An anti-biofouling patch and a preparation method and application thereof

Abstract

The application discloses a kind of marine biofouling prevention pasting cloth and its preparation method and application, belong to the technical field of antifouling material manufacturing;The application first uses silane coupling agent to modify antifouling particle nano-ZnO, which is blended with polyamide to prepare polyamide / ZnO composite fluff, then polyamide / ZnO composite fluff is flocked on the adhesive coated polypropylene fiber woven cloth, and the flocked surface is chemically modified to form a hydrophobic surface after drying, finally, the un-flocked side is coated with butyl rubber modified asphalt as a corrosion-resistant adhesive layer, and then the marine biofouling prevention pasting cloth is made by adding a non-stick pasting cloth;The application uses the way of physical and chemical combination secondary modification to prepare the pasting cloth material with marine biofouling prevention under the premise of not releasing harmful antifouling agent, uses the unstable characteristics of fluff to make marine organisms give up attaching to the flocked surface, and the pasting cloth can be cut and attached according to the specific application scene, which realizes the expansion of flocked method in the application of marine biofouling prevention.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of antifouling material manufacturing, and particularly relates to an antifouling cloth for marine organisms and a preparation method and application thereof. BACKGROUND

[0002] Marine organism fouling can increase the resistance of a ship, and the ship, marine resource development equipment and coastal facilities serving in a harsh marine environment are faced with serious problems of fouling, corrosion and fuel consumption, which further increases the environmental burden and causes huge economic losses and safety hazards.

[0003] Marine instruments and equipment and key devices are important means for carrying out marine investigation and observation, scientific research and marine resource development, and the surfaces of light-transmitting materials such as underwater optical windows, sensors and photographic lenses are affected by various factors such as scouring, corrosion and biological fouling. Meanwhile, the fouling materials such as barnacles, seaweed and mussels attached to the surfaces of the materials have a certain light absorption, and the light of different wavelengths absorbed by the fouling materials seriously interferes with the service performance and stability of the underwater optical equipment and increases the damage of the near-shore equipment. According to statistics, the annual loss caused by marine organism fouling is as high as tens of billions of dollars, and about 8-10% of the global offshore platforms have been involved in accidents, most of which are caused by marine organism fouling and marine corrosion.

[0004] Due to the complexity of the marine environment and the diversity of the biological community (>4000 species), marine antifouling is recognized as a worldwide problem. Many antifouling technologies have been applied to marine monitoring instruments, mainly including antifouling material design and antifouling paint, mechanical cleaning by brush, electrochemical electrolysis antifouling, ultraviolet lamp irradiation, ultrasonic prevention and control and the like.

[0005] So far, the antifouling coating is still the most common measure to prevent marine organisms from attaching to the surface of equipment. For example, the Chinese invention patent with the publication number CN103788811A and the application date of December 11, 2013 provides an environmentally friendly marine antifouling paint, which includes raw materials in parts by weight: epoxy phenolic resin 20-45 parts, titanium dioxide 0.5-1 part, biological antifouling agent 1-10 parts, titanium white 5-10 parts, kaolin 3-8 parts, mica powder 8-15 parts, solvent 18-28 parts, anti-settling agent 0.05-1 part and wetting dispersant 0.05-1 part. The paint contains pure natural biological antifouling agent, has a repelling effect on marine organisms, destroys the attachment ability of marine organisms and thus achieves the purpose of preventing pollution, and does not cause any toxic effect on the marine environment. However, such antifouling paint is prone to aging and cracking under sunlight, and even the seawater corrosion and scouring can easily cause the antifouling performance of the coating to decrease.

[0006] Sea lions can sway with the fluctuation of seawater due to a layer of fine and dense villi on the surface, which has the potential of biological antifouling. Therefore, it is feasible to use the principle of bionics to simulate the characteristics of large marine organisms to achieve biological antifouling through the epidermal structure, and to use the flocking method to mimic the biological structure characteristics to construct a new type of marine antifouling material. At present, the flocking method is commonly used to prepare fabrics, and the flocking method is less used in the preparation of marine antifouling materials, and there are problems such as limited substrate surface, large equipment coating difficulty, etc., which limits the application of the flocking method in marine antifouling. The Chinese invention patent with the publication number CN112127163A, the application date of which is September 21, 2020, describes a zwitterionic polymer modified vertical fiber marine antifouling material and a preparation method thereof. The invention uses zwitterionic polymer to modify the surface of the flocking fiber, introduces polymethacryloyl ethyl sulfobetaine, reduces the surface energy of the fiber surface, and improves the problem of biological adhesion of vertical fibers in marine antifouling. However, this method only modifies the surface, and the durability of the product is poor. At the same time, it is only suitable for regular surfaces, and it is difficult to handle parts such as elbows and corners, and the application is limited.

[0007] The Chinese invention patent with the publication number CN112127163A, the application date of which is September 21, 2020, describes a zwitterionic polymer modified vertical fiber marine antifouling material and a preparation method thereof. The invention uses zwitterionic polymer to modify the surface of the flocking fiber, introduces polymethacryloyl ethyl sulfobetaine, reduces the surface energy of the fiber surface, and improves the problem of biological adhesion of vertical fibers in marine antifouling. However, this method only modifies the surface, and the durability of the product is poor. At the same time, it is only suitable for regular surfaces, and it is difficult to handle parts such as elbows and corners, and the application is limited.

[0008] Therefore, it is of great practical significance and wide application prospect to study a kind of adhesive tape which can realize marine antifouling and is easy to coat by using the flocking method to mimic the biological structure characteristics. SUMMARY

[0009] In order to solve the defects in the prior art, the present application provides a kind of marine antifouling adhesive tape and its preparation method and application, under the premise of not releasing harmful antifouling agent, by using the way of physical and chemical combination secondary modification, marine antifouling adhesive tape material is prepared, marine organisms abandon the adhesion to the surface of flocking by the unstable characteristics of villi, and the adhesive tape can be cut and attached according to the specific application scene.

[0010] The technical scheme of the present application is as follows:

[0011] One of the objects of the present application is to provide a preparation method of marine antifouling adhesive tape, which comprises the following steps:

[0012] (1) using γ-aminopropyl triethoxysilane coupling agent to modify nano zinc oxide, the modified nano zinc oxide is marked as m-ZnO;

[0013] (2) after drying the polyamide particles in an oven, mix them with m-ZnO, melt and blend extrusion through a double screw extruder, and then granulate to obtain polyamide / ZnO composite material, and then obtain polyamide / ZnO composite filament by using a melt spinning machine after drying;

[0014] (3) the polyamide / ZnO composite filaments are cut by a cutting machine or crushed by a crusher, and then polyamide / ZnO composite fluff is prepared by cleaning, screening and electrostatic treatment;

[0015] (4) the polyamide / ZnO composite fluff is flocked on the polypropylene fiber woven cloth coated with glue, and the surface fluff is combed and the floating fluff is removed after drying;

[0016] (5) the flocked sample is soaked in potassium tert-butoxide and dicyclohexane 18-crown-6 ether for surface chemical modification treatment, and then silane reaction is added to form a flocking adhesive layer 4;

[0017] (6) the flocking adhesive layer 4 is washed and dried, a layer of butyl rubber modified asphalt is coated on the surface of the base film without flocking treatment as a corrosion-resistant adhesive layer 2, and then a non-stick cloth is attached to form an ocean anti-biofouling cloth, forming a non-stick cloth layer 1.

[0018] Further, in step (1), first, 95% ethanol solution is used to ultrasonically disperse nano-zinc oxide with a particle size of 50 nm, then the mixture is heated to 70-80°C in an oil bath with stirring, and pre-hydrolyzed for 1 h γ-aminopropyl triethoxysilane coupling agent is added, the mixture is separated by suction filtration after reaction for 3-5 h, and washed with ethanol three times, dried and ground into powder to obtain m-ZnO.

[0019] Further, in step (2), the drying conditions of polyamide and polyamide / ZnO composite material are both 80°C continuous drying for 12 h; the addition amount of m-ZnO in polyamide is 6 wt.%; the temperature of the first zone of the twin-screw extruder is 230-250°C, the temperature of the second zone is 260-280°C, the temperature of the third zone is 260-280°C, the temperature of the fourth zone is 230-250°C, and the temperature of the die head is 240-260°C, and the screw speed is 350 r / min; the spinning temperature of the melt spinning machine is 240-300°C, and the spinning speed is 10000-20000 m / min.

[0020] Further, in step (3), the length of the polyamide / ZnO composite filaments after cutting or crushing is 0.5 mm.

[0021] Further, in step (4), the glue is any one of acrylic resin, silicone rubber modified epoxy resin or polyurethane resin, the thickness of the glue coating is 0.2 mm, and the glue needs to be vacuumed for 45 min at room temperature before coating to remove bubbles in the glue.

[0022] Further, in step (4), the polyamide / ZnO composite fluff needs to be dried in a 40°C oven for 30 min before flocking.

[0023] Further, the step (4) is dried in the oven at 90 DEG C for 2h after the flocking treatment to accelerate the glue curing of the flocking layer.

[0024] Further, the silane in the step (5) can be selected from undecyl acetoxytrichlorosilane or perfluorotrichlorosilane.

[0025] The second object of the present application is to provide an anti-marine biofouling patch, which is characterized in that the anti-marine biofouling patch has four layers in total, including an anti-adhesion patch layer 1, an anti-corrosion glue layer 2, a polypropylene fiber woven cloth layer 3, and a flocking glue layer 4.

[0026] Further, the anti-marine biofouling patch has a width of 10-15 cm, the anti-corrosion glue layer 2 has a thickness of 0.7-1.2 mm, and the polypropylene fiber woven cloth layer 3 has a thickness of 0.3-0.6 mm.

[0027] Further, one side of the polypropylene fiber woven cloth layer 3 is formed into the flocking glue layer 4 by flocking polyamide / ZnO composite flocking, and the other side is provided with the anti-corrosion glue layer 2 composed of butyl rubber modified asphalt.

[0028] Further, the flocking coverage of the flocking glue layer 4 on the polypropylene fiber woven cloth layer 3 is greater than 85%.

[0029] Further, the anti-corrosion glue layer 2 is connected with the anti-adhesion patch by pasting to form the anti-adhesion patch layer 1.

[0030] Further, the anti-marine biofouling patch is used in a winding manner, and the next layer of patch and the previous layer of patch have an overlap of 0.5-1 cm.

[0031] The third object of the present application is to provide an application of the anti-marine biofouling patch in marine antifouling.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] 1. The present application innovates a preparation method of an anti-marine biofouling patch, which can prepare a patch material with anti-marine biofouling under the premise of not releasing harmful antifouling agents. The present application firstly uses a physical and chemical method, uses the unstable characteristics of flocking to make marine organisms give up attaching to the flocking surface, and uses a physical and chemical secondary chemical modification method to blend modified ZnO in polyamide to prepare a flocking matrix with antibacterial and antifouling effects. In addition, a surface silane modification method is further used to graft a large number of silicon hydroxyl alkane comb chains to the end of the amide bond, improve the water absorption of the polyamide material to form a hydrophobic surface, effectively reduce the attachment possibility of marine biofouling, and keep the patch surface clean.

[0034] 2、The functional layer is formed by flocking treatment on the polypropylene fiber woven cloth, and a butyl rubber modified asphalt adhesive layer is coated on the non-flocked surface, so that the anti-fouling patch cloth which can be cut and pasted is prepared; the disclosed anti-marine biofouling patch cloth can be pasted on the surface of steel, wood, ceramic and other materials, and the patch cloth can be cut and pasted according to the specific application scene, the size and shape requirements of the pasted object are small, the problem of difficult coating on large marine equipment is solved, the application of the flocking method in the anti-marine biofouling is greatly expanded, and the industrial production and application potential is great.

[0035] Reference signs

[0036] Figure 1 The electron microscope morphology of the anti-marine biofouling patch cloth described in Embodiment 1 of the present application is shown in the figure;

[0037] Figure 2 The structure schematic diagram of the anti-marine biofouling patch cloth described in Embodiment 1 of the present application is shown in the figure;

[0038] Wherein 1 is the anti-pasting cloth layer, 2 is the anti-corrosion adhesive layer, 3 is the polypropylene fiber woven cloth layer, and 4 is the flocking adhesive layer. DETAILED DESCRIPTION

[0039] The present application will be further described below in conjunction with the drawings and preferred embodiments, and the embodiments are only for illustrating the present application, not for limiting the scope of the present application.

[0040] The materials, reagents and the like used in the following examples can be obtained from commercial channels unless otherwise specified;

[0041] In the quantitative test in the following examples, three repeated experiments are set, and the average value is taken;

[0042] In the experimental method in the following examples, unless otherwise specified, it is a conventional method;

[0043] Embodiment 1

[0044] The present embodiment provides a preparation method of an anti-marine biofouling patch cloth, comprising the following steps:

[0045] S1, ZnO and 95% ethanol are added to a three-necked flask, ultrasonic dispersion is carried out for 30 min, and the flask is placed in a 75℃ oil bath pot for stirring, while pre-hydrolyzed 1h γ-aminopropyl triethoxysilane coupling agent KH550 is slowly added, and the reaction is carried out for 4h under the condition of 75℃ oil bath stirring, after the reaction is completed, the reaction product is separated by suction filtration and washed with ethanol for three times, the excessive KH550 is removed, the modified nano-ZnO is dried in a 60℃ oven for 12h and then ground into powder with a mortar, and the modified nano-ZnO is recorded as m-ZnO;

[0046] S2, drying the polyamide granules in an oven at 80°C for 12h, mixing the dried granules with m-ZnO, melt blending and extruding through a twin-screw extruder, and then pelletizing to prepare a polyamide / ZnO composite material, drying the composite material in an oven at 80°C for 12h, and then obtaining a polyamide / ZnO composite filament through a melt spinning machine; wherein the temperature of the first zone of the twin-screw extruder is 230-250°C, the temperature of the second zone is 260-280°C, the temperature of the third zone is 260-280°C, the temperature of the fourth zone is 230-250°C, and the temperature of the die head is 240-260°C; the screw rotation speed is 350r / min, and the spinning temperature of the melt spinning machine is 270°C; the spinning speed is 15000m / min;

[0047] S3, cutting or crushing the composite filament through a cutting machine or a crushing machine, and then cleaning, screening, and electrocoating to prepare polyamide / ZnO composite fluff with a length of 0.5mm and a diameter of 16μm, and drying in an oven at 40°C for 30min;

[0048]

[0049] S5, mixing 2mmol potassium tert-butoxide and 0.2mmol dicyclohexane and 18-crown-6 ether in a beaker at room temperature, immersing the flocking sample in the mixed solution for surface chemical modification treatment, then stirring at room temperature for 1h, adding 4mmol undecyl acetoxytrichlorosilane, and reacting at 50°C for 3h, and finally cleaning with ethanol and deionized water to remove surface residues, and drying to obtain a polyamide flocking surface.

[0050] S6, washing and drying the polyamide flocking surface, coating a layer of butyl rubber modified asphalt on the surface of the un-flocked base film as a 1.5mm corrosion-resistant adhesive layer, and then pasting a non-stick cloth to prepare an ocean anti-biofouling cloth with a width of 13cm.

[0051] Example 2

[0052] The embodiment provides a preparation method of an ocean anti-biofouling cloth, which comprises the following steps:

[0053] ​S1, in a three-necked flask, ZnO and 95% ethanol were added and ultrasonic dispersed for 30 min, and placed in an oil bath at 70°C for stirring, while slowly adding pre-hydrolyzed for 1 h γ-aminopropyl triethoxysilane coupling agent KH550, and reacted for 5 h under stirring at 70°C oil bath, after the reaction, separated by suction filtration and washed with ethanol three times, to remove the excess KH550, dried in an oven at 60°C for 12 h, and then ground into powder with a mortar, to obtain modified nano-ZnO, denoted as m-ZnO;

[0054] S2, the polyamide granules were dried in an oven at 80°C for 12 h, mixed with m-ZnO, and then extruded by a twin-screw extruder after melt blending, to obtain polyamide / ZnO composite materials, which were dried in an oven at 80°C for 12 h, and then obtained polyamide / ZnO composite filaments by a melt spinning machine; wherein the temperature of the first zone of the twin-screw extruder was 230-250°C, the temperature of the second zone was 260-280°C, the temperature of the third zone was 260-280°C, the temperature of the fourth zone was 230-250°C, and the temperature of the die head was 240-260°C; the screw rotation speed was 350 r / min, and the spinning temperature of the melt spinning machine was 24°C, and the spinning speed was 10000 m / min;

[0055] S3, the composite filaments were cut by a cutting machine or crushed by a crushing machine, and then cleaned, screened, and electrocoated to obtain polyamide / ZnO composite fluff with a length of 0.5 mm and a diameter of 16 μm, and dried in an oven at 40°C for 30 min;

[0056] S4, a polypropylene fiber woven cloth was used as a base film material, and the polyamide / ZnO composite fluff was flocked on the polypropylene fiber woven cloth coated with glue, and then cleaned and dried, and coated with a layer of 0.2 mm thick silicon rubber modified epoxy resin which had been vacuumized for 45 min to remove bubbles in the glue, flocked for 15 seconds, and the flocking coverage rate was 90%, and dried in an oven at 90°C for 2 h to accelerate the curing of the glue in the flocking layer, and then combed the surface fluff after drying to remove the floating fluff;

[0057] S5, 2 mmol of potassium tert-butoxide and 0.2 mmol of dicyclohexane and 18-crown-6 ether were mixed in a beaker at room temperature, and the flocked sample was immersed in the mixed solution for surface chemical modification treatment, and then stirred at room temperature for 1 h, 4 mmol of perfluorotrichlorosilane was added, and reacted at 50°C for 3 h, and finally cleaned with ethanol and deionized water to remove the surface residues, and dried to obtain a polyamide flocked surface.

[0058] S6, the polyamide flocked surface was washed and dried, a layer of butyl rubber modified asphalt was coated on the surface of the base film which was not subjected to flocked treatment as a 0.7 mm corrosion-resistant adhesive layer, and then a non-stick cloth was attached to prepare an ocean anti-biofouling cloth with a width of 10 cm.

[0059] Example 3

[0060] The embodiment provides an anti-biofouling patch, and a preparation method thereof, which comprises the following steps:

[0061] S1, adding ZnO and 95% ethanol into a three-necked flask, ultrasonic dispersion for 30 min, placing in an 80°C oil bath, stirring, slowly adding pre-hydrolyzed γ-aminopropyl triethoxysilane coupling agent KH550 for 1 h, reacting for 3 h under the condition of 80°C oil bath stirring, after the reaction is completed, separating by suction filtration and washing with ethanol for three times, removing the excessive KH550, drying in a 60°C oven for 12 h, and grinding into powder with a mortar to obtain modified nano-ZnO, denoted as m-ZnO;

[0062] S2, drying the polyamide granules in an 80°C oven for 12 h, mixing the dried granules with the m-ZnO, melt blending and extruding through a double-screw extruder, and then granulating to prepare a polyamide / ZnO composite material, drying the composite material in an 80°C oven for 12 h, and obtaining a polyamide / ZnO composite filament through a melt spinning machine; wherein the temperature of the first zone of the double-screw extruder is 230-250°C, the temperature of the second zone is 260-280°C, the temperature of the third zone is 260-280°C, the temperature of the fourth zone is 230-250°C, and the temperature of the die head is 240-260°C; the screw rotation speed is 350 r / min, and the spinning temperature of the melt spinning machine is 300°C; the spinning speed is 20000 m / min;

[0063] S3, after the composite filament is cut through a cutting machine or crushed through a crushing machine, the polyamide / ZnO composite fluff with a length of 0.5 mm and a diameter of 16 μm is prepared through cleaning, screening, electrocoating treatment and the like, and dried in a 40°C oven for 30 min;

[0064] S4, using a polypropylene fiber woven cloth as a base film material, the polyamide / ZnO composite fluff is flocked on the polypropylene fiber woven cloth coated with glue, and after cleaning and drying, a layer of 0.2 mm thick polyurethane resin which has been vacuumized for 45 min to remove bubbles in the glue is coated, flocking for 15 seconds, the flocking coverage rate is 88%, and the flocking layer is dried in a 90°C oven for 2 h to accelerate the glue curing, and after drying, the surface fluff is combed to remove the floating fluff;

[0065] S5, mixing 2 mmol potassium tert-butoxide and 0.2 mmol dicyclohexane and 18-crown-6 ether in a beaker at room temperature, immersing the flocking sample in the mixed solution for surface chemical modification treatment, then stirring at room temperature for 1 h, adding 4 mmol perfluorotrichlorosilane and reacting at 50°C for 3 h, and finally cleaning with ethanol and deionized water to remove the surface residues, and drying to obtain a polyamide flocking surface.

[0066] S6, washing and drying the polyamide flocked surface, coating a layer of butyl rubber modified asphalt on the surface of the un-flocked base film as a 1.2mm corrosion-resistant glue layer, and then pasting a non-stick cloth to make an ocean anti-biofouling cloth with a width of 15cm.

[0067] Comparative Example 1

[0068] The present embodiment provides a method for preparing a cloth, comprising the following steps:

[0069] S1, drying the polyamide granules in an 80℃ oven for 12h, mixing the dried granules with ZnO, and then extruding and granulating after melt blending through a double-screw extruder to prepare a polyamide / ZnO composite material, drying the composite material in an 80℃ oven for 12h, and then obtaining a polyamide / ZnO composite filament through a melt spinning machine; wherein the temperature of the first zone of the double-screw extruder is 230℃-250℃, the temperature of the second zone is 260℃-280℃, the temperature of the third zone is 260℃-280℃, the temperature of the fourth zone is 230℃-250℃, and the temperature of the die head is 240℃-260℃. The screw rotation speed is 350r / min, and the spinning temperature of the melt spinning machine is 270℃, and the spinning speed is 15000m / min;

[0070] S2, after cutting through a cutting machine or crushing through a crusher, the composite filament is washed, sieved, and electrocoated to prepare polyamide / ZnO composite flock with a length of 0.5mm and a diameter of 16μm, and then dried in a 40℃ oven for 30min;

[0071] S3, using a polypropylene fiber woven cloth as a base film material, flocking the polyamide / ZnO composite flock on the polypropylene fiber woven cloth coated with glue, and then coating a layer of 0.2mm-thick acrylic resin that has been vacuumed for 45min to remove bubbles in the glue, flocking for 15s, with a flocking coverage rate of 90%, drying in a 90℃ oven for 2h to accelerate the curing of the glue in the flocking layer, and then combing the surface flock after drying to remove loose flock;

[0072] S4, mixing 2mmol potassium tert-butoxide and 0.2mmol dicyclohexane and 18-crown-6 ether in a beaker at room temperature, immersing the flocked sample in the mixed solution for surface chemical modification treatment, stirring at room temperature for 1h, adding 4mmol undecyl acetoxytrichlorosilane and reacting at 50℃ for 3h, and finally washing with ethanol and deionized water to remove surface residues, and then drying to obtain a polyamide flocked surface.

[0073] S5, washing and drying the polyamide flocked surface, coating a layer of butyl rubber modified asphalt on the surface of the un-flocked base film as a 1.2mm corrosion-resistant glue layer, and then pasting a non-stick cloth to make an ocean anti-biofouling cloth with a width of 15cm.

[0074] Comparative Example 2

[0075] The embodiment provides a preparation method of the patch, comprising the following steps:

[0076] S1, adding ZnO and 95% ethanol into a three-necked flask, ultrasonic dispersion for 30 min, placing in a 75℃ oil bath pot for stirring, slowly adding a pre-hydrolyzed 1h γ-aminopropyl triethoxysilane coupling agent KH550, reacting for 4h under the condition of 75℃ oil bath stirring, after the reaction is completed, separating by suction filtration and washing with ethanol for three times, removing the excessive KH550, drying in a 60℃ oven for 12h, and then grinding into powder with a mortar to obtain modified nano ZnO, denoted as m-ZnO;

[0077] S2, drying the polyamide granules in an 80℃ oven for 12h, mixing the dried granules with the m-ZnO, and granulating after melt blending extrusion through a double-screw extruder to prepare a polyamide / ZnO composite material, drying the composite material in an 80℃ oven for 12h, and obtaining a polyamide / ZnO composite filament through a melt spinning machine; wherein the temperature of the first zone of the double-screw extruder is 230-250℃, the temperature of the second zone is 260-280℃, the temperature of the third zone is 260-280℃, the temperature of the fourth zone is 230-250℃, and the temperature of the die head is 240-260℃; the screw rotation speed is 350r / min, and the spinning temperature of the melt spinning machine is 270℃; the spinning speed is 15000m / min;

[0078] S3, after the composite filament is cut through a cutting machine or crushed through a crushing machine, the polyamide / ZnO composite fluff with a length of 0.5mm and a diameter of 16μm is prepared through cleaning, screening, electrocoating treatment and the like, and dried in a 40℃ oven for 30min;

[0079] S4, using a polypropylene fiber woven cloth as a base film material, the polyamide / ZnO composite fluff is flocked on the polypropylene fiber woven cloth coated with glue, and after cleaning and drying, a layer of 0.2mm-thick acrylic resin which has been vacuumized for 45min to remove bubbles in the glue is coated, flocking for 15s, the flocking coverage rate is 90%, and the flocking layer is accelerated to solidify the glue by drying in a 90℃ oven for 2h, and after drying, the surface fluff is combed to remove floating fluff;

[0080] S5, coating a layer of butyl rubber modified asphalt as a 1.5mm anticorrosive glue layer on the surface of the base film which is not subjected to flocking treatment, and then attaching an anti-sticking patch to prepare an ocean anti-biofouling patch with a width of 13cm.

[0081] Comparative example 3

[0082] The embodiment provides a preparation method of the patch, comprising the following steps:

[0083] S1, drying the polyamide granules in an 80℃ oven for 12h, mixing the dried granules with ZnO, melt blending and extruding through a twin-screw extruder, and then pelletizing to produce a polyamide / ZnO composite material, drying the composite material in an 80℃ oven for 12h, and then obtaining a polyamide / ZnO composite filament through a melt spinning machine; wherein the temperature of the first zone of the twin-screw extruder is 230-250℃, the temperature of the second zone is 260-280℃, the temperature of the third zone is 260-280℃, the temperature of the fourth zone is 230-250℃, and the temperature of the die head is 240-260℃. The screw rotation speed is 350r / min, and the spinning temperature of the melt spinning machine is 270℃, and the spinning speed is 15000m / min;

[0084] S2, after cutting through a cutting machine or crushing through a crusher, cleaning, screening, and electrocoating treatment, polyamide / ZnO composite fluff with a length of 0.5mm and a diameter of 16μm is obtained, and dried in a 40℃ oven for 30min;

[0085] S3, using a polypropylene fiber woven cloth as a base film material, polyamide / ZnO composite fluff is flocked on the polypropylene fiber woven cloth coated with glue, and after cleaning and drying, a layer of 0.2mm-thick acrylic resin that has been vacuumed for 45min to remove bubbles in the glue is coated, flocking for 15s, flocking coverage rate 90%, drying in a 90℃ oven for 2h to accelerate curing of the glue in the flocking layer, and after drying, the surface fluff is combed to remove loose fluff;

[0086] S4, coating a layer of butyl rubber modified asphalt as a 1.5mm anticorrosive glue layer on the surface of the base film that has not been subjected to flocking treatment, and then pasting a non-stick cloth to produce an ocean anti-biofouling cloth with a width of 13cm.

[0087] Comparative Example 4

[0088] The present example provides a method for preparing a cloth, comprising the following steps:

[0089] S1, adding ZnO and 95% ethanol in a three-necked flask, ultrasonic dispersion for 30min, placing in a 75℃ oil bath pot for stirring, while slowly adding pre-hydrolyzed γ-aminopropyl triethoxysilane coupling agent KH550 for 1h, reacting for 4h under the condition of stirring in a 75℃ oil bath, after the reaction is completed, separating by suction filtration and washing with ethanol for three times to remove excess KH550, drying in a 60℃ oven for 12h, and then grinding into powder with a mortar to obtain modified nano-ZnO, denoted as m-ZnO;

[0090] S2. Polyamide granules were dried in an 80℃ oven for 12 hours. The dried granules were mixed with m-ZnO and then melt-extruded through a twin-screw extruder to produce a polyamide / ZnO composite material. The composite material was then dried in an 80℃ oven for 12 hours and then melt-spun to obtain polyamide / ZnO composite filaments. The temperatures of the twin-screw extruder were as follows: Zone 1: 230℃~250℃; Zone 2: 260℃~280℃; Zone 3: 260℃~280℃; Zone 4: 230℃~250℃; Die head temperature: 240℃~260℃. The screw speed was 350 r / min, the melt spinning temperature was 270℃, and the spinning speed was 15000 m / min.

[0091] S3. After the composite filaments are cut by a cutting machine or crushed by a pulverizer, they are washed, sieved, and electroplated to produce polyamide / ZnO composite fluff with a length of 0.5 mm and a diameter of 16 μm, and then dried in an oven at 40℃ for 30 min.

[0092] S4. Using polypropylene fiber woven fabric as the base film material, polyamide / ZnO composite flocking is applied to the polypropylene fiber woven fabric coated with adhesive. After cleaning and drying, a 0.2mm thick layer of acrylic resin that has been vacuum-sealed for 45 minutes to remove air bubbles in the adhesive is applied. The flocking time is 15 seconds, and the flocking coverage is 70%. The flocking layer adhesive is dried in a 90℃ oven for 2 hours to accelerate the curing of the flocking layer. After drying, the surface flocking is combed to remove loose fibers.

[0093] S5. Mix 2 mmol potassium tert-butoxide and 0.2 mmol dicyclohexane and 18-crown-6 ether in a beaker at room temperature. Immerse the flocked sample in the mixture for surface chemical modification treatment. Then, stir and activate at room temperature for 1 h. Add 4 mmol undecylacetoxytrichlorosilane and react at 50 °C for 3 h. Finally, wash with ethanol and deionized water to remove surface residues. After drying, obtain a polyamide flocked surface.

[0094] S6. Wash and dry the polyamide flocked surface, apply a layer of butyl rubber modified asphalt as a 1.5mm anti-corrosion adhesive layer to the unflocked base film surface, and then apply an anti-adhesion cloth to make a 13cm wide marine anti-biofouling patch.

[0095] Performance testing

[0096] 1. Diatom adhesion experiment

[0097] The samples from Example 1 and Comparative Examples 1-4 were affixed to the surface of a bakelite board and placed in the same 25cm sterilized petri dish. 200ml of sterilized natural seawater was added, followed by 100ml of diatom solution (Small nautiloides and Feathered nautiloides), with a diatom quantity of 1×10⁻⁶. 5The sample was taken out after the experiment, and gently shaken in seawater for several times. The sample surface was washed with distilled water, and the sample was observed under an optical microscope at 10 times field of view. Ten different positions were selected to record the diatom adhesion, and the average value was calculated.

[0098] Test results:

[0099] Table 1: Diatom adhesion test results

[0100]

[0101] As can be seen from Table 1, in the diatom adhesion test, the surface of the anti-marine biofouling cloth prepared by the secondary modification method has very few diatoms, while the cloth without modification of nano-ZnO has more diatoms, and the cloth without fluff surface treatment has more diatoms, and the cloth without twice modification has many diatoms, and changing the fluff coverage can also affect the adhesion of diatoms. The adhesion of diatoms on the polypropylene woven cloth without fluff treatment is the most. It can be seen that the fluff method can greatly inhibit the adhesion of diatoms, and further modification can effectively reduce the adhesion of diatoms.

[0102] 2. Mussel adhesion experiment

[0103] The samples of the above embodiment 1 and comparative examples 1-4 were attached to the surface of the bakelite board and placed in sterile treated culture dishes, 8 small mussels with a diameter of 1 cm were placed in each culture dish, and 50 ml of sterile filtered pure seawater was added. After standing at room temperature for 48 h, the number of byssus of mussels was counted.

[0104] Test results:

[0105] Table 2: Mussel adhesion test results

[0106]

[0107] As can be seen from Table 2, the cloth prepared by the secondary modification method has the best experimental effect, i.e. the number of attached mussels is the least, and reducing the number of modifications or reducing the fluff coverage will increase the adhesion of mussels. In addition, it should be noted that the number of byssus discs of mussels attached to the polypropylene woven cloth without fluff treatment is the most, i.e. the fluff method can well inhibit the adhesion of mussels, and further modification can also reduce the number of mussels adhesion.

[0108] 3. Barnacle adhesion experiment

[0109] The samples of the above-mentioned Example 1 and Comparative Examples 1-4 were attached to the surface of a bakelite plate and were respectively put into a sterile treated culture dish, 20 white ridge barnacle cyprid larvae were added into each culture dish by using a disposable pipette, and the culture dishes were placed in dark condition at 25℃ for 40h, the number of the attached barnacles was observed, and the ratio of the number of the attached cyprid larvae to the total number of the added cyprid larvae was taken as the attachment ratio of the barnacles.

[0110] Test results:

[0111] Table 3: Barnacle attachment test results

[0112]

[0113] As can be seen from Table 3, the flocked modified sample can well inhibit the attachment of the barnacles. According to the attachment condition of the barnacle cyprid larvae, the surface of the substrate is not suitable for attachment, and the larvae will re-enter the seawater, thereby delaying the attachment. In the present test, the flocked modified patch is not suitable for the attachment condition of the barnacle cyprid larvae, and thus has the effect of biological antifouling.

[0114] The above-mentioned is only the embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation by using the content of the present application, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for preparing an anti-marine biofouling patch, characterized in that, The preparation method includes the following steps: (1) Nano zinc oxide was modified using γ-aminopropyltriethoxysilane coupling agent, and the modified nano zinc oxide was denoted as m-ZnO; (2) After drying the polyamide granules in an oven, they are mixed with m-ZnO, melt-blended and extruded by a twin-screw extruder, and then granulated to obtain a polyamide / ZnO composite material. After drying, polyamide / ZnO composite filaments are obtained by melt spinning. (3) Polyamide / ZnO composite filaments are cut by a cutting machine or crushed by a pulverizer, and then washed, sieved and electro-attached to obtain polyamide / ZnO composite fluff; (4) Using polypropylene fiber woven fabric layer (3) as base film material, the polyamide / ZnO composite fluff is flocked onto the polypropylene fiber woven fabric coated with glue, and after drying, the surface fluff is combed to remove the loose hair. (5) The flocked sample was immersed in potassium tert-butoxide and dicyclohexane-18-crown-6 ether for surface chemical modification treatment, and then silane was added to react and form a flocked adhesive layer (4), wherein the flocked coverage was greater than 85%; (6) Wash and dry the flocked adhesive layer (4), apply a layer of butyl rubber modified asphalt as an anti-corrosion adhesive layer (2) on the unflocked base film surface, and then apply an anti-adhesion cloth to make a marine anti-biofouling cloth to form an anti-adhesion cloth layer (1). In step (5), the silane is undecylacetoxytrichlorosilane or perfluorotrichlorosilane.

2. The method for preparing an anti-marine biofouling patch as described in claim 1, characterized in that, In step (1), 50 nm nano zinc oxide particles are first ultrasonically dispersed using 95% ethanol solution. Then, the mixture is stirred and heated to 70-80°C in an oil bath. γ-aminopropyltriethoxysilane coupling agent that has been pre-hydrolyzed for 1 h is added. After reacting for 3-5 h, the mixture is filtered and separated, washed three times with ethanol, dried, and ground into powder to obtain m-ZnO.

3. The method for preparing an anti-marine biofouling patch as described in claim 1, characterized in that, In step (2), the drying conditions for both polyamide and polyamide / ZnO composite material are continuous drying at 80℃ for 12h; the amount of m-ZnO added to polyamide is 6wt.%; the temperature of the first zone of the twin-screw extruder is 230℃~250℃, the temperature of the second zone is 260℃~280℃, the temperature of the third zone is 260℃~280℃, the temperature of the fourth zone is 230℃~250℃, the die head temperature is 240℃~260℃, and the screw speed is 350r / min; the spinning temperature of the melt spinning machine is 240℃~300℃, and the spinning speed is 10000~20000 m / min.

4. The method for preparing an anti-marine biofouling patch as described in claim 1, characterized in that, In step (3), the length of the polyamide / ZnO composite filament after cutting or crushing is 0.5 mm.

5. The method for preparing an anti-marine biofouling patch as described in claim 1, characterized in that, In step (4), the adhesive is any one of acrylic resin, silicone rubber modified epoxy resin or polyurethane resin. The thickness of the adhesive coating is 0.2 mm. Before coating, the adhesive needs to be vacuumed at room temperature for 45 minutes to remove air bubbles. The polyamide / ZnO composite flocking needs to be dried in an oven at 40°C for 30 minutes before flocking.

6. A marine biofouling-resistant patch prepared according to any one of claims 1 to 5, characterized in that, The structure of the anti-marine biofouling patch has four layers, including an anti-sticking fabric layer (1), an anti-corrosion adhesive layer (2), a polypropylene fiber woven fabric layer (3), and a flocking adhesive layer (4) that are bonded together in sequence; wherein the flocking coverage is greater than 85%.

7. The antifouling patch as described in claim 6, characterized in that, The width of the marine biofouling protection patch is 10-15cm, wherein the thickness of the anti-corrosion adhesive layer (2) is 0.7-1.2mm, and the thickness of the polypropylene fiber woven fabric layer (3) is 0.3-0.6mm.

8. The antifouling patch as described in claim 7, characterized in that, The polypropylene fiber woven fabric layer (3) has a flocked adhesive layer (4) formed on one side by flocking polyamide / ZnO composite fluff, and the other side is provided with the anti-corrosion adhesive layer (2) composed of butyl rubber modified asphalt; the anti-corrosion adhesive layer (2) is connected to the anti-adhesion cloth by being applied to form the anti-adhesion cloth layer (1).

9. The application of an antifouling patch prepared according to any one of claims 1 to 5 in marine antifouling.

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