Micro-reactive barrier material for marine biological fouling prevention as well as preparation method and application of micro-reactive barrier material

Abstract

The invention discloses a micro-reactive barrier material for marine biological fouling prevention as well as a preparation method and application of the micro-reactive barrier material. The material is prepared from the following raw materials in parts by mass: 75-87 parts of a graded composite material, 6-9 parts of a resin material, 2-5 parts of a curing agent, 0.1-0.7 part of a defoaming agent and 5-12 parts of slow-release inhibition particles, wherein the slow-release inhibition particles are composed of 35.4%-45.8% of a granulation base material and 54.2%-64.6% of active coated particles, and the active coated particles comprise calcium nitrite, myristic acid, palmitic acid and octadecanoic acid. The material can be used as a coating or prepared into a protective casting through a micro-reactive barrier prefabricating technology, a micro-porous reactive barrier is formed through natural erosion or hydraulic compression in different sea condition fields, a slow-release inhibition material is arranged in holes, a multi-stage, long-term and effective treatment mode can be provided for marine biofouling, and the service life of the material is prolonged. The material can be prefabricated and brushed, and is corrosion-resistant and high in strength, so that the risk that the material is damaged by extreme sea conditions is greatly reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine anti-biofouling, and particularly relates to a micro-reaction wall material for marine anti-biofouling and a preparation method and application thereof. BACKGROUND

[0002] With the rapid rise of marine development technology, the exploitation of marine resources, reclamation and island construction projects, port construction and other projects have developed rapidly, and the resulting marine biofouling has limited the development and utilization of marine resources by humans. Marine biofouling can cause ship navigation delays, offshore wharf corrosion, underwater probe signal shielding, seawater pipeline blockage, and offshore aquaculture yield reduction. How to reduce the damage caused by marine biofouling to human life and property and the marine ecosystem has become a difficult problem that needs to be solved urgently.

[0003] In the prior art, the following methods are usually used to deal with marine biofouling: 1. Physical anti-fouling, mainly through artificial intervention and cleaning of the fouling surface by artificial diving or submersible. The limitation of this method is that it is time-consuming and labor-intensive, has low efficiency, and occupies a long time, thereby affecting the efficiency of the wharf; if the fouling surface cannot be physically cleaned in time, secondary fouling will occur immediately. 2. Chemical anti-fouling, mainly through the release of toxicity by carrier or direct spraying. This method often leads to the mass killing of marine organisms, and such anti-fouling has poor durability in areas with turbulent water flow, resulting in generally poor results, and high toxicity also damages the marine ecosystem. 3. Biological inhibition, by artificially breeding natural enemies to prey on fouling organisms, this method changes the ecological environment of fouling organisms to inhibit the spread of fouling organisms. The disadvantage of this technology is that the natural enemies of fouling organisms require a stable living environment, and a certain abundance is often required to achieve inhibition, and the use scenario is too ideal; the fouling inhibition organisms also cause secondary pollution to the marine environment. Therefore, it is urgent to find a simple, efficient, widely applicable, and long-lasting method for inhibiting marine biofouling.

[0004] Permeable reactive barrier (PRB) technology is a common in-situ treatment technology in water pollution control. In recent years, solving various complex marine pollutants has become the focus of attention. The reaction wall-like material has become the main development trend of shore-based in-situ prevention of marine biofouling.

[0005] Patent CN118879145A discloses a self-polishing marine antifouling coating, mainly composed of a base material, an additive and a non-toxic antifouling agent. The non-toxic antifouling agent is a natural substance extracted from plants to prevent marine biofouling. From the repair method, this patent technology belongs to physical repair method, but due to its matrix material is multi-metal surface, there is a problem of coating and matrix applicability, the coating is difficult to solve the multi-level long-acting treatment problem of biological fouling, so the application scene is limited.

[0006] Patent CN118683696A discloses a method for removing marine attached organisms on the bottom of a ship. The method controls the temperature of the bottom of the ship to keep it within a range that is not conducive to the survival and attachment of barnacles and other organisms, thereby achieving the purpose of preventing and removing attached organisms. However, this method has limitations. Adjusting the temperature of the surrounding seawater of the protected object has high energy consumption and low efficiency, so it is difficult to promote.

[0007] The above-mentioned methods for dealing with marine biofouling can solve the problem of marine biofouling in experiments, but they have poor prevention and control ability in the face of the complexity of actual marine ecosystems and the uncontrollability of tidal currents. In order to solve the above problems, a new type of in-situ marine biofouling prevention and control material is urgently needed, which has the advantages of multi-level prevention and control of marine biofouling, long-lasting prevention and control, high prevention and control efficiency, low toxicity, strong environmental protection, etc., while also having the characteristics of traditional marine materials such as high strength, high impact resistance, corrosion resistance, etc. SUMMARY

[0008] In view of the shortcomings of the above-mentioned materials, in combination with the actual marine management difficulty and the needs of different marine engineering fields, the present application provides a micro-reaction wall material for marine biofouling prevention and its preparation method and application. The material is made into a protective casting by precasting micro-reaction wall technology, and after the material is solidified and formed, it is constructed in different marine conditions. The micro-porous reaction wall is formed by natural erosion or hydraulic pressure, and there is a slow-release inhibition material in the hole, which can perform multi-level and long-acting treatment on marine biofouling. Since the material can be precast, brushed, corrosion-resistant and has high strength, the risk of material damage by extreme marine conditions is greatly reduced.

[0009] To achieve the above-mentioned purpose, the following technical solutions are used: The micro-reaction wall material for marine biofouling prevention comprises the following raw materials by mass fraction: graded composite material 75-87 parts, resin material 6-9 parts, curing agent 2-5 parts, defoaming agent 0.1-0.7 parts, slow-release inhibition particles 5-12 parts; The raw materials of the slow-release inhibition particles include granulation base material and active coated particles. The active coated particle is composed of an active microsphere and a passivation layer coated on the active microsphere, the raw material of the active microsphere includes calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid, and the raw material of the passivation layer includes kerosene, glycerol, calcium stearate, and fatty alcohol polyoxyethylene ether.

[0010] Further, the active microsphere is prepared by mixing and granulating calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid, the active coated particle is prepared by mixing the active microsphere with kerosene, glycerol, calcium stearate, and fatty alcohol polyoxyethylene ether, and forming a passivation shell through a coating process, and the slow-release inhibition particle is obtained by granulating and forming after crushing the granulation base, adding water and stirring, and then adding the active coated particle.

[0011] Further, the slow-release inhibition particle is composed of the following raw materials in the following mass percentages: granulation base 35.4-45.8% and active coated particle 54.2-64.6%, the raw material of the active microsphere includes calcium nitrite 22.3-25.4 parts, myristic acid 27.6-38.3 parts, palmitic acid 25.2-32.6 parts, and octadecanoic acid 22.3-25.6 parts in terms of mass fraction, and the raw material of the passivation layer includes kerosene 15-30 parts, glycerol 5-15 parts, calcium stearate 30-60 parts, and fatty alcohol polyoxyethylene ether 10-20 parts.

[0012] Further, the graded composite material includes 2-4 mm basalt stones, 5-8 mm basalt stones, 6-9 mm basalt stones, 5-8 mm pebbles, powder, and fiber material.

[0013] Further, the resin material includes one or more of epoxy resin, polyurethane acrylate, unsaturated polyester resin, and vinyl ester resin mixed in any ratio. Preferably, the Shore D hardness of the resin material after curing is greater than or equal to 87.

[0014] Further, the curing agent includes one or more of amine curing agent, acid anhydride curing agent, polyurethane curing agent, acrylate curing agent, unsaturated polyester curing agent, and vinyl ester curing agent mixed in any ratio.

[0015] Further, the defoaming agent includes one or more of mineral oil-based defoaming agent, polyether-modified polyacrylate defoaming agent, aliphatic hydrocarbon defoaming agent, polyether-modified silicone defoaming agent, and short-chain silicone defoaming agent mixed in any ratio.

[0016] Illustratively, the resin material is polyurethane acrylate, the curing agent is polyurethane curing agent or acrylate curing agent, and the defoaming agent is polyether-modified silicone defoaming agent or short-chain silicone defoaming agent.

[0017] Exemplarily, the resin material is an unsaturated polyester resin, the curing agent is an unsaturated polyester curing agent such as a peroxide type unsaturated polyester curing agent, and the defoaming agent is a mineral oil based defoaming agent.

[0018] Exemplarily, the resin material is a vinyl ester resin, the curing agent is a vinyl ester curing agent such as a peroxide type vinyl ester curing agent, and the defoaming agent is a polyether modified polyacrylate defoaming agent.

[0019] Preferably, the resin material is an epoxy resin, the curing agent is an amine type curing agent, and the defoaming agent is a polyether modified siloxane defoaming agent.

[0020] Further, the granulation base material includes one or more of heavy burned magnesium, electrically fused magnesium, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, borax, boric acid, mixed in any proportion.

[0021] Further, the graded composite material includes, in terms of mass fraction, 5.7-9.2 parts of 2-4 mm basalt stone, 29.8-32.4 parts of 5-8 mm basalt stone, 0.5-1.7 parts of 6-9 mm basalt stone, 17.4-31.6 parts of 5-8 mm pebble, 39.2-43.7 parts of powder, and 0.07-0.12 parts of fiber material; wherein the powder includes one or more of SiO2 powder, silicon carbide powder, Al2O3 powder, fly ash, and carbon black, mixed in any proportion; and the fiber material includes copper plated steel fiber or / and sheared corrugated steel fiber.

[0022] Further, the copper plated steel fiber has a length of 13±1 mm and a diameter of 0.2±0.02 mm, and the sheared corrugated steel fiber has a length of 12±2 mm and a diameter of 1.4±0.5 mm.

[0023] Further, the 2-4 mm basalt stone, the 5-8 mm basalt stone, and the 6-9 mm basalt stone have a bulk density ≥3.0 g / cm 3 and a compressive strength ≥270 Mpa.

[0024] Further, the 5-8 mm pebble is natural pebble, has a mass content of SiO2 ≥98 parts, and a compressive strength ≥100 Mpa.

[0025] Further, the heavy burned magnesium has a purity greater than 92%.

[0026] Further, the electrically fused magnesium has a purity greater than 92%.

[0027] Further, the raw materials of the granulation base material include 20-60 parts of dead burned magnesium, 20-50 parts of electrically fused magnesium, 10-20 parts of ammonium dihydrogen phosphate (60 mesh), 5-15 parts of diammonium hydrogen phosphate (60 mesh), 5-15 parts of borax (80 mesh), and 0-5 parts of boric acid.

[0028] Further, the powder is a powder composite material including the following raw materials: 30-50 parts of SiO2 powder, 10-25 parts of silicon carbide powder, 15-30 parts of Al2O3 powder, 10-20 parts of fly ash, and 1-5 parts of carbon black.

[0029] The application further provides a preparation method of the micro-reaction wall material for marine anti-biofouling. Preparation of the active coated particles: calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid are mixed and granulated to obtain active microspheres, which can be extruded or kneaded by a granulator to form active microspheres, and the particle size can be 0.5-5 mm, for example, 0.5-1 mm, 1-1.5 mm, 1.5-2 mm, 2-2.5 mm, 2.5-3 mm, 3-3.5 mm, 3.5-4 mm, 4-4.5 mm, 4.5-5 mm, and any combination of mixed gradation particle sizes; then the active microspheres are mixed with kerosene, glycerol, calcium stearate, and fatty alcohol polyoxyethylene ether, and a passivation shell is coated by a rolling coating process to obtain the active coated particles; the preparation of the active microspheres can be carried out at room temperature to 65℃, for example, at 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, or 65℃; the rolling coating process is carried out at a temperature below 145℃, the coating time is ≤30 seconds, and the thickness of the coating layer after cooling and solidification can be 100-500 μm; for example, the rolling coating temperature is 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, or 145℃. Preparation of the slow-release inhibition particles: the granulation base material is broken, water is added and stirred, the mass of water can be 0.12% of the total mass of the granulation base material, and then the active coated particles are added before the granulation base material is solidified; the slow-release inhibition particles are formed by kneading and granulating with a granulator at room temperature, and the particle size can be 3-8 mm or adjusted according to the needs. The graded composite material, the resin material, the curing agent, the defoaming agent, and the slow-release inhibition particles are mixed to obtain the micro-reaction wall material for marine anti-biofouling.

[0030] The application further provides an application of the micro-reaction wall material for marine anti-biofouling, which is stirred with water to prepare a slurry, used as a coating material or injected into a mold to obtain the micro-reaction wall for marine anti-biofouling.

[0031] The technical principle of the present application is as follows: The micro-reaction wall material of the present application adopts a graded composite material, a resin material, a curing agent and a defoaming agent system as a base material, and the base material has high compactness and strong corrosion resistance after curing without intervention of a pore-forming material, so that it can provide strong support in a complex sea state environment; meanwhile, the system material has good adhesion and can be directly coated as a coating material; in addition, the base material formula is added with a fiber material to further increase the shock resistance and impact resistance of the material itself.

[0032] The present application adopts a part of the aggregate as a material of the slow-release inhibition particle, the slow-release inhibition particle can be directly mixed with the aggregate and directly participate in the prefabrication, the slow-release inhibition particle is prepared into a porous micro-particle by compounding with a granulation base material, the active coated calcium nitrite in the active coated particle can be used as an inhibitor of the fouling organisms in water, can effectively reduce the ability of the fouling organisms to seize food in the sea, affect the movement ability of the barnacle and shellfish organisms, and even cause the organisms to die, and the released nitrite can be used by nitrifying bacteria and denitrifying bacteria in seawater, and finally converted into non-toxic nitrogen. Myristic acid, palmitic acid and octadecanoic acid have inhibition function on the fouling organisms, and can effectively kill the barnacles and shellfish organisms. The coating process adopts kerosene, glycerol, fatty alcohol polyoxyethylene ether and other additives to granulate and knead the coated material, the main purpose is to prevent the slow-release inhibition particle from being corroded by the acid and alkali of the granulation base material during preparation, and to maintain the highest activity, and the coating film prepared by granulation and kneading can play a slow-release role in the later seawater inhibition experiment.

[0033] The slow-release inhibition particle is composed of a plurality of inhibitors, wherein the granulation base material uses ammonium dihydrogen phosphate, diammonium hydrogen phosphate and magnesium compound to generate a gel material, the gel material can be compounded with a plurality of inhibitors for granulation, or a single inhibitor can be used as a core and the gel material can be used as a shell to prepare the slow-release inhibition particle, the size of the sphere can be adjusted, the gradation can be adjusted, the ammonium phosphate material will generate a large amount of ammonia gas during hydration, and the ammonia gas bubbles can be sealed in the base material during the reaction of the material, forming a pore defect, so as to increase the porosity of the slow-release inhibition particle, and lay a foundation for the formation of the micro-reaction wall water channel in the later stage, part of the active coated particles will be curled in the micropore or gathered around it, thereby greatly increasing the active sites of the slow-release inhibition particle and reducing the fracturing distance.

[0034] The slow-release mechanism of the slow-release inhibitory particles of the present invention is as follows: after the slow-release inhibitory particles are mixed and formed with the granulation matrix material, they are constructed in a marine environment. When the seawater depth increases, the micropores of some of the slow-release inhibitory particles are fractured, and then inhibitors of marine biological fouling materials burst out. Since the slow-release inhibitory particles have multi-graded properties, they can be distributed in large quantities in the matrix for long-term release. At the same time, the slow-release inhibitory particles have a multi-layer structure and there are multiple types of inhibitors between different shells, which can also increase the slow-release effect. After the slow-release inhibitory particles are fractured, some particles are deformed, enabling them to form a micro-reaction wall structure inside the matrix. When seawater impacts the interior, some particles can be washed inside the matrix with the ocean current, thereby accelerating the wear of the slow-release inhibitory particle shell and increasing the contact area of ​​the active substance, ultimately realizing a multi-stage purification process of "fracture / flushing-damage-release-inhibition" for biological fouling.

[0035] Compared with the prior art, the present invention has the following beneficial effects: 1. The micro-reaction wall material for marine biofouling prevention prepared by the present invention uses graded composite materials, resin materials, curing agents, and defoaming agents as the base materials of the support materials. This material is mainly prepared by polymerization of rock-based mineral materials. It does not require any anti-corrosion technology and can effectively achieve applications in various harsh working conditions such as acid and alkali corrosion resistance, seawater and high-salt environment corrosion resistance; in terms of mechanics, it has the advantages of high compressive and flexural strength, good shock absorption stability, etc.; this material has high viscosity during the polymerization process, can be bonded to metals and building materials, and has high bonding strength; this material has ultra-high precision and excellent machinability, the accuracy after demoulding can reach 0.1mm / m, and strong thermal stability; the above advantages can replace existing shore-based support materials, shore-based anti-corrosion materials, marine Troy A-class drilling platforms, island infrastructure materials, etc. in the marine field.

[0036] 2. The marine anti-biofouling micro-reaction wall material prepared by the present invention uses reaction wall technology to target marine fouling. The slow-release inhibitory particles can be used as aggregates to polymerize into a matrix with the rock-based mineral materials, and serve as pore-forming agents for the micro-reaction wall in the matrix. The pore-forming mechanism is physical pore-forming. Compared with the chemical gasification pore-forming system, it has the advantages of not affecting the overall structure, high strength, and controllable pore size grading. The slow-release inhibitory particle granulation base material uses a porous material generated by ammonium dihydrogen phosphate, diammonium hydrogen phosphate and magnesium compounds with a porosity of 34~56%. The porous material can provide multiple sites for adsorption of active ingredients for anti-biofouling, thereby increasing the anti-biofouling efficiency; at the same time, the pore size and connectivity of the porous material are adjustable, and thus the strength of the slow-release inhibitory particles can be adjusted, providing different anti-fracturing strengths for matrix materials with different depth requirements.

[0037] 3. The slow-release inhibitory particles of the micro-reaction wall material for marine anti-biofouling prepared by the present invention adopt a multi-site composite anti-biofouling active agent. The surface of the active agent is coated with a passivation shell. During the mixing reaction with ammonium dihydrogen phosphate, diammonium hydrogen phosphate and magnesium compound, it does not participate in the acid-base neutralization reaction, thereby ensuring its own activity. As the granulation base material of the slow-release inhibitory particles is continuously eroded and consumed, some active sites will continue to precipitate, achieving multi-level inhibition and long-lasting biological inhibition. The active substance of the slow-release inhibitory particles is an environmentally friendly material and does not pollute the ocean.

[0038] 4. The invention's refined sustained-release inhibitory particles are damaged and pore-forming as ocean pressure and ocean current erosion cause them to break. As the damage mechanism gradually extends, some pores are gradually opened up, forming pores without affecting the strength. After the surface of the sustained-release inhibitory particles is damaged, most of the residues will be stuck in the matrix material and "peristalsize in the core-shell cavity" as they are flushed by seawater. This method, on the one hand, reduces the chance of the active substance being washed away, and on the other hand, can effectively increase the contact area between the active substance and marine fouling organisms. DETAILED DESCRIPTION

[0039] The present invention will be further described with reference to specific embodiments. It should be understood that these embodiments are intended to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that, after reading the content of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined in the present application.

[0040] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for the purpose of describing specific specific embodiments, rather than for the purpose of limiting the scope of protection of the present invention. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art. The test methods for which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under the conditions recommended by the manufacturers. In addition to the specific methods, equipment, and materials used in the examples, any methods, equipment, and materials of the prior art that are similar or equivalent to the methods, equipment, and materials described in the examples of the present invention may also be used to implement the present invention, based on the prior art mastery of those skilled in the art and the description of the present invention.

[0041] Example 1. The present invention provides a micro-reaction wall material for marine anti-biofouling, comprising the following raw materials in parts by mass: 75-87 parts of graded composite material, 6-9 parts of resin material, 2-5 parts of curing agent, 0.1-0.7 parts of defoaming agent, and 5-12 parts of slow-release inhibitory particles.

[0042] The graded composite material comprises, in terms of mass fraction, 5.7-9.2 parts of 2-4 mm basalt stone, 29.8-32.4 parts of 5-8 mm basalt stone, 0.5-1.7 parts of 6-9 mm basalt stone, 17.4-31.6 parts of 5-8 mm pebble, 39.2-43.7 parts of powder, and 0.07-0.12 parts of fiber material; the 2-4 mm basalt stone, 5-8 mm basalt stone and 6-9 mm basalt stone have a volume density of ≥3.0 g / cm 3 and a compressive strength of ≥270 Mpa; the 5-8 mm pebble is natural pebble, has a mass content of SiO2 of ≥98 parts, and a compressive strength of ≥100 Mpa. The powder comprises one or more of SiO2 powder, silicon carbide powder, Al2O3 powder, fly ash and carbon black in any proportion; for example, the powder is a powder composite material comprising, in terms of mass fraction, 30-50 parts of SiO2 powder, 10-25 parts of silicon carbide powder, 15-30 parts of Al2O3 powder, 10-20 parts of fly ash and 1-5 parts of carbon black. The fiber material comprises copper-plated steel fiber or / and sheared corrugated steel fiber; the copper-plated steel fiber has a length of 13±1 mm and a diameter of 0.2±0.02 mm; the sheared corrugated steel fiber has a length of 12±2 mm and a diameter of 1.4±0.5 mm.

[0043] The resin material includes one or more of epoxy resin, polyurethane acrylate, unsaturated polyester resin, vinyl ester resin mixed in any ratio. The curing agent includes one or more of amine curing agent, acid anhydride curing agent, polyurethane curing agent, acrylate curing agent, unsaturated polyester curing agent, vinyl ester curing agent mixed in any ratio. The defoaming agent includes one or more of mineral oil-based defoaming agent, polyether-modified polyacrylate defoaming agent, aliphatic hydrocarbon defoaming agent, polyether-modified silicone defoaming agent, short-chain silicone defoaming agent mixed in any ratio. Exemplarily, the resin material is polyurethane acrylate, the curing agent is polyurethane curing agent or acrylate curing agent; the defoaming agent is polyether-modified silicone defoaming agent, short-chain silicone defoaming agent. Exemplarily, the resin material is unsaturated polyester resin, the curing agent is unsaturated polyester curing agent such as peroxide unsaturated polyester curing agent, and the defoaming agent is mineral oil-based defoaming agent. Exemplarily, the resin material is vinyl ester resin, the curing agent is vinyl ester curing agent such as peroxide vinyl ester curing agent; and the defoaming agent is polyether-modified polyacrylate defoaming agent. Preferably, the resin material is epoxy resin, the curing agent is amine curing agent, and the defoaming agent is polyether-modified silicone defoaming agent. Exemplarily, the resin material is epoxy resin G-Tack 1050A, the curing agent is amine curing agent G-Tack 1050B, and the Shore D hardness of the resin material after curing is greater than or equal to 87; the defoaming agent is BYK530. The resin material is epoxy resin G-Tack 1090A, the curing agent is amine curing agent G-Tack 1090B, and the Shore D hardness of the resin material after curing is greater than or equal to 87; the defoaming agent is BYK530.

[0044] The slow-release inhibiting granule is composed of raw materials in the following mass percentages: granulation base 35.4-45.8%, active coated granule 54.2-64.6%; the active coated granule is composed of active microspheres and a passivation layer coated on the active microspheres; the active microspheres are prepared by mixing and granulating calcium nitrite, myristic acid, palmitic acid and octadecanoic acid; the active coated granule is prepared by mixing the active microspheres with kerosene, glycerol, calcium stearate and fatty alcohol polyoxyethylene ether, and forming a passivation shell through a roller compaction coating process; the slow-release inhibiting granule is prepared by crushing the granulation base, adding water and stirring, and adding the active coated granule before the granulation base is solidified, and then granulating and molding to obtain the slow-release inhibiting granule.

[0045] The granulation base material includes one or more of heavy burned magnesium, electrically fused magnesium, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, borax, boric acid mixed in any ratio. The purity of the heavy burned magnesium is greater than 92%. The purity of the electrically fused magnesium is greater than 92%. Exemplarily, the raw materials of the granulation base material include, in mass fraction: 20-60 parts of heavy burned magnesium, 20-50 parts of electrically fused magnesium, 10-20 parts of ammonium dihydrogen phosphate, 5-15 parts of diammonium hydrogen phosphate, 5-15 parts of borax, and 0-5 parts of boric acid.

[0046] The raw materials of the active microspheres include, in mass fraction: 22.3-25.4 parts of calcium nitrite, 27.6-38.3 parts of myristic acid, 25.2-32.6 parts of palmitic acid, and 22.3-25.6 parts of octadecanoic acid; and the raw materials of the passivation layer include: 15-30 parts of kerosene, 5-15 parts of glycerol, 30-60 parts of calcium stearate, and 10-20 parts of fatty alcohol polyoxyethylene ether.

[0047] In addition, the application also provides a preparation method of the micro-reaction wall material for marine anti-biofouling, which is prepared according to the proportion range of each raw material in Example 1 and includes the following steps: Preparation of the active coated particles: the calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid are mixed and granulated to obtain active microspheres, which can be extruded or kneaded by a granulator to form active microspheres with a particle size of 0.5-5 mm. Exemplarily, the particle size is 0.5-1 mm, 1-1.5 mm, 1.5-2 mm, 2-2.5 mm, 2.5-3 mm, 3-3.5 mm, 3.5-4 mm, 4-4.5 mm, 4.5-5 mm, or any combination of the above. Then, the active microspheres are mixed with kerosene, glycerol, calcium stearate, and fatty alcohol polyoxyethylene ether, and a passivation shell is coated by a roller coating process to obtain active coated particles. The preparation of the active microspheres can be carried out at a temperature of room temperature to 65°C. Exemplarily, the temperature is 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or 65°C. The roller coating process is carried out at a temperature of 145°C or lower, and the coating time is ≤30 seconds. After cooling and solidification, the thickness of the coating layer can be 100-500 μm. Exemplarily, the roller coating temperature is 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 145°C. Preparation of the slow-release inhibition particles: the granulation base material is broken and stirred with water, and the mass of the water can be 0.12% of the total mass of the granulation base material. Then, the active coated particles are added before the granulation base material solidifies. The slow-release inhibition particles are formed by kneading and granulating in a granulator at room temperature, and the particle size can be 3-8 mm or adjusted according to the needs. The graded composite material, resin material, curing agent, defoaming agent and slow-release inhibiting particles are mixed to obtain the micro-reaction wall material for marine anti-biofouling.

[0048] In the embodiment 3, the application further provides a use of the micro-reaction wall material for marine anti-biofouling, wherein the micro-reaction wall material for marine anti-biofouling in the embodiment 1 is stirred with water to prepare a slurry, and the slurry is used as a coating or is injected into a mold to prepare the micro-reaction wall for marine anti-biofouling.

[0049] In the embodiment 4, the micro-reaction wall material for marine anti-biofouling is prepared by the method in the embodiment 2.

[0050] The graded composite material 78wt%, resin material 8wt%, curing agent 2.7wt%, defoaming agent 0.2wt% and slow-release inhibiting particles 11.1wt% are added into an inclined stirrer, the rotor rotates at 240(rpm) and the tray rotates at 50(rpm), and then the mixture is stirred uniformly and injected into a mold.

[0051] The graded composite material includes 5.7-9.2 parts of 2-4mm basalt stone, 29.8-32.4 parts of 5-8mm basalt stone, 0.5-1.7 parts of 6-9mm basalt stone, 17.4-31.6 parts of 5-8mm pebble, 39.2-43.7 parts of powder and 0.07-0.12 parts of fiber material, according to the mass fraction. 3 The volume density of the 2-4mm basalt stone, 5-8mm basalt stone and 6-9mm basalt stone is greater than or equal to 3.0g / cm

[0052] The slow-release inhibiting particles are composed of 38.5wt% granulation base material and 61.5wt% active coated particles, wherein the mass percentage of each raw material in the granulation base material is 32% of heavy-burned magnesium, 32% of electrically fused magnesium, 16% of ammonium dihydrogen phosphate, 9% of diammonium hydrogen phosphate and 11% of borax; the mass percentage of each raw material in the active microspheres in the active coated particles is 23.4wt% of calcium nitrite, 29.1wt% of myristic acid, 25.2wt% of palmitic acid and 22.3wt% of octadecanoic acid; and the raw materials of the passivation layer include kerosene, glycerol, calcium stearate and fatty alcohol polyoxyethylene ether.

[0053] Example 5, the graded composite material 75wt%, resin material 9wt%, curing agent 2.9wt%, defoaming agent 0.2wt%, slow-release inhibition particles 12.9wt% are added to the inclined stirrer, the rotor speed is 240(rpm), the speed of the tray is 50(rpm), and the mold is injected after uniform stirring.

[0054] The rest is consistent with example 4.

[0055] Example 6, the graded composite material 75wt%, resin material 9wt%, curing agent 2.9wt%, defoaming agent 0.2wt%, slow-release inhibition particles 12.9wt% are added to the inclined stirrer, the rotor speed is 240(rpm), the speed of the tray is 50(rpm), and the mold is injected after uniform stirring.

[0056] The slow-release inhibition particles are composed of 24.5wt% granulation base material and 75.5wt% active coated particles. The mass percentage of each raw material in the granulation base material is: heavy burned magnesium 30wt%, electrically fused magnesium 35wt%, ammonium dihydrogen phosphate 15wt%, diammonium hydrogen phosphate 9wt%, borax 11wt%; The mass percentage of each raw material in the active microspheres of the active coated particles is: calcium nitrite 23.4wt%, myristic acid 29.1wt%, palmitic acid 25.2wt%, octadecanoic acid 22.3wt%).

[0057] The rest is consistent with example 4.

[0058] Example 7, the difference from example 4 is that the powder is SiO2 powder, and the raw materials of the passivation layer include: kerosene 20 parts, glycerol 10 parts, calcium stearate 40 parts, and fatty alcohol polyoxyethylene ether 15 parts.

[0059] Example 8, the difference from example 7 is that the powder is a composite material, which includes SiO2 powder 40 parts, fly ash 15 parts.

[0060] Example 9, the difference from example 7 is that the powder is a composite material, which includes SiO2 powder 40 parts, silicon carbide powder 20 parts, Al2O3 powder 20 parts, fly ash 15 parts, and carbon black 3 parts.

[0061] Preparation example 1: The graded composite material 78wt%, resin material 8wt%, curing agent 2.7wt%, defoaming agent 0.2wt%, slow-release inhibition particles 11.1wt% are added to the inclined stirrer, the rotor speed is 240(rpm), the speed of the tray is 50(rpm), and the mold is injected after uniform stirring.

[0062] The sustained-release inhibiting particles are composed of 100wt% active coated particles, and the mass percentage of each raw material of the active microspheres in the active coated particles is: calcium nitrite 23.4wt%, myristic acid 29.1wt%, palmitic acid 25.2wt%, and octadecanoic acid 22.3wt%.

[0063] The rest is consistent with Example 4.

[0064] Preparation Example 2: The graded composite material 78wt%, the resin material 8wt%, the curing agent 2.7wt%, the defoaming agent 0.2wt%, and the sustained-release inhibiting particles 11.1wt% are added into the inclined stirrer, the rotor rotation speed is 240(rpm), and the material pan rotation speed is 50(rpm). After uniform stirring, the mixture is injected into the mold.

[0065] The sustained-release inhibiting particles are composed of 100wt% granulation base material, and the mass percentage of each raw material in the granulation base material is: dead-burned magnesium 32wt%, fused magnesium 32wt%, ammonium dihydrogen phosphate 16wt%, diammonium hydrogen phosphate 9wt%, and borax 11wt%.

[0066] The rest is consistent with Example 4.

[0067] Preparation Example 3: The graded composite material 78wt%, the resin material 8wt%, the curing agent 2.7wt%, and the defoaming agent 0.2wt% are added into the inclined stirrer, the rotor rotation speed is 240(rpm), and the material pan rotation speed is 50(rpm). After uniform stirring, the mixture is injected into the mold.

[0068] The rest is consistent with Example 4.

[0069] The resin material used in the above Examples 4-9 and Preparation Examples 1-3 is epoxy resin G-Tack 1050A, the curing agent is amine curing agent G-Tack 1050B, and the Shore D hardness of the resin material after curing is greater than or equal to 87; the defoaming agent is BYK530.

[0070] The test is performed according to GB / T 17671-1999 “Cement mortar strength test method (ISO method)”.

[0071] Table 1. Material structure and biological performance of Examples and Preparation Examples Type 7d Compressive Strength 7d Flexural Strength 7d+7d (Sea Water) Compressive Strength 7d+7d (Sea Water) Flexural Strength 20d Bug Death Rate 20d Mussel Death Rate 7d+7d (Sea Water) Porosity Example 4 126.4 Mpa 28.7 Mpa 115.3 Mpa 26.4 Mpa 87% 92% 6.72% Example 5 120.8 Mpa 27.4 Mpa 112.7 Mpa 26.2 Mpa 94% 95% 10.61% Example 6 121.5 Mpa 26.1 Mpa 113.4 Mpa 25.3 Mpa 93% 93% 9.74% Example 7 125.8 Mpa 28.1 Mpa 114.7 Mpa 26.1 Mpa 86% 92% 6.75% Example 8 126.0 Mpa 27.8 Mpa 115.1 Mpa 25.4 Mpa 87% 93% 6.69% Example 9 126.6 Mpa 28.9 Mpa 114.9 Mpa 26.5 Mpa 88% 92% 6.75% Preparation 1 135.7 Mpa 31.5 Mpa 133.5 Mpa 31.2 Mpa 12% 9% 0.89% Preparation 2 125.3 Mpa 26.9 Mpa 117.5 Mpa 28.2 Mpa 7% 3% 6.83% Preparation 3 145.2 Mpa 35.1 Mpa 147.8.5 Mpa 36.4 Mpa 1% 1% 0.23% The 20d net pattern barnacle mortality and mussel mortality refer to: mature larvae are divided into groups of 100 each, and are placed in a grid box together with the test piece, and are tested at a place 15m away from the sea level in Bohai. The number of dead larvae is counted after 20 days.

[0072] Those skilled in the art should understand that the specific embodiments described above are only examples and not limiting, and various modifications, combinations, partial combinations and replacements of the embodiments of the present application can be made according to design requirements and other factors, as long as they are within the scope of the appended claims or their equivalents, i.e. belong to the scope of the rights to be protected by the present application.

Claims

1. A micro-reaction wall material for marine biofouling prevention, characterized in that: The method comprises the following raw materials in parts by weight: 75-87 parts of graded composite material, 6-9 parts of resin material, 2-5 parts of curing agent, 0.1-0.7 parts of defoaming agent, and 5-12 parts of slow-release inhibitor particles; The raw materials of the slow-release inhibition granules include granulation base material and active coated granules; The active coated particles are composed of active microspheres and a passivation layer coated on the active microspheres. The raw materials of the active microspheres include calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid. The raw materials of the passivation layer include kerosene, glycerol, calcium stearate, and fatty alcohol polyoxyethylene ether.

2. The micro-reaction wall material for marine anti-biofouling according to claim 1, characterized in that: The active microspheres are prepared by mixing and granulating calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid; the active coated particles are prepared by mixing the active microspheres with kerosene, glycerin, calcium stearate, and fatty alcohol polyoxyethylene ether, and forming a passivation shell through a coating process; the sustained-release inhibitory particles are prepared by crushing the granulation base material, adding water and stirring, and then adding the active coated particles to granulate and shape them to obtain the sustained-release inhibitory particles.

3. The micro-reaction wall material for marine anti-biofouling according to claim 1 or 2, characterized in that: The sustained-release inhibition particles are composed of the following raw materials in percentage by mass: 35.4-45.8% of a granulation base material and 54.2-64.6% of active coated particles; the raw materials of the active microspheres include, by mass, 22.3-25.4 parts of calcium nitrite, 27.6-38.3 parts of myristic acid, 25.2-32.6 parts of palmitic acid, and 22.3-25.6 parts of octadecanoic acid; the raw materials of the passivation layer include 15-30 parts of kerosene, 5-15 parts of glycerol, 30-60 parts of calcium stearate, and 10-20 parts of fatty alcohol polyoxyethylene ether.

4. The micro-reaction wall material for marine anti-biofouling according to claim 1, characterized in that: The graded composite material includes: 2-4mm basalt stones, 5-8mm basalt stones, 6-9mm basalt stones, 5-8mm pebbles, powder, and fiber materials; The resin material includes one or more of epoxy resin, polyurethane acrylate, unsaturated polyester resin, and vinyl ester resin mixed in any proportion; The curing agent includes one or more of an amine curing agent, an acid anhydride curing agent, a polyurethane curing agent, an acrylate curing agent, an unsaturated polyester curing agent, and a vinyl ester curing agent, mixed in any proportion; The defoaming agent includes one or more of a mineral oil-based defoaming agent, a polyether-modified polyacrylate defoaming agent, an aliphatic hydrocarbon defoaming agent, a polyether-modified silicone defoaming agent, and a short-chain silicone defoaming agent, mixed in any proportion; The granulation base material comprises one or more of dead-burned magnesium, fused magnesium, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, borax and boric acid, mixed in any proportion.

5. The micro-reaction wall material for marine anti-biofouling according to claim 4, characterized in that: Calculated by mass, the graded composite material includes: 5.7 to 9.2 parts of 2-4 mm basalt stones, 29.8 to 32.4 parts of 5-8 mm basalt stones, 0.5 to 1.7 parts of 6-9 mm basalt stones, 17.4 to 31.6 parts of 5-8 mm pebbles, 39.2 to 43.7 parts of powder, and 0.07 to 0.12 parts of fiber material; wherein the powder includes one or more of SiO2 powder, silicon carbide powder, Al2O3 powder, fly ash, and carbon black mixed in any proportion; the fiber material includes copper-plated steel fiber and / or shear corrugated steel fiber.

6. The micro-reaction wall material for marine anti-biofouling according to claim 5, characterized in that: The length of the copper-plated steel fiber is 13±1 mm and the diameter is 0.2±0.02 mm; the length of the shear corrugated steel fiber is 12±2 mm and the diameter is 1.4±0.5 mm.

7. The micro-reaction wall material for marine anti-biofouling according to claim 4, characterized in that: The resin material is epoxy resin, the curing agent is an amine curing agent, and the defoaming agent is a polyether-modified silicone defoaming agent; or / and the volume density of the 2-4 mm basalt stones, 5-8 mm basalt stones, and 6-9 mm basalt stones is ≥3.0 g / cm 3 , compressive strength ≥270Mpa; Or / and the 5-8 mm pebbles are natural pebbles, with a SiO2 mass content of ≥98 parts and a compressive strength of ≥100 MPa; or / and the purity of the dead-burned magnesia is greater than 92%; Or / and the purity of the fused magnesium is greater than 92%.

8. The micro-reaction wall material for marine anti-biofouling according to claim 4, characterized in that: The raw materials of the granulation base material include, by weight, 20-60 parts of dead-burned magnesia, 20-50 parts of fused magnesia, 10-20 parts of ammonium dihydrogen phosphate, 5-15 parts of diammonium hydrogen phosphate, 5-15 parts of borax, and 0-5 parts of boric acid; Or / and in terms of parts by mass, the powder includes the following raw materials: 30-50 parts of SiO2 powder, 10-25 parts of silicon carbide powder, 15-30 parts of Al2O3 powder, 10-20 parts of fly ash, and 1-5 parts of carbon black.

9. The method for preparing a micro-reaction wall material for marine anti-biofouling according to any one of claims 1 to 8, characterized in that: The following steps are involved: Preparation of active coated particles: Calcium nitrite, myristic acid, palmitic acid, and octadecanoic acid are mixed and granulated to obtain active microspheres; the active microspheres are then mixed with kerosene, glycerin, calcium stearate, and fatty alcohol polyoxyethylene ether, and a coating process is performed to form a passivation shell to prepare active coated particles; Preparation of slow-release inhibitory granules: crush the granulation base material, add water and stir, add active coated particles before the granulation base material solidifies, and granulate to obtain slow-release inhibitory granules; The graded composite material, resin material, curing agent, defoaming agent and slow-release inhibition particles are mixed to obtain a micro-reaction wall material for marine biofouling prevention.

10. The use of the micro-reactive wall material for marine biofouling prevention according to any one of claims 1 to 8, characterized in that: The micro-reaction wall material for marine biofouling prevention is added with water and stirred to prepare slurry, which is used as a coating or the slurry is injection-molded to prepare the micro-reaction wall for marine biofouling prevention.