer which are sequentially stacked.

[0066] Method 3: The inner layer raw material is heated and melted or mixed with a solvent to form a solution, and then dried to prepare the inner layer film. The intermediate layer raw material is heated and melted or mixed with a solvent to form a solution, which is coated on the surface of the inner layer film and dried to form the intermediate layer film. The surface layer raw material is heated and melted or mixed with a solvent to form a solution, which is coated on the surface of the intermediate layer film and dried to obtain the inner layer, the intermediate layer and the surface layer which are sequentially stacked.

[0067] Preferably, before placing in the substrate layer prepared in step (1) in step (2), there is also a step of pre-treating the substrate layer.

[0068] Preferably, the pre-treatment includes ultrasonic cleaning with water, ethanol and acetone in sequence, drying, and plasma corona treatment.

[0069] Preferably, the drying includes air drying or low-temperature vacuum drying at 30-45 °C (such as 32 °C, 34 °C, 36 °C, 38 °C, 40 °C, 42 °C or 44 °C, etc.).

[0070] In the present invention, by using plasma corona treatment on the surface layer, active hydrogen is generated on the surface of the surface layer, which is convenient for the infiltration of the anti-fouling coating solution and can improve the ultraviolet grafting rate.

[0071] Preferably, placing in the substrate layer prepared in step (1) in step (2) includes placing the anti-fouling coating solution on the substrate layer prepared in step (1) by any one or a combination of at least two of brushing, spraying, dip coating, spin coating, casting coating, roll coating, laser coating, electrophoretic coating or impregnation.

[0072] Preferably, the light source for ultraviolet light irradiation includes any one or a combination of at least two of ultraviolet fluorescent lamps, mercury lamps, LED ultraviolet light sources, xenon lamps or argon mercury lamps.

[0073] Preferably, the wavelength range of the ultraviolet light is 100-400 nm (such as 130 nm, 160 nm, 190 nm, 220 nm, 250 nm, 280 nm, 310 nm, 340 nm or 170 nm, etc.), the irradiation time of the ultraviolet light is 10-300 s (such as 10 s, 30 s, 60 s, 90 s, 120 s, 150 s, 180 s, 210 s, 240 s or 270 s, etc.), and the irradiation intensity of the ultraviolet light is 50-2000 mW / cm 2 (such as 200 mW / cm 2 , 600 mW / cm 2 , 800 mW / cm 2 , 1000 mW / cm 2 , 1500 mW / cm 2 , 1800 mW / cm 2 , 2000 mW / cm 2 , 2400 mW / cm 2 or 2800 mW / cm 2 etc.).

[0074] Preferably, after the ultraviolet light irradiation in step (2), a cleaning step is further included.

[0075] Preferably, the concentration of the polymer anti-fouling material in the anti-fouling coating solution in step (2) is 0.1-100 g / L, such as 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 60 g / L, 70 g / L, 80 g / L or 90 g / L, etc.

[0076] In the present invention, the concentration of the polymer anti-fouling material in the anti-fouling coating solution is preferably 0.1-100 g / L. If the concentration of the polymer anti-fouling material is too high, the solution viscosity will increase, which will hinder the diffusion of the anti-fouling coating solution on the polyethylene surface, resulting in uneven grafting reaction. Discontinuous or too thick grafting layers may be formed on the surface, and even polymer agglomeration may be caused, instead reducing the effective grafting density; if the concentration of the polymer anti-fouling material is too small, the grafting points are sparse, a continuous anti-fouling coating cannot be formed, the surface coverage rate is low, and the anti-fouling effect is significantly reduced.

[0077] Preferably, the solvent includes any one or a combination of at least two of water, trifluoroethanol, hexafluoroisopropanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, acetone, ethanol, methanol, isopropanol, trifluoroacetic acid, dichloromethane, ether, toluene, carbon tetrachloride, cyclohexane or hexane.

[0078] In a third aspect, the present invention provides an application of the thin film material with anti-fouling function as described in the first aspect in a photobioreactor, aquaculture, or marine anti-fouling material.

[0079] Compared with the prior art, the present invention has at least the following beneficial effects:

[0080] In the present invention, the anti-fouling coating in the thin film material with anti-fouling function can reduce the attachment of biological fouling and promote fouling release. At the same time, by adding anti-fouling aids to the substrate layer, the substrate layer can fix the anti-fouling aids, making them stably present and slowly release. The anti-fouling aids can produce an avoidance effect or an inhibitory effect on proteins, bacteria, algal cells, etc. The two work together to improve the anti-fouling effect and have a long anti-fouling duration. The change in light transmittance of the thin film material with anti-fouling function after being cultured in Chlorella vulgaris algal solution for 7 days is ≤16%, and the adsorption density of microalgal cells is ≤2.45×10 6 / cm 2 , preferably, the change in light transmittance is ≤12%, and the adsorption density of microalgal cells is ≤2.32×10 6 / cm 2 . Description of the Drawings

[0081] Figure 1 Infrared spectra of the polymer anti-fouling material and its monomer provided in Preparation Example 1;

[0082] Figure 2 Ultraviolet absorption spectra of the polymer anti-fouling material and its monomer provided in Preparation Example 1;

[0083] Figure 3 For the polymer anti-fouling material provided in Preparation Example 3 1 HNMR spectrum;

[0084] Figure 4 Infrared spectra of tannic acid and tannic acid-rare earth complexes provided in Preparation Example 7;

[0085] Figure 5 Water contact angles measured for the polyethylene film provided in Comparative Example 1, the thin film material with anti-fouling function provided in Comparative Example 2, and the thin film material with anti-fouling function provided in Example 1 at the initial time, after being soaked in water for 1 week and half a month;

[0086] Figure 6 Test results of the anti-microalgae adsorption performance on the surface of the thin film material with anti-fouling function provided in Example 1. Detailed Embodiments

[0087] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0088] The sources of some components in the examples and comparative examples are as follows:

[0089] Polyethylene: grade STL FS7000, manufacturer is Satellite Chemical Co., Ltd.

[0090] Preparation Example 1

[0091] A polymer anti-fouling material, specifically polymer anti-fouling material A-1, which has the following structure:

[0092]

[0093] It is prepared by the following method:

[0094] Dissolve 1117.4 mg of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (denoted as SBAA), 168.1 mg of trifluoroethyl methacrylate (denoted as TFB) and 25 mg of 4-allyloxy-benzophenone (denoted as AOHBP) in 20 mL of trifluoroethanol in sequence. After dissolving them in sequence, add azobisisobutyronitrile. The mass of the azobisisobutyronitrile is 1% of the total mass of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, trifluoroethyl methacrylate and 4-allyloxy-benzophenone. Perform three vacuum pumping and nitrogen purging treatments on the system to make the reaction system proceed in a nitrogen atmosphere. Heat up to 70 °C and react for 24 h. After the reaction is completed, dropwise add the solution into ether to precipitate and stir for 30 min. After filtration, place the precipitate in a vacuum drying oven at 40 °C to dry, and redissolve it in 10 mL of trifluoroethanol. After complete dissolution, dropwise add the solution into 100 mL of ether to precipitate and stir for 30 min. After filtration, place the precipitate in a vacuum drying oven at 40 °C to dry to remove the unreacted trifluoroethyl methacrylate; then redissolve the solid in 10 mL of trifluoroethanol. After complete dissolution, dropwise add the solution into 100 mL of absolute ethanol to precipitate and stir for 30 min. After filtration, place the precipitate in a vacuum drying oven at 40 °C to dry, and repeat twice to remove the unreacted [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide and 4-allyloxy-benzophenone. Finally, dissolve the precipitation product in deionized water to form a 20 mL polymer solution. Dialyze the polymer solution in 1 L of deionized water for 48 h, and replace the deionized water regularly 3 times every 12 h. Pre-freeze the liquid in the dialysis bag for 5 h and then vacuum freeze-dry it for 60 h to obtain the polymer anti-fouling material A-1 (denoted as PSBA).

[0095] Preparation Example 2

[0096] A polymer anti-fouling material, specifically polymer anti-fouling material A-2, which has the following structure:

[0097]

[0098] It is prepared by the following method:

[0099] 1169.1 mg of [3-(methacrylamido)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt, 168.1 mg of trifluoroethyl methacrylate, 25 mg of 4-allyloxy-benzophenone, and azobisisobutyronitrile were successively dissolved in 20 mL of trifluoroethanol. The mass of azobisisobutyronitrile is 1% of the total mass of [3-(methacrylamido)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt, trifluoroethyl methacrylate, and 4-allyloxy-benzophenone. The system was evacuated and purged with nitrogen three times to carry out the reaction system in a nitrogen atmosphere. The temperature was raised to 70 °C and reacted for 24 h. After the reaction, the solution was dropped into ether to obtain a precipitate and stirred for 30 min. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C to dry, and then redissolved in 10 mL of trifluoroethanol. After complete dissolution, the solution was added dropwise to 100 mL of ether to precipitate and stirred for 30 min. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C to dry to remove the unreacted trifluoroethyl methacrylate; then the solid was redissolved in 10 mL of trifluoroethanol. After complete dissolution, the solution was added dropwise to 100 mL of absolute ethanol to precipitate and stirred for 30 min. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C to dry, and this was repeated twice to remove the unreacted [3-(methacrylamido)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt and 4-allyloxy-benzophenone. Finally, the precipitated product was dissolved in deionized water to form a 20 mL polymer solution. The polymer solution was dialyzed in 1 L of deionized water for 48 h, and the deionized water was changed regularly 3 times every 12 h. The liquid in the dialysis bag was pre-frozen for 5 h and then vacuum freeze-dried for 60 h to obtain the polymer anti-fouling material A-2.

[0100] Preparation Example 3

[0101] A polymer anti-fouling material, specifically polymer anti-fouling material A-3, which is different from Preparation Example 1 in that polymer anti-fouling material A-3 has the following structure:

[0102]

[0103] In its preparation, 1117.4 mg of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 168.1 mg of trifluoroethyl methacrylate and 25 mg of 4-allyloxy-benzophenone were replaced with 1169.1 mg of [3-(methacrylamido)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt, 168.1 mg of 4-(trifluoromethyl)styrene and 25.2 mg of 4-allyloxy-2-hydroxybenzophenone; the mass of azobisisobutyronitrile was 1% of the total mass of [3-(methacrylamido)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt, 4-(trifluoromethyl)styrene and 4-allyloxy-2-hydroxybenzophenone. Other conditions were the same as those in Preparation Example 1.

[0104] Preparation Example 4

[0105] A polymer antifouling material, specifically polymer antifouling material A-4, which has the following structure:

[0106]

[0107] It was prepared by the following method:

[0108] 1160.5 mg of 2-hydroxyethyl acrylate, 168.1 mg of hexafluorobutyl acrylate and 25.2 mg of 4-allyloxy-2-hydroxybenzophenone were successively dissolved in 20 mL of tetrahydrofuran. They were successively dissolved in 20 mL of tetrahydrofuran. The system was evacuated and purged with nitrogen three times to carry out the reaction system in a nitrogen atmosphere. The temperature was raised to 75 °C and reacted for 24 h. After the reaction, the solution was slowly dropped into 100 mL of petroleum ether and stirred for 30 min to obtain a precipitate. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C and dried, and then redissolved in 10 mL of tetrahydrofuran. After complete dissolution, the solution was added dropwise to 100 mL of petroleum ether for precipitation and stirred for 30 min. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C and dried to remove unreacted hexafluorobutyl acrylate, and then redissolved in 10 mL of tetrahydrofuran. The solution was added dropwise to 100 mL of ethanol for precipitation and stirred for 30 min. After filtration, the precipitate was placed in a vacuum drying oven at 40 °C and dried to remove unreacted 2-hydroxyethyl acrylate and 4-allyloxy-2-hydroxybenzophenone. Then the precipitated product was dissolved in deionized water to form a 20 mL polymer solution. The polymer solution was dialyzed in 1 L of deionized water for 48 h, and deionized water was replaced regularly three times every 12 h. The liquid in the dialysis bag was pre-frozen for 5 h and then vacuum freeze-dried for 60 h to obtain the polymer antifouling material A-4.

[0109] Preparation Example 5

[0110] A polymer antifouling material, specifically polymer antifouling material B-1, which is different from Preparation Example 1 in that polymer antifouling material B-1 has the following structure:

[0111]

[0112] During its preparation, trifluoroethyl methacrylate is not added, and the mass of azobisisobutyronitrile is 1% of the total mass of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide and 4-allyloxy-benzophenone, and other conditions are the same as those in Preparation Example 1.

[0113] Preparation Example 6

[0114] A polymer antifouling material, specifically polymer antifouling material B-2, which is different from Preparation Example 1 in that polymer antifouling material B-2 has the following structure:

[0115]

[0116] During its preparation, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide is not added, and the mass of azobisisobutyronitrile is 1% of the total mass of trifluoroethyl methacrylate and 4-allyloxy-benzophenone, and other conditions are the same as those in Preparation Example 1.

[0117] Preparation Example 7

[0118] An antifouling aid, specifically tannic acid-lanthanum complex, and the tannic acid-lanthanum complex is prepared by the following method: Add 20 mL of deionized water to a three-necked flask, add 1 mmol of tannic acid (denoted as TA) to the deionized water and stir until completely dissolved, then add 3 mmol of lanthanum nitrate and stir until completely dissolved. Then, gradually add ammonia water (mass percentage concentration is 25%) to the three-necked flask until the pH is 7, react at room temperature (25°C) for 2 h, and then centrifuge the reactant suspension in a high-speed refrigerated centrifuge at a speed of 8000 rpm for 6 min. Put the centrifuged precipitate into a vacuum drying oven at 80°C and dry for 8 h, then wash with deionized water and ethanol respectively, filter, and put the solid into a vacuum drying oven at 80°C and dry for 8 h to obtain the tannic acid-lanthanum complex (denoted as TA-LA).

[0119] Example 1

[0120] This embodiment provides a thin film material with anti-fouling function and its preparation method. The thin film material with anti-fouling function includes an inner layer, an intermediate layer, a surface layer, and an anti-fouling coating which are stacked in sequence. Both the inner layer and the surface layer include an anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 7). Based on the total mass of the inner layer being 100%, the mass percentage of the anti-fouling aid is 3.56%; based on the total mass of the surface layer being 100%, the mass percentage of the anti-fouling aid is 3.56%; the anti-fouling coating includes a polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1).

[0121] The preparation method includes the following steps:

[0122] (a) Mix 1.5 g of an anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 7), 40 g of a polyethylene resin (STLFS7000), 0.4 g of a plasticizer (dibutyl phthalate), 0.02 g of antioxidant 1010, and 0.2 g of a lubricant (stearic acid) to prepare the inner layer raw material.

[0123] (b) Mix 20 g of a polyethylene resin (STL FS7000), 0.2 g of a plasticizer (oleic acid amide), 0.01 g of an antioxidant (antioxidant 264), and 0.1 g of a lubricant (stearic acid) to prepare the intermediate layer raw material.

[0124] (c) Mix 1.5 g of an anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 7), 40 g of a polyethylene resin (STLFS7000), 0.4 g of a plasticizer (oleic acid amide), 0.02 g of an antioxidant (antioxidant 264), and 0.2 g of a lubricant (stearic acid) to prepare the surface layer raw material.

[0125] (d) Use the three-layer melt co-extrusion blow molding method to form the inner layer raw material obtained in step (a), the intermediate layer raw material obtained in step (b), and the surface layer raw material obtained in step (c) into a base film including an inner layer, an intermediate layer, and a surface layer stacked in sequence. The thickness of the inner layer is 0.03 mm, the thickness of the intermediate layer is 0.04 mm, and the thickness of the surface layer is 0.03 mm.

[0126] (e) Mix the polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1) and a solvent (deionized water) to prepare an anti-fouling coating solution. The concentration of the polymer anti-fouling material in the anti-fouling coating solution is 0.5 g / L;

[0127] The surface layer of the substrate film prepared in step (d) was ultrasonically cleaned successively with water, ethanol, and acetone, dried, then treated with plasma corona at a power of 50 W for 30 s, then immersed in the above anti-fouling coating solution for 0.5 h and taken out, dried, and irradiated with ultraviolet light. The wavelength range of the ultraviolet light was 365 nm, the irradiation time of the ultraviolet light was 180 s, and the irradiation intensity of the ultraviolet light was 2000 mW / cm 2 , and washed with deionized water to obtain the film material with anti-fouling function, denoted as PE-La-PSBA.

[0128] Example 2

[0129] This example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the polymer anti-fouling material A-1 provided in Preparation Example 1 is replaced with the polymer anti-fouling material A-2 provided in Preparation Example 2 with the same mass, and other conditions are the same as those in Example 1.

[0130] Example 3

[0131] This example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the polymer anti-fouling material A-1 provided in Preparation Example 1 is replaced with the polymer anti-fouling material A-3 provided in Preparation Example 3 with the same mass, and other conditions are the same as those in Example 1.

[0132] Example 4

[0133] This example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the polymer anti-fouling material A-1 provided in Preparation Example 1 is replaced with the polymer anti-fouling material A-4 provided in Preparation Example 4 with the same mass, and other conditions are the same as those in Example 1.

[0134] Example 5

[0135] This example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the polymer anti-fouling material A-1 provided in Preparation Example 1 is replaced with the polymer anti-fouling material B-1 provided in Preparation Example 5 with the same mass, and other conditions are the same as those in Example 1.

[0136] Example 6

[0137] This example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the polymer anti-fouling material A-1 provided in Preparation Example 1 is replaced with the polymer anti-fouling material B-2 provided in Preparation Example 6 with the same mass, and other conditions are the same as those in Example 1.

[0138] Example 7

[0139] This embodiment provides a thin film material with anti-fouling function and its preparation method. The difference from Embodiment 1 is only that tannic acid-lanthanum complex is replaced with copper 8-hydroxyquinoline of the same mass, and other conditions are the same as those in Embodiment 1.

[0140] Example 8

[0141] This embodiment provides a thin film material with anti-fouling function and its preparation method. The thin film material with anti-fouling function includes an inner layer, an intermediate layer, a surface layer and an anti-fouling coating which are stacked in sequence. The inner layer, the intermediate layer and the surface layer all include an anti-fouling aid (tannic acid-lanthanum complex). Calculated based on the total mass of the inner layer being 100%, the mass percentage of the anti-fouling aid in the inner layer is 5.80%; calculated based on the total mass of the surface layer being 100%, the mass percentage of the anti-fouling aid in the surface layer is 5.80%; the anti-fouling coating includes a polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1).

[0142] The preparation method includes the following steps:

[0143] (a) Mix 2.5 g of anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 7), 40 g of polyethylene resin (STLFS7000), 0.4 g of plasticizer (dibutyl phthalate), 0.02 g of antioxidant 1010, and 0.2 g of lubricant (stearic acid) to prepare the inner layer raw material.

[0144] (b) Mix 20 g of polyethylene resin (STL FS7000), 0.2 g of plasticizer (oleic acid amide), 0.01 g of antioxidant (antioxidant 264), and 0.1 g of lubricant (stearic acid) to prepare the intermediate layer raw material.

[0145] (c) Mix 2.5 g of anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 7), 40 g of polyethylene resin (STLFS7000), 0.4 g of plasticizer (oleic acid amide), 0.02 g of antioxidant (antioxidant 264), and 0.2 g of lubricant (stearic acid) to prepare the surface layer raw material.

[0146] (d) Use the inner layer raw material prepared in step (a), the intermediate layer raw material prepared in step (b), and the surface layer raw material prepared in step (c) to make a base film including an inner layer, an intermediate layer and a surface layer stacked in sequence by a three-layer melt co-extrusion blow molding method. The thickness of the inner layer is 0.03 mm, the thickness of the intermediate layer is 0.04 mm, and the thickness of the surface layer is 0.03 mm.

[0147] (e) Mix the polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1) and a solvent (deionized water) to prepare an anti-fouling coating solution, wherein the concentration of the polymer anti-fouling material in the anti-fouling coating solution is 5 g / L;

[0148] The surface layer of the substrate film prepared in step (d) was ultrasonically cleaned successively with water, ethanol, and acetone, dried, then treated with plasma corona at a power of 50 W for 10 s, then immersed in the above anti-fouling coating solution for 0.5 h and taken out, dried, and irradiated with ultraviolet light. The wavelength range of the ultraviolet light is 365 nm, the irradiation time of the ultraviolet light is 300 s, and the intensity of the ultraviolet light irradiation is 3000 mW / cm 2 , and washed with deionized water to obtain the film material with anti-fouling function.

[0149] Example 9

[0150] This example provides a film material with anti-fouling function and its preparation method. The anti-fouling film material includes an inner layer, a middle layer, a surface layer, and an anti-fouling coating arranged in layers in sequence. The surface layer includes an anti-fouling aid (tannic acid-lanthanum complex). Based on the total mass of the inner layer being 100%, the mass percentage of the anti-fouling aid in the inner layer is 1.22%; based on the total mass of the surface layer being 100%, the mass percentage of the anti-fouling aid in the surface layer is 1.22%; the anti-fouling coating includes a polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1).

[0151] The preparation method includes the following steps:

[0152] (a) Mix 0.5 g of anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 6), 40 g of polyethylene resin (STLFS7000), 0.4 g of plasticizer (dibutyl phthalate), 0.02 g of antioxidant 1010, and 0.2 g of lubricant (stearic acid) to prepare the inner layer raw material.

[0153] (b) Mix 20 g of polyethylene resin (STL FS7000), 0.2 g of plasticizer (oleic acid amide), 0.01 g of antioxidant (antioxidant 264), and 0.1 g of lubricant (stearic acid) to prepare the middle layer raw material.

[0154] (c) Mix 0.5 g of anti-fouling aid (tannic acid-lanthanum complex provided in Preparation Example 6), 40 g of polyethylene resin (STLFS7000), 0.4 g of plasticizer (oleic acid amide), 0.02 g of antioxidant (antioxidant 264), and 0.2 g of lubricant (stearic acid) to prepare the surface layer raw material.

[0155] (d) The inner layer raw material prepared in step (a), the intermediate layer raw material prepared in step (b), and the surface layer raw material prepared in step (c) are made into a film comprising an inner layer, an intermediate layer, and a surface layer stacked in sequence by a three-layer co-extrusion blow molding method. The thickness of the inner layer is 0.03 mm, the thickness of the intermediate layer is 0.04 mm, and the thickness of the surface layer is 0.03 mm, obtaining a base material layer.

[0156] (e) Mix a polymer anti-fouling material (polymer anti-fouling material A-1 provided in Preparation Example 1) and a solvent (deionized water) to prepare an anti-fouling coating solution. The concentration of the polymer anti-fouling material in the anti-fouling coating solution is 0.1 g / L;

[0157] The surface layer of the base film prepared in step (d) is ultrasonically cleaned with water, ethanol, and acetone in sequence, dried, then treated with plasma corona at a power of 50 W for 60 s, then immersed in the above anti-fouling coating solution for 0.5 h and taken out, dried, and irradiated with ultraviolet light. The wavelength range of the ultraviolet light is 365 nm, the irradiation time of the ultraviolet light is 30 s, and the intensity of the ultraviolet light irradiation is 200 mW / cm 2 , and washed with deionized water to obtain the film material with anti-fouling function.

[0158] Comparative Example 1

[0159] This comparative example provides a polyethylene film and its preparation method. The difference from Example 1 is only that the polyethylene film comprises an inner layer, an intermediate layer, and a surface layer stacked in sequence, does not include an anti-fouling coating, and the inner layer and the surface layer do not include an anti-fouling auxiliary agent (tannic acid-lanthanum complex).

[0160] In the preparation method, the anti-fouling auxiliary agent (tannic acid-lanthanum complex) is not added in steps (a) and (c), step (e) is not included, and a polyethylene film is prepared through steps (a)-(d), denoted as PE. Other conditions are the same as those in Example 1.

[0161] Comparative Example 2

[0162] This comparative example provides a film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the film material with anti-fouling function does not include an anti-fouling coating, step (e) is not included in the preparation method, and a film material with anti-fouling function is prepared through steps (a)-(d), denoted as PE-La. Other conditions are the same as those in Example 1.

[0163] Comparative Example 3

[0164] This comparative example provides a thin film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the inner layer and the surface layer do not include the anti-fouling additive (tannic acid-lanthanum complex), and the anti-fouling additive (tannic acid-lanthanum complex) is not added in steps (a) and (c) of the preparation method, and other conditions are the same as those in Example 1.

[0165] Comparative Example 4

[0166] This comparative example provides a thin film material with anti-fouling function and its preparation method. The difference from Example 1 is only that the inner layer and the surface layer do not include the anti-fouling additive (tannic acid-lanthanum complex), and the anti-fouling additive (tannic acid-lanthanum complex) is not added in steps (a) and (c) of the preparation method. The anti-fouling additive (tannic acid-lanthanum complex) is added to the anti-fouling coating solution in step (e), and the mass percentage of the anti-fouling additive (tannic acid-lanthanum complex) in the anti-fouling coating solution is 3.56%, and other conditions are the same as those in Example 1.

[0167] The following tests were carried out on the thin film materials with anti-fouling function provided in the above Examples 1-9 and Comparative Examples 2-4 and the polyethylene film provided in Comparative Example 1:

[0168] (1) Water contact angle: The water contact angle was measured using a contact angle measuring instrument, and the water contact angles at 5 different positions were measured and the average value was taken.

[0169] (2) Anti-microalgae adsorption performance: Chlorella sp. was used as a biological sample to test the anti-fouling performance. Before the culture experiment, the standard curve of the dry cell weight (CW) of algal cells and the optical density (OD 680 ) of the Chlorella sp. algal solution at 680 nm was measured, and its equation was: DCW = 0.1429×OD 680 +0.0059, the unit of DCW is g / L, and the linear correlation coefficient between DCW and OD 680 was determined. Chlorella sp. was cultured in a microcirculating flow pool environment, the flow rate of the water was 0.2 m / s, the culture medium was BG11 medium, the culture temperature was maintained at 25±1°C, the pH value of the Chlorella sp. algal solution was 7.0±0.3, and the light intensity of the light source was 200 μmol / (m 2 ·s). The thin film materials with anti-fouling function to be tested and the polyethylene film were immersed in the Chlorella sp. algal solution, and the OD 680 value of the Chlorella sp. algal solution was measured every morning and evening, and the dry cell weight of algal cells was obtained, and the growth trend of Chlorella sp. was recorded accordingly for 7 days;

[0170] The transmittance of the thin film materials with anti-fouling function and the polyethylene film before and after being placed in the Chlorella sp. algal solution for 7 days was measured, and the difference in transmittance before and after being placed in the Chlorella sp. algal solution for 7 days was the change in transmittance;

[0171] The film material with anti-fouling function and the polyethylene film that had been placed in the Chlorella vulgaris solution for 7 days were placed in a 50 mL centrifuge tube containing 20 mL of deionized water, sonicated in an ultrasonic cleaner for 30 min, and the number of algal cells was counted using a hemocytometer under a microscope. The cell density attached to the surface was calculated to obtain the adsorption density of microalgal cells.

[0172] The test results are shown in Table 1 below:

[0173] Table 1

[0174]

[0175] As can be seen from the content of Table 1, the change in light transmittance of the film material with anti-fouling function prepared in the present invention was ≤ 16% after being cultured in the Chlorella vulgaris solution for 7 days, and the adsorption density of microalgal cells was ≤ 2.45×10 6 / cm 2 .

[0176] Figure 1 The infrared spectra of the polymer anti-fouling material and its monomer provided for Preparation Example 1 are shown. Among them, PSBA is the polymer anti-fouling material A-1, SBAA is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, TFB is trifluoroethyl methacrylate, and AOHBP is 4-allyloxy-benzophenone. Compared with the monomer SBAA, the infrared absorption peaks of PSBA showed C=O and C-F absorption peaks at 1659 cm -1 and 1327 cm -1 , while the C=C absorption peak at 1615 cm -1 disappeared, indicating that the polymer anti-fouling material was successfully prepared.

[0177] Figure 2 The ultraviolet absorption spectra of the polymer anti-fouling material and its monomer for Preparation Example 1 are shown. PSBA had an ultraviolet absorption peak at 290 nm, proving the existence of the benzophenone structure, which can absorb ultraviolet light energy to form triplet acetonyl biradicals for photochemical reactions.

[0178] Figure 3 The 1 HNMR spectrum of the polymer anti-fouling material provided for Preparation Example 3 is shown. It can be seen from this that the hydrophilic monomer, hydrophobic monomer, and photo-reactive monomer reacted to prepare an anti-fouling functional polymer.

[0179] Figure 4 The infrared spectra of tannic acid and tannic acid-rare earth complex provided for Preparation Example 7 are shown. Among them, TA is tannic acid and TA-La is tannic acid-rare earth complex. It can be seen from this that the tannic acid-rare earth complex was successfully prepared.

[0180] Figure 5 Results of measuring the water contact angles of the polyethylene film provided in Comparative Example 1 (denoted as PE), the film material with anti-fouling function provided in Comparative Example 2 (denoted as PE-La), and the film material with anti-fouling function provided in Example 1 (denoted as PE-La-PSBA) at the initial stage, after being soaked in water for one week, taken out and dried on the surface, and after being soaked in water for half a month, taken out and dried on the surface. It can be seen from this that the film material with anti-fouling function provided in Example 1 has good hydrophilic wettability.

[0181] Figure 6 Results of the anti-microalgae adsorption performance test on the surfaces of the polyethylene film (PE) provided in Comparative Example 1 and the film material with anti-fouling function (PE-La-PSBA) provided in Example 1. The anti-fouling test was carried out under a flowing state to simulate the cultivation process of microalgae and test the anti-microalgae adsorption performance of the film material with anti-fouling function. The obtained results are as Figure 6 shown, where the ordinate of the growth curve is the dry weight of algal cells (g / L), and the ordinates of the other curves are the light transmittance (%). Chlorella vulgaris cultured in a microcirculating flow pool culture environment showed a positive growth trend from the 1st to the 6th day. When it reached the 6th day, the dry weight of Chlorella vulgaris cells would reach 0.32 g / L, and then showed a trend of slow growth, as Figure 6 shown in the growth curve. At the same time, with the extension of the culture time, the light transmittance of both PE and PE-La-PSBA showed a downward trend, as Figure 6 shown in the curves of PE and PE-La-PSBA. When cultured on the 7th day, the light transmittance decreased to about 29.3% and 67% respectively, and the decrease in the light transmittance of PE-La-PSBA was smaller. This indicates that the film material with anti-fouling function described in this application can greatly reduce the adsorption density of microalgae cells, maintain good light transmittance, and has excellent anti-fouling performance.

[0182] Compared with Example 1, if the polymer anti-fouling material does not contain hydrophilic groups (Example 6), the change in light transmittance increases, the adsorption density of microalgae cells increases, and the anti-fouling performance deteriorates.

[0183] Compared with Example 1, if the film material with anti-fouling function does not include an anti-fouling coating and the substrate layer does not include an anti-fouling additive (Comparative Example 1), the change in light transmittance increases significantly, the adsorption density of microalgae cells increases significantly, and the anti-fouling effect is poor.

[0184] Compared with Example 1, if the anti-fouling coating is not included (Comparative Example 2), the change in light transmittance increases, the adsorption density of microalgae cells increases, and the anti-fouling effect deteriorates.

[0185] Compared with Example 1, if the substrate layer does not include an anti-fouling additive (Comparative Example 3), the change in light transmittance increases, the adsorption density of microalgae cells increases, and the anti-fouling effect deteriorates.

[0186] Compared with Example 1, if the substrate layer does not include an anti-fouling additive and the anti-fouling coating includes an anti-fouling additive (Comparative Example 4), since the polymer anti-fouling material in the anti-fouling coating forms a very thin layer on the substrate layer through photo-grafting, the anti-fouling coating cannot coat and fix the anti-fouling additive. After being placed in the chlorella algal solution for a period of time, the anti-fouling additive falls off from the anti-fouling coating, resulting in a short anti-fouling duration and a deteriorated anti-fouling effect.

[0187] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A thin film material with anti-fouling function, characterized in that, The thin film material with anti-fouling function includes a substrate layer and an anti-fouling coating which are stacked in sequence. The substrate layer includes a resin and an anti-fouling aid, and the anti-fouling coating includes a polymer anti-fouling material.

2. The thin film material with anti-fouling function according to claim 1, characterized in that, The anti-fouling aid includes any one or a combination of at least two of metal-organic complexes, organosilicon compounds, metal chlorides, metal oxides, quaternary ammonium salt compounds or chlorophenol compounds; Preferably, the metal element in the metal-organic complex is selected from any one or a combination of at least two of titanium, silver, copper, zinc, aluminum, molybdenum, germanium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium or scandium; Preferably, the organic ligand in the metal-organic complex is selected from any one or a combination of at least two of tannic acid, 8-hydroxyquinoline, sorbic acid, 3-methyl-4-isopropylphenol, hydroxybenzoic acid, pyrithione, hexahydro-1,3,5-tris(hydroxyethyl)melamine, 1,2-benzisothiazol-3-one, 2-hydroxypyridine-N-oxide, 2-1 six-level must-be-N-oxide, gallate or catechin; Preferably, the organosilicon compound includes any one or a combination of at least two of methylsilane, ethylsilane, propenylsilane, aminosilane or epoxy silane; Preferably, the metal chloride includes any one or a combination of at least two of silver chloride, copper chloride, zinc chloride, rare earth chloride or aluminum chloride; Preferably, the metal oxide includes any one or a combination of at least two of zinc oxide, aluminum oxide, titanium dioxide, rare earth oxide or zirconium oxide; Preferably, the quaternary ammonium salt compound includes any one or a combination of at least two of cetyltrimethylammonium chloride, cetyl dimethylbenzylammonium chloride, hexadecanamide propyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, didodecyldimethylammonium chloride, dicocodimethylammonium chloride, trioctylmethylammonium chloride, cocamidopropyltrimethylammonium chloride, tallow bis(hydroxyethyl)methylammonium chloride, dodecyl bis(hydroxyethyl)methylammonium chloride, dodecyl dimethylbenzylammonium chloride, octadecyl dimethylbenzylammonium chloride, distearylmethylbenzylammonium chloride, lauryltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide, lauramidopropyltrimethylammonium chloride, cocoyl bis(hydroxyethyl)methylammonium chloride, dodecyltrimethylammonium chloride or docosyltrimethylammonium chloride; Preferably, the chlorophenol compound includes any one or a combination of at least two of tribrominated trichlorobenzene, dichlorophenol or p-dichlorophenol.

3. The thin film material with anti-fouling function according to claim 1 or 2, characterized in that, The resin includes any one or a combination of at least two of polyethylene, polypropylene, polyvinyl chloride, acetic acid-vinyl acetate copolymer, polyethylene terephthalate, polycarbonate, polyamide, polyethersulfone, polytetrafluoroethylene, polystyrene, polyurethane, polymethyl methacrylate or polylactic acid; Preferably, based on the total mass of the substrate layer being 100%, the mass percentage of the anti-fouling aid in the substrate layer is 0.01% - 10%; Preferably, the substrate layer further comprises other additives; Preferably, the other additives include any one or a combination of at least two of antioxidants, ultraviolet absorbers, nucleating agents, plasticizers, toughening agents, stabilizers, dispersants, lubricants, colorants, light stabilizers or antistatic agents.

4. The thin film material with anti-fouling function according to any one of claims 1 to 3, characterized in that The polymer antifouling material contains antifouling functional groups and photoreactive groups, and the polymer antifouling material has any one of the structures shown in Formula I, Formula II or Formula III: Wherein, R1, R2 and R3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X, Y and Z are each independently selected from an ester group, an amide group, an ether group, an aromatic group having 6 to 12 carbon atoms, an alkyleneoxy group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms; R4 is selected from hydrophilic groups; R5 is selected from hydrophobic groups; R6 is selected from photoreactive groups; Wherein a is an integer from 1 to 200, b is an integer from 1 to 200, and c is an integer from 1 to 200.

5. The thin film material with anti-fouling function according to claim 4, wherein, The hydrophilic group contains any one or a combination of at least two of a carboxyl group, an amino group, a hydroxyl group, a phosphate group or a sulfonic acid group; Preferably, the hydrophilic group is selected from any one of the following groups: Preferably, the hydrophobic group is selected from any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a siloxane group having 1 to 20 carbon atoms or a fluorine-substituted alkyl group having 1 to 20 carbon atoms; Preferably, the hydrophobic group is selected from any one of the following groups: Wherein, n is 1 to 20; Preferably, the photoreactive group is selected from any one of the following groups:

6. The thin film material with anti-fouling function according to any one of claims 1 to 5, characterized in that The polymer antifouling material is selected from any one of the following structures:

7. The thin film material with anti-fouling function according to any one of claims 1 to 6, characterized in that, The antifouling coating further comprises coating additives; Preferably, the coating additives include any one or a combination of at least two of a leveling agent, a dispersant, an antifoaming agent, an emulsifier, a diluent, a drying agent, a preservative, a pigment or a filler.

8. A method for preparing a thin film material with anti-fouling function as described in any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: (1) Mix an antifouling additive, a resin and optionally other additives to prepare a substrate layer; (2) Mix the polymer antifouling material, a solvent and optionally coating additives to form an antifouling coating solution, then place it on the substrate layer prepared in step (1), dry it, and irradiate it with ultraviolet light to obtain the thin film material with antifouling function.

9. The preparation method according to claim 8, characterized in that, Before the step of placing in step (2) on the substrate layer prepared in step (1), there is also a step of pretreating the substrate layer; Preferably, the pretreatment includes ultrasonic cleaning with water, ethanol and acetone in sequence, drying, and plasma corona; Preferably, the wavelength range of the ultraviolet light is 100 to 400 nm, the irradiation time of the ultraviolet light is 10 to 300 s, and the irradiation intensity of the ultraviolet light is 50 to 2000 mW / cm 2 ; Preferably, after the ultraviolet light irradiation in step (2), there is also a step of cleaning; Preferably, the concentration of the polymer antifouling material in the antifouling coating solution in step (2) is 0.1 to 100 g / L; Preferably, the solvent includes any one or a combination of at least two of water, trifluoroethanol, hexafluoroisopropanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, acetone, ethanol, methanol, isopropanol, trifluoroacetic acid, dichloromethane, diethyl ether, toluene, carbon tetrachloride, cyclohexane or hexane.

10. Use of a thin film material with anti-fouling function as described in any one of claims 1 to 7 in a photobioreactor, aquaculture, and marine anti-fouling materials.

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