CN116575246A - Antifouling paint for netting and application thereof - Google Patents

Antifouling paint for netting and application thereof Download PDF

Info

Publication number
CN116575246A
CN116575246A CN202310451963.2A CN202310451963A CN116575246A CN 116575246 A CN116575246 A CN 116575246A CN 202310451963 A CN202310451963 A CN 202310451963A CN 116575246 A CN116575246 A CN 116575246A
Authority
CN
China
Prior art keywords
anhydride
film
groups
forming resin
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310451963.2A
Other languages
Chinese (zh)
Inventor
张庆华
侯阳
胡建坤
吕建国
焦磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghai Laboratory
Original Assignee
Donghai Laboratory
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghai Laboratory filed Critical Donghai Laboratory
Priority to CN202310451963.2A priority Critical patent/CN116575246A/en
Publication of CN116575246A publication Critical patent/CN116575246A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/141—Hydrophilic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/146—Soilproof, soil repellent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1635—Elasticity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the technical field of marine antifouling, and discloses an antifouling paint for a netting and application thereof. The antifouling paint comprises a film-forming resin; the preparation method of the film-forming resin comprises the following steps: taking anhydride and 1, 4-cyclohexanedimethanol as raw materials, and carrying out polycondensation reaction between anhydride groups and hydroxyl groups to prepare a compound I; the method comprises the steps of (1) taking a compound I, an anhydride-containing compound and/or dibasic acid and dihydric alcohol as raw materials, and carrying out polycondensation reaction between an anhydride group and/or carboxyl and hydroxyl to prepare a carboxyl-containing polymer II; the polymer II containing carboxyl and the compound containing at least two epoxy groups are used as raw materials to carry out ring-opening reaction between the epoxy groups and the carboxyl to prepare the film-forming resin. The film-forming resin synthesized by a special method is adopted in the anti-fouling paint, so that the film-forming resin has good hydrophilicity, flexibility and elasticity, can exert good anti-fouling effect after the paint forms a coating on the netting, and reduces the influence of the coating on the expansion and contraction capability of the netting.

Description

Antifouling paint for netting and application thereof
Technical Field
The invention relates to the technical field of marine antifouling, in particular to an antifouling paint for a netting and application thereof.
Background
As fishery resources decline, marine fishery is transitioning from fishing to farming. The development of the breeding industry to the deep sea is already a consensus of the sea-leaning countries. However, the unavoidable attachment of marine organisms to the marine aquaculture industry causes a significant hazard. The polluted fishing net reduces the culture capacity of the net cage, compresses the mesh area and increases the load of the net cage under the flushing of water flow, so that the cage body is deformed, the polluted organisms can erode and destroy the fishing net, and the service life of the net cage is greatly shortened. Fouling organisms growing on the surface of the net body reduce the mesh area to cause blockage, so that the convection of seawater inside and outside is influenced, nutrition exchange, dissolved oxygen diffusion and metabolic waste discharge are blocked, the yield of aquatic products can be influenced, and the damage to the environment caused by water eutrophication is easy to cause. The complex biofouling community evolved on the surface of the net cage can indirectly trigger further deposition, breed bacteria and parasites, reduce the yield of aquatic products, seriously cause dysplasia and even death, and seriously affect the economic benefit.
Currently, the marine aquaculture industry often uses methods of physical removal, use of anti-fouling agents, and biological control to control biofouling. The physical removal method generally adopts a plurality of methods such as periodic net replacement, mechanical cleaning, pollution prevention or cage rotating design, chemical control agent and the like to solve the problem of pollution of the fishing net, and has the advantages of complex process, high labor intensity, time and labor waste. The use of biological control techniques to solve the marine biofouling problem has tremendous potential market value, but the high cost limits its application in the mariculture industry. The use of a net anti-fouling coating is the current mainstream anti-fouling method, and the anti-fouling coating is coated on a fishing net in a dip-coating mode, so that the anti-fouling period of the net is required to be at least more than six months in mariculture.
The patent CN202010384888.9, the patent CN201910811485.5 and the patent CN201911206394.5 respectively use resins such as chlorohydrin resin, modified polyethylene resin, polyurethane resin and the like as film forming substances, wherein the polyurethane resin has good flexibility, but has higher cost, is unstable in storage and is easy to gel; the chlorinated polyether resin and the modified polyethylene resin can hardly be hydrolyzed and polished, and the antifouling effect is poor. The patent CN201210554914.3 uses zinc acrylate and acrylic silicon resin as film forming substances, and the coating has poor flexibility, and obviously reduces the expansion and contraction capability after covering the netting, thereby affecting the normal work of the netting. In addition, because the antifouling effect of the film forming substances is limited, a large amount of copper antifouling agents are often added into the netting antifouling paint on the market to realize antifouling efficiency, the antifouling paint does not meet the environmental protection requirement, and the antifouling paint also has potential risks for aquatic organisms.
Disclosure of Invention
The invention provides an antifouling paint for a netting, which aims to solve the technical problem that the conventional antifouling paint for the netting is difficult to achieve both flexibility and antifouling effect. The film-forming resin synthesized by a special method is adopted in the antifouling paint, and has good hydrophilicity, flexibility and elasticity, so that the paint can play a good antifouling role after a coating is formed on a net, and the influence of the coating on the telescopic capability of the net is reduced.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides an anti-fouling coating for a netting comprising a film-forming resin; the preparation method of the film-forming resin comprises the following steps:
(1) Using anhydride and 1, 4-cyclohexanedimethanol as raw materials to perform esterification reaction between anhydride groups and hydroxyl groups to prepare a compound I;
(2) Taking a compound I, a compound containing anhydride and/or dibasic acid and dihydric alcohol as raw materials, and carrying out polycondensation reaction between anhydride groups and carboxyl groups and hydroxyl groups or carrying out polycondensation reaction between carboxyl groups and hydroxyl groups to prepare a polymer II containing carboxyl groups;
(3) The polymer II containing carboxyl and the compound containing at least two epoxy groups are used as raw materials to carry out ring-opening reaction between the epoxy groups and the carboxyl to prepare the film-forming resin.
The film-forming resin synthesized by the method contains a plurality of hydrophilic groups (including carboxyl groups, hydroxyl groups, ester groups and the like), so that the film-forming resin can be endowed with good hydrophilicity, and after an antifouling coating is formed on a net, the coating can be hydrolyzed and self-polished in seawater, thereby playing a good antifouling role. Through experiments, the anti-fouling paint disclosed by the invention can realize a better anti-fouling effect without adding copper anti-fouling agents.
According to the invention, after the polymer 1 is synthesized, the acid anhydride-containing compound and/or the dibasic acid and the dihydric alcohol are utilized to carry out first chain extension, and then the compound containing at least two epoxy groups is utilized to carry out second chain extension, so that the obtained film-forming resin has higher molecular weight through two chain extensions, thereby endowing the film-forming resin with better film-forming performance, and a linear structure with larger molecular weight exists in the film-forming resin, and the structure can endow the film-forming resin with better flexibility and elasticity, thereby reducing the influence of the antifouling coating on the telescopic capability of the netting, and further enhancing the quick drying capability of the coating.
Preferably, step (1) comprises the steps of: the method comprises the steps of taking itaconic anhydride, 1, 4-cyclohexanedimethanol and an initiator as raw materials, carrying out esterification reaction between anhydride groups and hydroxyl groups, and carrying out addition polymerization reaction of alkenyl groups to prepare the compound I.
The itaconic anhydride containing alkenyl is used in the step (1), and an initiator is added to enable alkenyl to carry out polyaddition reaction, so that the film-forming resin has a three-dimensional space network, and the coating is endowed with a good instant thixotropic stabilization effect, so that the coating shows good sagging resistance, and the disposable infiltration coating rate of the coating to the netting is improved.
Preferably, in the step (3), the compound containing at least two epoxy groups is polyethylene glycol diglycidyl ether.
The polyethylene glycol diglycidyl ether has higher hydrophilicity, so that the antifouling coating has better self-polishing property in seawater; meanwhile, compared with an epoxy macromolecular compound containing a plurality of crosslinking groups, the polyethylene glycol diglycidyl ether has a structure with smaller molecular weight and two epoxy groups, so that the crosslinking density of the prepared film-forming resin is relatively low, and the abrasion rate of the film-forming resin in seawater is improved; in addition, the relatively low degree of crosslinking also enables the film-forming resin to have a relatively high number of high molecular weight linear structures, which enables the film-forming resin to have better flexibility and elasticity. Therefore, the polyethylene glycol diglycidyl ether is selected to chain-extend the polymer II, so that the antifouling effect of the coating can be improved to a greater extent, and the influence of the antifouling effect on the telescopic capability of the netting is reduced.
Further, the epoxy value of the polyethylene glycol diglycidyl ether is 0.35-0.80.
Preferably, in the step (2), the anhydride-containing compound is hexahydrophthalic anhydride, and the dibasic acid is adipic acid.
Preferably, in the step (2), the dihydric alcohol is one or two of neopentyl glycol and tetraethylene glycol.
Preferably, the specific process of step (1) comprises the following steps: under the protection of inert gas, itaconic anhydride, 1, 4-cyclohexanedimethanol and solvent I are mixed and react for 2.5 to 3.5 hours at the temperature of 60 to 70 ℃, then a part of initiator is added to react for 1 to 2 hours at the temperature of 85 to 95 ℃, then the rest initiator is added to react for 1 to 2 hours at the temperature of 85 to 95 ℃.
Further, in the step (1), the mass ratio of the itaconic anhydride to the initiator is 1:0.005-0.008.
Further, in the step (1), the mass ratio of the part of the initiator to the rest of the initiator is 2.5-3.5:1.
Preferably, the specific process of step (2) comprises the following steps: adding a compound containing anhydride and/or dibasic acid, dihydric alcohol, a polycondensation catalyst and a solvent II into the product obtained in the step (1), reacting for 1-2 h at 155-165 ℃, then heating to 175-185 ℃ for continuous reaction for 1-2 h, heating to 195-205 ℃ for continuous reaction for 6-24 h, and finally heating to 225-235 ℃ for 30-40 min.
In the process of chain extension of the compound I by using the acid anhydride-containing compound and/or the dibasic acid and the dibasic alcohol, four stages of 155-165 ℃ -175-185 ℃ -195-205 ℃ -225-235 ℃ are set, wherein the main reactions are sequentially that the acid anhydride reacts with the active alcohol hydroxyl, the active acid reacts with the active alcohol hydroxyl, the inert or sterically bulky functional group reacts, and the ending is carried out (the monomer concentration of the last stage is reduced, and the temperature rise is helpful for the reaction completion).
Further, in the step (2), the polycondensation catalyst is monobutyl tin oxide, and the molar ratio of the dihydric alcohol to the polycondensation catalyst is 1:0.009-0.015.
Preferably, the specific process of step (3) comprises the following steps: adding a compound containing at least two epoxy groups, a solvent III and a ring-opening reaction catalyst into the product obtained in the step (2), and reacting for 8-10 h at 150-160 ℃.
Further, in the step (3), the ring-opening reaction catalyst is triphenylphosphine, and the mass ratio of the compound containing at least two epoxy groups to the ring-opening reaction catalyst is 1:0.015-0.025.
Preferably, in the step (1), the molar ratio of the anhydride to the 1, 4-cyclohexanedimethanol is 1:0.3-0.5.
Preferably, the molar ratio of the anhydride in the step (1) to the anhydride-containing compound and/or the dibasic acid and the dihydric alcohol in the step (2) is 1:1.0-1.7:1.0-1.5.
Preferably, the molar ratio of the anhydride in step (1) to the epoxy groups in the compound containing at least two epoxy groups in step (3) is 1:35-165.
Preferably, the number average molecular weight of the film-forming resin is 9900 to 12500.
Preferably, the antifouling paint comprises the following components in parts by weight: 35-60 parts of film-forming resin dispersion liquid, 0-5 parts of auxiliary resin, 1-5 parts of mechanical accelerator, 0-16 parts of antifouling agent, 0-7 parts of pigment, 0-2 parts of plasticizer, 3-7 parts of auxiliary agent and 10-25 parts of coating solvent.
Further, the solid content in the film-forming resin dispersion is 50 to 55%.
Further, the auxiliary resin includes one or more of rosin resin, butyl resin, styrene-butadiene resin, phenolic resin, silicone resin, amino resin, urea resin, chloroether resin, modified polyethylene resin and polyurethane resin.
Further, the mechanical promoter comprises glass fibers and/or sheet quartz.
Further, the antifouling agent includes one or more of cuprous oxide, copper pyrithione, zinc pyrithione, zineb, boric acid, seaNine211, diuron, borneol, bromopyrroconitrile, metoclopramide, borneol, propylene glycol menthyl carbonate, borax, menthol, tannic acid, matrine, capsaicin, metaldehyde, molluscacide, 6-chloroindole, osthole and rotenone.
Further, the plasticizer includes one or more of dibutyl phthalate, dioctyl phenyl phosphate, chlorinated paraffin, dioctyl phenyl phosphite and polyacrylamide.
Further, the auxiliary agent comprises one or more of dispersing agent, leveling agent, anti-settling thixotropic agent and antioxidant.
Further, the paint solvent includes one or more of xylene, butanol, solvent oil, and propylene glycol methyl ether.
In a second aspect, the invention provides the use of said antifouling paint in antifouling of a netting.
Preferably, the application comprises the steps of: and dip-coating the antifouling coating on the surface of the netting to form the antifouling coating.
Compared with the prior art, the invention has the following advantages:
(1) In the anti-fouling paint, the film-forming resin synthesized by a special method is adopted, so that the paint has high hydrophilicity, and has good anti-fouling performance after a coating is formed on a net, the dosage of copper anti-fouling agents in the paint is greatly reduced, and the anti-fouling paint can meet the environmental protection requirement;
(2) The film-forming resin adopted in the antifouling paint has higher flexibility and elasticity, and can reduce the influence of the antifouling coating on the telescopic capacity of the netting, so that the netting can work normally;
(3) The film-forming resin adopted in the anti-fouling paint has a three-dimensional space network, so that the paint has a good instant thixotropic stabilization effect, and the disposable infiltration coating rate of the paint to a net is improved.
Detailed Description
The invention is further described below with reference to examples.
General examples
An antifouling paint for a netting comprises film-forming resin; the preparation method of the film-forming resin comprises the following steps:
(1) Using itaconic anhydride, 1, 4-cyclohexanedimethanol and an initiator as raw materials, carrying out esterification reaction between anhydride groups and hydroxyl groups, and carrying out addition polymerization reaction of alkenyl groups to prepare a compound I;
(2) Taking a compound I, a compound containing anhydride and/or dibasic acid and dihydric alcohol as raw materials, and carrying out polycondensation reaction between anhydride groups and carboxyl groups and hydroxyl groups or carrying out polycondensation reaction between carboxyl groups and hydroxyl groups to prepare a polymer II containing carboxyl groups;
(3) The polymer II containing carboxyl and the compound containing at least two epoxy groups are used as raw materials to carry out ring-opening reaction between the epoxy groups and the carboxyl to prepare the film-forming resin.
In step (2), the anhydride-containing compound is hexahydrophthalic anhydride, the dibasic acid is adipic acid, and the dihydric alcohol is one or two of neopentyl glycol and tetraethylene glycol; in the step (3), the compound containing at least two epoxy groups is polyethylene glycol diglycidyl ether with an epoxy value of 0.35-0.80.
As a specific embodiment, the specific process of step (1) includes the following steps: under the protection of inert gas, itaconic anhydride, 1, 4-cyclohexanedimethanol and a solvent I are mixed, the molar ratio of the itaconic anhydride to the 1, 4-cyclohexanedimethanol is 1:0.3-0.5, the mass ratio of the itaconic anhydride to the initiator is 1:0.005-0.008, the itaconic anhydride and the initiator react for 2.5-3.5 hours at the temperature of 60-70 ℃, then a part of the initiator is added, the reaction is carried out for 1-2 hours at the temperature of 85-95 ℃, then the rest initiator is added, the mass ratio of the part of the initiator to the rest initiator is 2.5-3.5:1, and the reaction is continued for 1-2 hours at the temperature of 85-95 ℃.
As a specific embodiment, the specific process of step (2) includes the following steps: adding an anhydride-containing compound and/or diacid, dihydric alcohol, a polycondensation catalyst and a solvent II into the product obtained in the step (1), wherein the molar ratio of the itaconic anhydride to the anhydride-containing compound and/or diacid and dihydric alcohol in the step (2) is 1:1.0-1.7:1.0-1.5, the molar ratio of the dihydric alcohol to the polycondensation catalyst is 1:0.009-0.015, reacting for 1-2 h at 155-165 ℃, then heating to 175-185 ℃ for continuous reaction for 1-2 h, heating to 195-205 ℃ for continuous reaction for 6-24 h, and finally heating to 225-235 ℃ for 30-40 min.
As a specific embodiment, the specific process of step (3) includes the following steps: adding a compound containing at least two epoxy groups, a solvent III and a ring-opening reaction catalyst into the product obtained in the step (2), wherein the molar ratio of the anhydride in the step (1) to the epoxy groups in the compound containing at least two epoxy groups in the step (3) is 1:35-165, the mass ratio of the compound containing at least two epoxy groups to the ring-opening reaction catalyst is 1:0.015-0.025, and reacting for 8-10 h at 150-160 ℃.
In one embodiment, the film-forming resin has a number average molecular weight of 9900 to 12500.
As a specific embodiment, the composition comprises the following components in parts by weight: 35-60 parts of film-forming resin dispersion liquid, 0-5 parts of auxiliary resin, 1-5 parts of mechanical accelerator, 0-16 parts of antifouling agent, 0-7 parts of pigment, 0-2 parts of plasticizer, 3-7 parts of auxiliary agent and 10-25 parts of coating solvent.
In the above embodiments:
the solid content in the film-forming resin dispersion liquid is 50-55%;
the auxiliary resin can be selected from one or more of rosin resin, butyl resin, styrene-butadiene resin, phenolic resin, organic silicon resin, amino resin, urea resin, chloroether resin, modified polyethylene resin and polyurethane resin;
the mechanical promoter may be selected from glass fibers and/or platy quartz;
the antifouling agent can be selected from one or more of cuprous oxide, copper pyrithione, zinc pyrithione, zineb, boric acid, seaNine211, diuron, borneol, bromopyrrocarbonitrile, metopyrimidine, borneol, propylene glycol menthyl carbonate, borax, menthol, tannic acid, matrine, capsaicin, metaldehyde, molluscacidamine, 6-chloroindole, osthole and rotenone;
the plasticizer can be selected from one or more of dibutyl phthalate, dioctyl phenyl phosphate, chlorinated paraffin, dioctyl benzene phosphite and polyacrylamide;
the auxiliary agent can be one or more selected from dispersing agents, leveling agents, anti-settling thixotropic agents and antioxidants;
the paint solvent may be selected from one or more of xylene, butanol, solvent oil and propylene glycol methyl ether.
The antifouling paint is used for preventing the pollution of the netting, and comprises the following steps: and dip-coating the antifouling coating on the surface of the netting to form the antifouling coating.
Preparation example 1: preparation of film-forming resins
A film-forming resin R1 dispersion was prepared by the following steps:
(1) Under the protection of nitrogen, 61.6g (0.55 mol) of itaconic anhydride and 28.8g (0.2 mol) of 1, 4-cyclohexanedimethanol are taken, 91g of dimethylbenzene is heated to 60 ℃ and kept for 3 hours, 0.3g of Azodiisobutyronitrile (AIBN) is added, the temperature is raised to 90 ℃, after 1.5 hours of reaction, 0.1g of AIBN is added, and the reaction is continued for 1.5 hours.
(2) 138.6g (0.9 mol), 83.2g (0.8 mol) of neopentyl glycol and 1.5g of monobutyl tin oxide are added into the product obtained in the step (1), the mixture is heated to 160 ℃ after being mixed, the temperature is maintained for 1h, the temperature is increased to 180 ℃ after being kept for 1h, the temperature is increased to 200 ℃ after being kept until the water yield reaches the theoretical value (9.9 g) (about 24 h), the temperature is continuously increased to 230 ℃ after being kept for 0.5h, the temperature is reduced to 90 ℃, 150g of calculated amount of dimethylbenzene is added, the solid content is maintained at 50%, the measured acid value is 84, and the GPC measured molecular weight is 1200.
(3) Adding 225g of polyethylene glycol diglycidyl ether (epoxy value 0.35-0.40), 230g of xylene and triphenylphosphine (Ph) into the product obtained in the step (2) 3 P) 5g, the reaction temperature is maintained at 150 ℃, the reaction is carried out for about 9 hours,after the liquid became a dark yellow liquid and the acid value was less than 3, the reaction was ended to obtain a film-forming resin R1 dispersion. The theoretical solid content of the resin is 50 percent, and the actual measured solid content is 51.8 percent. The final molecular weight M was measured by GPC w 36832M n 9934 and a dispersity of 3.71.
The synthetic route for this preparation is as follows:
the amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 1.
Preparation example 2: preparation of film-forming resins
A film-forming resin R2 dispersion was prepared by the following steps:
(1) Under the protection of nitrogen, 61.6g (0.55 mol) of itaconic anhydride and 28.8g (0.2 mol) of 1, 4-cyclohexanedimethanol are taken, 91g of dimethylbenzene is heated to 60 ℃ and kept for 3 hours, 0.3g of Azodiisobutyronitrile (AIBN) is added, the temperature is raised to 90 ℃, after 1.5 hours of reaction, 0.1g of AIBN is added, and the reaction is continued for 1.5 hours.
(2) 115.5g (0.75 mol), 83.2g (0.8 mol) of neopentyl glycol and 1.5g of monobutyl tin oxide are added into the product obtained in the step (1), the mixture is heated to 160 ℃ after being mixed, the temperature is maintained for 1h, the temperature is raised to 180 ℃ after being kept for 1h, the temperature is raised to 200 ℃ after being kept for 1h, the water yield reaches a theoretical value (12.6 g) (about 24 h), the temperature is continuously raised to 230 ℃ after being kept for 0.5h, the temperature is reduced to 90 ℃, 145g of calculated amount of dimethylbenzene is added, the solid content is maintained at 50%, the measured acid value is 57, and the GPC measured molecular weight is 2000.
(3) 150g (epoxy value 0.35-0.40) of polyethylene glycol diglycidyl ether, 154g of xylene and triphenylphosphine (Ph) are added to the product obtained in the step (2) 3 P) 3.5g, the reaction temperature was maintained at 150℃and the reaction was carried out for about 9 hours until the liquid became a dark yellow liquid and the acid value was less than 3, and the reaction was ended to obtain a film-forming resin R2 dispersion. The theoretical solid content of the resin is 50 percent, and the actual solid content is 52.1 percent. The final molecular weight M was measured by GPC w 43327, M n 12489 the dispersity is3.47。
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 1.
Preparation example 3: preparation of film-forming resins
A film-forming resin R3 dispersion was prepared by the following steps:
(1) Under the protection of nitrogen, 61.6g (0.55 mol) of itaconic anhydride and 28.8g (0.2 mol) of 1, 4-cyclohexanedimethanol are taken, 91g of dimethylbenzene is heated to 60 ℃ and kept for 3 hours, 0.3g of Azodiisobutyronitrile (AIBN) is added, the temperature is raised to 90 ℃, after 1.5 hours of reaction, 0.1g of AIBN is added, and the reaction is continued for 1.5 hours.
(2) 84.7g (0.55 mol), 83.2g (0.8 mol) of neopentyl glycol and 1.5g of monobutyl tin oxide are added into the product obtained in the step (1), the mixture is heated to 160 ℃ after being mixed, the temperature is maintained for 1h, the temperature is increased to 180 ℃ after being kept for 1h, the temperature is increased to 200 ℃ after being kept for 1h, the water yield reaches a theoretical value (17.1 g) (about 24 h), the temperature is continuously increased to 230 ℃ after being kept for 0.5h, the temperature is reduced to 90 ℃, 124g of calculated amount of dimethylbenzene is added, the solid content is maintained at 50%, the measured acid value is 23, and the GPC measured molecular weight is 3000.
(3) 60g (epoxy value 0.35-0.40) of polyethylene glycol diglycidyl ether, 62g of xylene and 62g of triphenylphosphine (Ph) are added to the product obtained in the step (2) 3 P) 1.5g, the reaction temperature was maintained at 150℃and the reaction was carried out for about 9 hours until the liquid became a dark yellow liquid and the acid value was less than 3, and the reaction was ended to obtain a film-forming resin R3 dispersion. The theoretical solid content of the resin is 50 percent, and the actual solid content is 52.2 percent. The final molecular weight M was measured by GPC w 47836, M n 11593 and a dispersity of 4.13.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 1.
Preparation example 4: preparation of film-forming resins
The procedure of preparation example 2 was followed to prepare a film-forming resin R4 dispersion, differing from preparation example 2 only in: 83.2g (0.8 mol) of neopentyl glycol in the step (2) was changed to 41.6g (0.4 mol) of neopentyl glycol and 77.7g (0.4 mol) of tetraethylene glycol, and the other raw materials and the production process were the same as those of production example 2.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 1.
Preparation example 5: preparation of film-forming resins
The procedure of preparation example 2 was followed to prepare a film-forming resin R5 dispersion, differing from preparation example 2 only in: 150g (epoxy value 0.35-0.40) of polyethylene glycol diglycidyl ether in the step (3) is changed into 75g (epoxy value 0.70-0.80) of polyethylene glycol diglycidyl ether, and the rest raw materials and the preparation process are the same as those of the preparation example 2.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 1.
Preparation example 6: preparation of film-forming resins
The procedure of preparation example 4 was followed to prepare a film-forming resin R6 dispersion, differing from preparation example 4 only in: 115.5g (0.75 mol) of hexahydrophthalic anhydride in step (2) was changed to 109.6g (0.75 mol) of adipic acid, and the other raw materials and the production process were the same as those in production example 4.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 2.
Preparation example 7: preparation of film-forming resins
The procedure of preparation example 4 was followed to prepare a film-forming resin R7 dispersion, differing from preparation example 4 only in: 150g (epoxy value 0.35-0.40) of polyethylene glycol diglycidyl ether in the step (3) is changed to 568g of acrylic epoxy resin, and the other raw materials and the preparation process are the same as those of preparation example 4.
The preparation method of the acrylic epoxy resin used in the preparation example refers to patent ZL201811652868.4, and comprises the steps of dropwise adding 100g of isobornyl methacrylate, 60g of glycidyl methacrylate, 20g of lauryl methacrylate, 20g of butyl methacrylate, 2.0g of AIBN and 202g of xylene at 90 ℃ for 3 hours, and preserving heat for 3 hours to obtain the epoxy resin with 50% of solid content.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 2.
Preparation example 8: preparation of film-forming resins
The film-forming resin R8 dispersion was prepared following the procedure in preparation example 2, differing from preparation example 2 only in: in the step (1), azobisisobutyronitrile was not added, and the other raw materials and the preparation process were the same as those of preparation example 2.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 2.
Preparation example 9: preparation of film-forming resins
The procedure of preparation example 2 was followed to prepare a film-forming resin R9 dispersion, differing from preparation example 2 only in: in the step (2), a gradient heating method is not adopted, namely, the process of heating to 160 ℃ after mixing, heating to 180 ℃ after maintaining for 1h, continuously maintaining for 1h, heating to 200 ℃ after maintaining until the water yield reaches a theoretical value (12.6 g) (about 24 h) is changed into the process of heating to 200 ℃ after mixing, and maintaining until the water yield reaches the theoretical value (11.8 g), and the other raw materials and the preparation process are the same as those of the preparation example 2.
The amounts of the reactants, intermediates (i.e., the product of step (2)) and film-forming resin used in this preparation are shown in Table 2.
Preparation example 10
The procedure of preparation example 2 was followed to prepare a film-forming resin R10 dispersion, differing from preparation example 2 only in: the solid content of the product of the step (2) was adjusted to be the same as that of R2 as the film-forming resin R10 without performing the step (3), and the rest of raw materials and the preparation process were the same as those of the preparation example 2.
The amounts of the reactants used in this preparation and the data for the detection of the film-forming resin dispersion are shown in Table 2.
TABLE 1 reactant amounts and product detection data for preparation examples 1 to 5
Note that:
1 CHDM:1, 4-cyclohexanedimethanol (hereinafter the same applies);
2 GDGE1: polyethylene glycol diglycidyl ether (epoxy value 0.35-0.40) (hereinafter the same);
3 GDGE2: polyethylene glycol diglycidyl ether (epoxy value 0.70 to 0.80) (hereinafter the same applies).
TABLE 2 reactant amounts and product detection data for preparation examples 6 to 10
Analysis of detection results:
(1) Compared with R4, the elongation at break of R7 is obviously reduced, which indicates that the toughness of the film-forming resin can be improved by adopting polyethylene glycol diglycidyl ether for chain extension compared with the acrylic epoxy resin, and the influence of the antifouling coating on the telescopic capability of the netting can be reduced. The reason for this is presumed to be: the acrylic epoxy resin has a structure with larger molecular weight and a plurality of epoxy groups, and when the acrylic epoxy resin is formed into a plurality of crosslinking points, the crosslinking density is higher, so that the toughness of the acrylic epoxy resin is lower; the polyethylene glycol diglycidyl ether is a structure with smaller molecular weight and only contains two end epoxy groups, and can realize chain extension and simultaneously lead the film-forming resin to have more linear structures with large molecular weight, thus leading the film-forming resin to have larger toughness.
(2) Compared with R2, R10 cannot form a film, and the elongation at break cannot be tested, which indicates that the film forming performance of the resin can be improved and a flexible paint film can be formed by adopting polyethylene glycol diglycidyl ether to chain-extend the product in the step (2), so that the influence of the stretching capability of the netting can be born. The reason for this is presumed to be: by using polyethylene glycol diglycidyl ether for chain extension, the resin can be further chain-extended to form macromolecular compounds, so that the film-forming resin has better flexibility.
Examples 1 to 11: antifouling paint for low-copper netting and application of antifouling paint to netting
The antifouling paints for low copper wire netting of examples 1 to 11 were prepared according to the formulations shown in tables 3 and 4 (the amounts of the respective components were in mass percent, that is, the unit was wt%), and were denoted as R1Cu to R11Cu, wherein the film-forming resin dispersions used in R1Cu to R10Cu were the R1 to R10 dispersions prepared in preparation examples 1 to 10, respectively, and the film-forming resin dispersion used in R11Cu was the R7 dispersion prepared in preparation example 7.
The anti-fouling coating is formed on the surface of the netting by dip-coating the netting with the anti-fouling coatings R1 Cu-R9 Cu for the low copper netting. The antifouling coatings were subjected to antifouling evaluation and abrasion rate test, and the results are shown in table 2.
Table 3 coating formulations and performance test data for examples 1-7
Note that:
1 method for 6 months of antifouling evaluation: the net is subjected to real sea net hanging test in Zhejiang Zhoushan screw gate sea area after the net is dip-coated with the antifouling paint, and the net antifouling paint is evaluated by adopting an indirect comparison method because the net lacks direct national standard: the samples of comparative examples 1 and 2 were analyzed in comparison with the commercial samples, and the samples were evaluated as excellent in that the amount of the samples was less adhered than the commercial samples, and were evaluated as poor in that the samples were difficult to distinguish, and the samples were significantly more fouling organisms than the commercial samples (hereinafter the same applies);
2 method for detecting abrasion rate: the coating abrasion amount (hereinafter also referred to) was recorded according to GB/T31411-2015, which was measured on a monthly basis.
Table 4 coating formulations and performance test data for examples 1-7
Note that:
1 comparative example 1: supplied by Hainan Kewei functional materials Co., ltd (hereinafter);
2 comparative example 2: from boatsSupplied by Hengtai paint Co., ltd in mountain city (the same applies hereinafter).
Analysis of detection results:
(1) Compared with R2Cu, the one-time infiltration coating rate of the R8Cu coating on the netting is lower, which shows that in the process of preparing the film-forming resin, the one-time infiltration coating rate of the coating on the netting can be improved by carrying out polyaddition reaction on alkenyl in itaconic anhydride by using an initiator after polycondensation of itaconic anhydride and 1, 4-cyclohexanedimethanol. The reason for this is presumed to be: the polyaddition reaction can lead the film-forming resin to have a three-dimensional space network, endow the coating with a good instant thixotropic stabilizing effect, and lead the coating to show good sagging resistance, thereby improving the one-time infiltration coating rate of the coating to the netting.
(2) Compared with R2Cu, the one-time infiltration coating rate of the R9Cu coating on the netting is low, which indicates that in the process of preparing the film-forming resin, when the chain extension of the compound I is carried out by using the anhydride-containing compound and/or the dibasic acid and the dibasic alcohol, the one-time infiltration coating rate of the coating on the netting can be improved by adopting a gradient heating mode. The reason for this is presumed to be: the gradient heating mode is favorable for the formation of a film-forming resin three-dimensional space network, so that the antifouling paint has a good instant thixotropic stabilizing effect.
(3) Compared with R4Cu, the antifouling performance of R11Cu is obviously reduced, which indicates that in the process of preparing film-forming resin, the antifouling performance of the coating can be improved by adopting polyethylene glycol diglycidyl ether for chain extension compared with acrylic epoxy resin. The reason for this is presumed to be: compared with acrylic acid epoxy resin, the polyethylene glycol diglycidyl ether has higher hydrophilicity, so that the antifouling coating has better self-polishing property in seawater; meanwhile, unlike acrylic epoxy resin, polyethylene glycol diglycidyl ether has a structure with smaller molecular weight and only two end epoxy groups, so that the crosslinking density of the prepared film-forming resin is relatively low, and the abrasion rate of the film-forming resin in seawater is improved.
Examples 8 to 14: antifouling paint for copper-free netting and application of antifouling paint to netting
The antifouling paints for copper-free netting of examples 8 to 14 were prepared according to the formulations shown in Table 3, and were designated as S1 to S7, wherein the film-forming resin dispersions used in S1 to S7 were R1 to R7 dispersions prepared in preparation examples 1 to 7, respectively.
The low copper anti-fouling paint S1-S7 is adopted to dip-coat the net, and the anti-fouling paint is formed on the surface of the net. The antifouling coatings were subjected to antifouling evaluation and abrasion rate test, and the results are shown in table 2.
Table 3 coating formulations and performance test data for examples 8-14
Analysis of detection results:
as can be seen from tables 1 and 2, the antifouling properties of the low copper antifouling paints R1Cu to R6Cu and the copper-free antifouling paints S1 to S7 are significantly higher than those of the commercial antifouling paints (comparative example 1 and comparative example 2), indicating that the film-forming resins prepared in the present invention can impart a better antifouling property to the antifouling paint for a netting. In addition, the team of the invention observed that the net with the low copper antifouling paint had biofouling after 6 months, and the net with the copper-free antifouling paint had biofouling rate of almost 0, i.e. no macroscopic biofouling (thanks to the efficient green antifouling agent bromopyrrole nitrile).
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (10)

1. An antifouling paint for a netting is characterized by comprising film-forming resin; the preparation method of the film-forming resin comprises the following steps:
(1) Using anhydride and 1, 4-cyclohexanedimethanol as raw materials to perform esterification reaction between anhydride groups and hydroxyl groups to prepare a compound I;
(2) Taking a compound I, a compound containing anhydride and/or dibasic acid and dihydric alcohol as raw materials, and carrying out polycondensation reaction between anhydride groups and carboxyl groups and hydroxyl groups or carrying out polycondensation reaction between carboxyl groups and hydroxyl groups to prepare a polymer II containing carboxyl groups;
(3) The polymer II containing carboxyl and the compound containing at least two epoxy groups are used as raw materials to carry out ring-opening reaction between the epoxy groups and the carboxyl to prepare the film-forming resin.
2. The antifouling paint according to claim 1, wherein step (1) comprises the steps of: the method comprises the steps of taking itaconic anhydride, 1, 4-cyclohexanedimethanol and an initiator as raw materials, carrying out esterification reaction between anhydride groups and hydroxyl groups, and carrying out addition polymerization reaction of alkenyl groups to prepare the compound I.
3. The antifouling paint according to claim 1, wherein:
in the step (3), the compound containing at least two epoxy groups is polyethylene glycol diglycidyl ether; and/or
In the step (2), the anhydride-containing compound is hexahydrophthalic anhydride, and the dibasic acid is adipic acid; and/or
In the step (2), the dihydric alcohol is one or two of neopentyl glycol and tetraethylene glycol.
4. The antifouling paint according to claim 2, wherein the specific process of step (1) comprises the steps of: mixing itaconic anhydride, 1, 4-cyclohexanedimethanol and a solvent I under the protection of inert gas, reacting for 2.5-3.5 hours at the temperature of 60-70 ℃, adding a part of initiator, reacting for 1-2 hours at the temperature of 85-95 ℃, adding the rest of initiator, and continuing to react for 1-2 hours at the temperature of 85-95 ℃.
5. The antifouling paint according to claim 1, wherein the specific process of step (2) comprises the steps of: adding an anhydride-containing compound and/or dibasic acid, dihydric alcohol, a polycondensation catalyst and a solvent II into the product obtained in the step (1), reacting for 1-2 h at 155-165 ℃, then heating to 175-185 ℃ for continuous reaction for 1-2 h, heating to 195-205 ℃ for continuous reaction for 6-24 h, and finally heating to 225-235 ℃ for 30-40 min.
6. The antifouling paint according to claim 1, wherein the specific process of step (3) comprises the steps of: and (3) adding a compound containing at least two epoxy groups, a solvent III and a ring-opening reaction catalyst into the product obtained in the step (2), and reacting for 8-10 h at 150-160 ℃.
7. The antifouling paint according to any of claims 1,4 to 6, wherein:
in the step (1), the molar ratio of the anhydride to the 1, 4-cyclohexanedimethanol is 1:0.3-0.5; and/or
The molar ratio of the anhydride in the step (1) to the anhydride-containing compound and/or the dibasic acid and the dihydric alcohol in the step (2) is 1:1.0-1.7:1.0-1.5; and/or
The molar ratio of the anhydride in the step (1) to the epoxy groups in the compound containing at least two epoxy groups in the step (3) is 1:35-165.
8. The antifouling paint of claim 1, wherein the film-forming resin has a number average molecular weight of 9900 to 12500 Da.
9. The antifouling paint according to claim 1, comprising the following components in parts by weight: 35-60 parts of film forming resin dispersion liquid, 0-5 parts of auxiliary resin, 1-5 parts of mechanical accelerator, 0-16 parts of antifouling agent, 0-7 parts of pigment, 0-2 parts of plasticizer, 3-7 parts of auxiliary agent and 10-25 parts of coating solvent.
10. Use of an antifouling paint as claimed in any one of claims 1 to 9 for antifouling of netting.
CN202310451963.2A 2023-04-25 2023-04-25 Antifouling paint for netting and application thereof Pending CN116575246A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310451963.2A CN116575246A (en) 2023-04-25 2023-04-25 Antifouling paint for netting and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310451963.2A CN116575246A (en) 2023-04-25 2023-04-25 Antifouling paint for netting and application thereof

Publications (1)

Publication Number Publication Date
CN116575246A true CN116575246A (en) 2023-08-11

Family

ID=87533178

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310451963.2A Pending CN116575246A (en) 2023-04-25 2023-04-25 Antifouling paint for netting and application thereof

Country Status (1)

Country Link
CN (1) CN116575246A (en)

Similar Documents

Publication Publication Date Title
USRE41208E1 (en) Acid-capped quaternized polymer and compositions comprising such polymer
JP6797442B2 (en) Method for preparing main chain decomposition type zinc polyacrylate resin prepared by the monomer method
EP1496088B1 (en) Antifouling coating
JPS6257464A (en) Metal-containing resin composition
EP3222682B1 (en) Two-part anti-fouling paint composition, anti-fouling paint film, anti-fouling base member, and method for manufacturing anti-fouling base member
CN86103331A (en) The base-material of antifouling paint
EP3783075A1 (en) Antifouling coating composition, antifouling coating film, antifouling substrate, rosin compound for antifouling coating composition and method for producing antifouling coating composition
CN101942265B (en) Epoxy coal asphalt anti-corrosion paint and manufacturing method
CN109415595B (en) Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing substrate with antifouling coating film, and antifouling method
CN116575246A (en) Antifouling paint for netting and application thereof
JPH05155980A (en) Water-base dispersion
CN1294216C (en) Anti-bacterial non-lead cation electro-deposition coating composition
CN1224643C (en) Resin composition, method for producing polymer containing boron and anti-pollution paint
KR20130093840A (en) Resin for antifouling patint having excellent discoloration-resistance and crack-resistance and antifouling paint composition comprising the same
CN112111217A (en) Modified graphene oxide bio-based polyurethane anticorrosive paint and preparation method thereof
JP2003512400A (en) Biological support matrix, methods of making and using it
KR101638774B1 (en) Composition for manufacturing of anti-fauling marine structure and method of preparing the anti-fauling marine structure using the same
KR20130131277A (en) Antifouling coating
CN105820687A (en) Fishing net coating
CN1196064A (en) Resin containing amine bonded thereto and antifouling paint
CN111574662A (en) Preparation method of dimethyldiallylammonium chloride-unsaturated anhydride copolymer, antifouling agent and preparation method thereof, and antifouling paint
JP3110065B2 (en) Flexible cured product-forming antifouling composition for use in water and cured product thereof
KR102360904B1 (en) Water soluble antifouling paint for attachment prevention of marine organism
CN114292589B (en) Preparation method of antifouling paint for low-modulus fishing net
CN114605593B (en) Water-based self-cleaning polyurethane dispersoid, sterilization composition, preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination