Preparation method of controllable self-slow-release antifouling material

Abstract

The invention belongs to the technical field of antifouling material preparation methods, and particularly relates to a controllable self-slow-release antifouling material preparation method, which comprises: (1) uniformly mixing a plurality of antifouling agent powders to obtain a mixed material A, (2) uniformly mixing the mixed material A with a hydrolysis material powder to obtain a mixed material B, and (3) carrying out spray drying on the mixed material B to obtain the controllable self-slow-release antifouling material. (3) uniformly mixing the mixed material B with a cross-linking agent and a plasticizer to obtain a mixed material C, and (4) molding the mixed material C through injection, extrusion, pressing, pouring and other processes to prepare the controllable self-sustained-release antifouling material, the antifouling agent powder is an organic or inorganic antifouling agent, the hydrolysis material powder is a material capable of being degraded in water, and the controllable self-sustained-release antifouling material is prepared from the hydrolysis material powder. The cross-linking agent is a chemical additive capable of cross-linking the hydrolysis material, the plasticizer is a material capable of increasing the plasticity of the hydrolysis material, and the controllable self-slow-release antifouling material is prepared and can be used for preparing a controllable self-slow-release antifouling electrode which is stable, reliable and capable of efficiently releasing various antifouling ions.

Description

Technical field:

[0001] The present invention belongs to the technical field of antifouling material preparation methods, and specifically relates to a method for preparing a controllable self-slow-release antifouling material used in the fields of marine engineering equipment, ships, offshore platforms, etc., especially in complex local structures with narrow spaces, difficulty in power supply and antifouling coating. Background technology:

[0002] The problem of biofouling in the marine environment is a long-standing challenge that not only seriously affects the operating efficiency and life of ships, offshore platforms and other facilities, but also poses a threat to the safety and economy of marine engineering equipment. Traditional marine antifouling methods mainly include antifouling coatings, electrolytic antifouling, ultrasonic antifouling, biological antifouling, physical antifouling, mechanical cleaning and biological competition antifouling. Among them, antifouling coatings inhibit biological attachment by releasing antifouling agents. They are generally effective on the coating surface, but have poor antifouling effects on the water tank space; electrolytic antifouling and ultrasonic antifouling generate antifouling ions and ultrasonic antifouling through electrolysis, both of which require power supply, which is difficult to achieve for narrow and complex structures in marine equipment; physical antifouling and mechanical cleaning reduce attachment through special surface structures, which are easy to wear the internal structure, and can only be cleaned regularly, and cannot be protected in real time.

[0003] In the prior art, Chinese Patent No. 202210025424.8 discloses an environmentally friendly antifouling coating, which includes the following raw materials: 25-50% anionic and cationic polymer modified emulsion, 5-15% anionic and cationic polymer antifouling agent, 5-10% antialgae agent, 7-15% color filler, 1-2% water-based additive, 0.5-1% film-forming additive, and the balance is water; based on the mass of the anionic and cationic polymer modified emulsion as 100%, the anionic and cationic polymer modified emulsion includes the following raw materials in mass percentage: 1-3% anionic polymerizable monomer, 1-3% cationic polymerizable monomer, triisopropyl The invention discloses an environmentally friendly antifouling coating comprising 10-20% of methyl acrylate silicone, 25-40% of acrylate monomer, 0.5-1.5% of acrylic acid, 1-2% of emulsifier, 0.3-0.6% of inorganic peroxide initiator, 0.05-0.1% of sodium bicarbonate, 0.3-0.5% of pH regulator, and the balance of water. The method for preparing the environmentally friendly antifouling coating comprises the following steps: mixing water, water-based auxiliary agent, anionic and cationic polymer antifouling agent, anti-algae agent and pigment and filler, and then grinding to obtain grinding liquid; mixing the grinding liquid with anionic and cationic polymer modified emulsion and film-forming auxiliary agent to obtain the environmentally friendly antifouling coating used as marine antifouling coating. Chinese patent 202410583889.4 discloses an environmentally friendly ship antifouling coating suitable for long-term freshwater / delicate seawater outfitting, which comprises the following components by weight: 15-30 parts of a degradable polyurethane resin, 20-25 parts of an MEP resin, 10-30 parts of a modified halloysite loaded with a biological antifouling agent, 10-20 parts of an abrasion accelerator, 0-30 parts of a pigment and filler, 0-10 parts of other additives, and 10-40 parts of a solvent; a method for preparing an environmentally friendly ship antifouling coating suitable for long-term freshwater / delicate seawater outfitting, comprising the following steps: Halloysite and the first part of the solvent are mixed and dispersed uniformly to obtain a modified halloysite dispersion loaded with a biological antifouling agent; a degradable polyurethane resin, a MEP resin, an abrasion accelerator, other additives and the second part of the solvent are mixed and dispersed uniformly, and then a pigment and filler are added and dispersed at high speed or ground to a fineness of less than 80 μm, and filtered to obtain a resin powder dispersion; wherein the sum of the amounts of the first part of the solvent and the second part of the solvent is equal to the total amount of the solvent; after the modified halloysite dispersion loaded with a biological antifouling agent and the resin powder dispersion are mixed, they are stirred and dispersed uniformly, and filtered to obtain an environmentally friendly ship antifouling coating.Chinese Patent 202110541987.8 discloses a power-free, long-life, self-driven anti-fouling device for a ship's seawater box environment, which consists of an anti-fouling electrode and a mounting base. The anti-fouling electrode is the main functional structure, and uses the potential difference between dissimilar metals to drive the accelerated dissolution of the cathode plate, so that it produces copper ions reaching an effective anti-fouling concentration; the anti-fouling electrode consists of a cathode metal plate, an anode metal plate, a splint, and fasteners. The cathode metal plate and the anode metal plate are fixed by splints and fasteners at both ends. The number of fasteners is determined by the total number of anode and cathode plates, so that each anode and cathode plates are fixed and not loose; the cathode metal plate is made of an inert metal material, and the anode metal plate is made of a copper alloy selected from pure copper, red copper, bronze, brass or copper alloys doped with other metal elements. The material of the splint is consistent with that of the anode metal plate.

[0004] However, the above existing technologies have problems such as uncontrollable release rate and environmental pollution, and it is difficult to effectively protect narrow structures with electricity, especially the anti-fouling of complex local structures such as seawater tanks that are difficult to power, permeable structures of small aircraft, and high-precision motion mechanisms. Therefore, it is of great significance to study and develop a controllable self-slow-release antifouling material. Summary of the invention:

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and to develop a method for preparing a controllable self-release antifouling material so as to prepare an antifouling material that can stably and efficiently release antifouling ions.

[0006] In order to achieve the above-mentioned object, the specific process of the preparation method of a controllable self-slow-release antifouling material according to the present invention comprises the following four steps:

[0007] (1) mixing several antifouling agent powders uniformly to obtain a mixed material A;

[0008] The antifouling agent powder is an organic or inorganic antifouling agent, including cuprous oxide, cuprous thiocyanate, zinc oxide, copper sulfate, copper naphthenate, acid copper, organotin, DDT (bis(p-chlorophenyl)trichloroethane), Econea (bromopyrrole nitrile), pyridine triphenyl borane, copper pyrithione, zinc pyrithione, DCOIT (4,5-dichloro-2-n-octyl-3-isothiazolinone), 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine (Irgarol 1051), zinc ethylenebisdithiocarbamate (Zineb), and N-(2,4,6-trichlorophenyl) maleimide (TCPM);

[0009] (2) mixing the mixed material A and the hydrolyzed material powder evenly to obtain a mixed material B;

[0010] The hydrolyzable material powder is a material that can be degraded in water, including polyacrylamide, polyacrylic acid, polyvinyl pyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, starch, gum arabic, sodium alginate, bone meal, gelatin, casein, cellulose, etc.;

[0011] (3) uniformly mixing the mixed material B with the cross-linking agent and the plasticizer to obtain a mixed material C;

[0012] The cross-linking agent is a chemical auxiliary agent capable of cross-linking the hydrolyzed material, including boric acid, formaldehyde, glyoxal, glutaraldehyde, dimethylol urea, trimethylol melamine, etc.;

[0013] Plasticizers are materials that can increase the plasticity of hydrolyzed materials, including glycerol, phthalates, aliphatic dibasic acid esters, fatty acid esters, benzene polyesters, polyol esters, epoxy hydrocarbons, alkyl sulfonates, etc.;

[0014] (4) preparing the mixed material C into a controllable self-release antifouling material by injection, extrusion, pressing, casting or other processes;

[0015] Wherein, the weight ratio of the hydrolyzed material powder to the mixed material A is 0.1-1000:1;

[0016] The weight ratio of the crosslinking agent to the hydrolyzed material powder is 0-0.5:1;

[0017] The weight ratio of the plasticizer to the hydrolyzed material powder is 0-0.5:1.

[0018] Compared with the prior art, the present invention uses antifouling agent powder and hydrolyzable material powder as raw materials, adds a crosslinking agent and a plasticizer, and forms them through injection, extrusion, pressing, casting and other processes to prepare a controllable self-slow-release antifouling material, which can be used to prepare a controllable self-slow-release antifouling electrode that stably, reliably and efficiently releases a variety of antifouling ions; wherein the antifouling agent powder is an organic or inorganic antifouling agent, the hydrolyzable material powder is a material that can be degraded in water, the weight ratio of the two is 1:0.1-1000, the crosslinking agent is a chemical auxiliary agent that can crosslink the hydrolyzable material, and the plasticizer is a material that can increase the plasticity of the hydrolyzable material. Specific implementation method:

[0019] The present invention will be further described below by way of examples.

[0020] Embodiment 1:

[0021] The specific process of the preparation method of a controllable self-sustaining antifouling material involved in this embodiment is as follows:

[0022] (1) Econea, DCOIT and cuprous oxide (labeling agent) were mixed in a weight ratio of 1:1:1 to obtain a mixed material A;

[0023] (2) mixing mixed material A and polyvinyl alcohol in a weight ratio of 1:10 to obtain mixed material B;

[0024] (3) mixing the mixed material B with glutaraldehyde and glycerol to obtain a mixed material C;

[0025] The weight ratio of polyvinyl alcohol to glutaraldehyde and glycerol in the mixed material B is 1:0.001;

[0026] (4) The mixed material C is prepared into a controllable self-release antifouling material by injection molding process, which is recorded as A1.

[0027] Embodiment 2:

[0028] The specific process of the preparation method of a controllable self-sustaining antifouling material involved in this embodiment is as follows:

[0029] (1) Econea, DCOIT and cuprous oxide (labeling agent) were mixed in a weight ratio of 1:1:1 to obtain a mixed material A;

[0030] (2) mixing the mixed material A and polyvinyl alcohol in a weight ratio of 1:5 to obtain a mixed material B;

[0031] (3) mixing the mixed material B with glutaraldehyde and ethylene glycol to obtain a mixed material C;

[0032] The weight ratio of polyvinyl alcohol to glutaraldehyde and ethylene glycol in mixed material B is 1:0.001;

[0033] (4) The mixed material C is prepared into a controllable self-release antifouling material through an extrusion molding process, which is recorded as A2.

[0034] The controlled self-release antifouling materials A1 and A2 were subjected to laboratory immersion tests. The release efficiency of antifouling ions was calibrated by measuring the copper content in seawater. The test solution was natural seawater (100L, seawater was replaced every 1d). The test period was 60 days. On the 7th, 20th and 60th days of the test, the seawater was stirred evenly and water samples were collected. The copper concentration in the water samples was detected by inductively coupled plasma mass spectrometry according to HY / T147.1-2013. The results are shown in the following table:

[0035]

[0036] It can be seen that antifouling ions can be released effectively and stably.

Claims

1. A method for preparing a controllable self-release antifouling material, characterized in that: The antifouling agent powder and the hydrolyzed material powder are used as raw materials, a crosslinking agent and a plasticizer are added, and a controllable self-sustaining antifouling material is prepared.

2. The method for preparing a controllable self-sustaining antifouling material according to claim 1, characterized in that: The specific process is: (1) mixing several antifouling agent powders uniformly to obtain a mixed material A; (2) mixing the mixed material A and the hydrolyzed material powder evenly to obtain a mixed material B; (3) uniformly mixing the mixed material B with the cross-linking agent and the plasticizer to obtain a mixed material C; (4) The mixed material C is prepared into a controllable self-release antifouling material through injection, extrusion, pressing, casting and other processes.

3. The method for preparing a controllable self-sustaining antifouling material according to claim 1 or 2, characterized in that: The antifouling agent powder is an organic or inorganic antifouling agent, the hydrolyzed material powder is a material that can be degraded in water, the crosslinking agent is a chemical auxiliary agent that can crosslink the hydrolyzed material, and the plasticizer is a material that can increase the plasticity of the hydrolyzed material.

4. The method for preparing a controllable self-sustaining antifouling material according to claim 3, characterized in that: The weight ratio of the antifouling agent powder to the hydrolyzed material powder is 1:0.1-1000; the weight ratio of the crosslinking agent and the plasticizer to the hydrolyzed material powder is 0-0.5:1, excluding 0:

1.

5. The method for preparing a controllable self-sustaining antifouling material according to claim 3, characterized in that: Antifouling agent powders include cuprous oxide, cuprous thiocyanate, zinc oxide, copper sulfate, copper naphthenate, acid copper, organic tin, DDT, Econea, pyridine triphenyl borane, copper pyrithione, zinc pyrithione, DCOIT, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine, zinc ethylenebisdithiocarbamate, and N-(2,4,6-trichlorophenyl)maleimide.

6. The method for preparing a controllable self-sustaining antifouling material according to claim 3, characterized in that: The hydrolyzed material powder includes polyacrylamide, polyacrylic acid, polyvinyl pyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, starch, gum arabic, sodium alginate, bone meal, gelatin, casein and cellulose.

7. The method for preparing a controllable self-sustaining antifouling material according to claim 3, characterized in that: Cross-linking agents include boric acid, formaldehyde, glyoxal, glutaraldehyde, dimethylol urea, and trimethylol melamine.

8. The method for preparing a controllable self-sustaining antifouling material according to claim 3, characterized in that: Plasticizers include glycerol, phthalates, aliphatic dibasic acid esters, fatty acid esters, benzene polyesters, polyol esters, epoxy hydrocarbons, and alkyl sulfonates.

9. The method for preparing a controllable self-sustaining antifouling material according to claim 1, characterized in that: No crosslinking agents or plasticizers are added.

10. The method for preparing a controllable self-sustaining antifouling material according to claim 1, 2 or 9, characterized in that: The controllable self-sustaining antifouling material is prepared and used for preparing the controllable self-sustaining antifouling electrode.

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