CN114907740B - Antifouling resin for marine antifouling paint based on micro-nano hydrogel and preparation method thereof - Google Patents

Antifouling resin for marine antifouling paint based on micro-nano hydrogel and preparation method thereof Download PDF

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CN114907740B
CN114907740B CN202210579242.5A CN202210579242A CN114907740B CN 114907740 B CN114907740 B CN 114907740B CN 202210579242 A CN202210579242 A CN 202210579242A CN 114907740 B CN114907740 B CN 114907740B
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resin
antifouling
monomer
auxiliary
hydrophilic
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CN114907740A (en
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胡建坤
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Zhejiang University of Science and Technology ZUST
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Zhejiang University of Science and Technology ZUST
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Abstract

The invention relates to the technical field of marine antifouling, and discloses antifouling resin for marine antifouling paint based on micro-nano hydrogel and a preparation method thereof. The antifouling resin comprises a main resin and an auxiliary resin dispersed in the main resin in a micro-nano state; the auxiliary resin is hydrophilic resin with water swelling property; the main body resin is self-polishing resin; the auxiliary resin has a higher hydrophilicity than the main resin. The invention combines the main resin with self-polishing capability with the auxiliary resin capable of migrating to the surface of the coating to form the hydrogel layer, can play a better antifouling role, has a longer antifouling period, and can reduce the use of an antifouling agent.

Description

Antifouling resin for marine antifouling paint based on micro-nano hydrogel and preparation method thereof
Technical Field
The invention relates to the technical field of marine antifouling, in particular to an antifouling resin for marine antifouling paint based on micro-nano hydrogel and a preparation method thereof.
Background
Marine biofouling problems continue to plague people in the course of the development of marine economy and maritime industry. Marine biofouling not only increases the resistance to vessel navigation and fuel consumption and accelerates the corrosion and degradation of hull materials, but also can destroy the ecological balance of the water area. The international paint company in the united kingdom has counted for bilge fouling and fuel consumption: if the ship bottom is stained 5%, the fuel consumption is increased by 10%; if the fouling of the ship bottom is more than 50%, the burnup is increased by more than 40%.
After the organic tin antifouling paint of the specific weapon is completely forbidden in 1 st 2008, a main stream paint compound system taking copper acrylate/zinc/silicon resin as a carrier, cuprous oxide as a main antifouling agent and an organic micromolecular antifouling agent as an auxiliary antifouling agent is gradually formed. However, in such an antifouling system, the carrier itself has poor antifouling effect, and a large amount of an antifouling agent needs to be added, so that the toxicity of the antifouling agent can cause damage to the marine environment and ecology after long-term use.
For example, patent CN201511017972.2 discloses a self-polishing antifouling paint and a preparation method thereof, wherein in 100 parts by mass of the antifouling paint, 18 to 24 parts of resin, 50 to 55 parts of antifouling agent, 0.5 to 1.5 parts of graphene microchip, 3 to 6 parts of pigment and filler, 1 to 2 parts of dispersant, 1 to 2 parts of organic bentonite and the balance of organic solvent are calculated by solids; wherein the resin consists of hydroxy acrylic resin, zinc acrylate resin and rosin; the antifouling agent consists of copper pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, cuprous oxide and zinc oxide. Although the use of organic tin is avoided, the use amount of the organic micromolecular auxiliary antifouling agent is 6%, the use amount of the main antifouling agent cuprous oxide is 30-35%, the marine ecological environment is still damaged, and the development requirement of the environment-friendly antifouling paint under the new environment is difficult to meet.
Disclosure of Invention
The invention provides an antifouling resin for marine antifouling paint based on micro-nano hydrogel and a preparation method thereof, aiming at solving the technical problem that the dosage of an antifouling agent in the conventional marine antifouling paint is too large. The invention combines the main resin with self-polishing capability with the auxiliary resin capable of migrating to the surface of the coating to form the hydrogel layer, can play a better antifouling role, has a longer antifouling period, and can reduce the use of an antifouling agent.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides an antifouling resin for marine antifouling paint based on a micro-nano hydrogel, comprising a main resin, and an auxiliary resin dispersed in the main resin in a micro-nano state; the auxiliary resin is hydrophilic resin with water swelling property; the main body resin is self-polishing resin; the auxiliary resin has a higher hydrophilicity than the main resin.
In an antifouling coating layer formed after coating with a marine antifouling paint, a main resin constitutes a main structure of the coating layer, and an auxiliary resin is dispersed therein in a micro-nano state. After the micro-nano auxiliary resin is contacted with seawater, the micro-nano auxiliary resin with stronger hydrophilicity gradually migrates to the surface of the coating, and continuously absorbs water and swells to form micro-nano hydrogel in the migration process, and finally a smooth hydrogel film is formed on the surface of the coating, so that the effect of preventing biological adhesion is exerted. Although the hydrogel film can improve the antifouling effect of the coating to a certain extent, the hydrogel film can be gradually degraded in the process of contacting with seawater for a long time, the self-polishing resin is adopted in the invention, and the hydrogel film formed by the auxiliary resin on the surface of the coating and the main resin on the surface layer can be gradually degraded and fall off under the action of the seawater, so that the auxiliary resin in the coating is further released, a new hydrogel film is formed on the surface of the coating, and the antifouling effect is continuously exerted.
Through the mode, the antifouling resin provided by the invention can play a better antifouling effect, has a longer antifouling period, and can reduce the use amount of the antifouling agent in the marine antifouling paint, so that the damage of the antifouling agent to the marine environment and ecology is reduced. Through experiments, when the antifouling resin is used in marine antifouling paint, cuprous oxide is not required to be added into the paint, and the better antifouling effect can be achieved by only adding 5-14 wt% of organic micromolecular auxiliary antifouling agent.
In addition, in the anti-fouling resin of the present invention, since the auxiliary resin exists in the host resin in a micro-nano state, there is less entanglement of molecular chains with the host resin, facilitating migration of the auxiliary resin to the coating surface, while absorbing water to form a surface hydrogel layer to exert an effect of preventing adhesion of organisms.
Preferably, the antifouling resin further comprises a micro-nano accelerator; the micro-nano accelerator is an amphiphilic molecule.
The micro-nano accelerator can promote the formation of hydrophilic micro-areas and hydrophobic micro-areas in auxiliary resin, so that the coating has better antifouling effect, and the specific mechanism is as follows: in the process of transferring the auxiliary resin to the surface of the main resin, the hydrophilic micro-areas can absorb water and swell, and finally, a hydrogel layer is formed on the surface of the coating layer, so that the effects of lubrication and pollution prevention are exerted; the molecular chains in the hydrogel layer are not connected through covalent bonds, so that the hydrogel layer is easy to polish and abrade when contacted with water, and the hydrophobic micro-areas are less contacted with water and have slower polishing speed, so that the hydrogel layer can be prevented from being polished too fast, and the antifouling period of the coating is prolonged.
In addition, the amphipathy of the micro-nano accelerator is utilized, and the hydrophilic-hydrophobic difference of the auxiliary resin and the main resin is matched, so that the auxiliary resin forms a micro-nano state in the main resin in the preparation process of the anti-fouling resin, and the auxiliary resin is beneficial to migration to the surface of the anti-fouling coating after the anti-fouling coating is contacted with water.
Preferably, the mass ratio of the main resin to the auxiliary resin to the micro-nano accelerator is 1:0.2-0.6:0.05-0.15.
Preferably, the micro-nano accelerator comprises an amphiphilic polymer with a molecular weight of 1000-6000; the monomer of the amphiphilic polymer comprises an anhydride monomer and/or a polybasic acid monomer, and further comprises a polyalcohol monomer.
Further, the ratio of the total molar amount of the acid anhydride-based monomer and the polybasic acid-based monomer to the molar amount of the polyhydric alcohol-based monomer is 1.05-1.35:1 or 1:1.1-1.5.
Preferably, the auxiliary resin is a hydrophilic addition polymerization resin and/or a hydrophilic polyurethane resin; the hydrophilic polyaddition resin comprises hydrophilic monomers and hydrophobic monomers in a mass ratio of 1:0-0.5; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃; the hydrophilic and/or hydrophobic monomers include acrylic monomers.
Further, the hydrophilic monomers also include N-vinyl pyrrolidone and/or acrylamide.
Preferably, the hydrophilic polyurethane resin is hyperbranched hydrophilic polyurethane resin; the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) Taking polytetrahydrofuran ether glycol and dihydroxyacid with the mass ratio of 1:6-10 as raw materials, and carrying out esterification reaction to obtain hyperbranched polyester;
(B) Taking dihydroxyl acid and diisocyanate with the mass ratio of 1:4.5-5.5:0.8-1.2 and hyperbranched polyester prepared in the step (A) as raw materials to carry out polymerization reaction to prepare the hyperbranched hydrophilic polyurethane resin.
Compared with non-hyperbranched hydrophilic polyurethane resin, the hyperbranched hydrophilic polyurethane resin has proper degradation speed, is favorable for the paint to exert better long-term antifouling effect, and specifically: the hyperbranched hydrophilic polyurethane resin can be self-degraded, so that after the surface hydrogel layer formed by the auxiliary resin is damaged, the main resin of the surface layer is timely degraded and the internal auxiliary resin is released, a new surface hydrogel layer is formed, and a good antifouling effect is given to the coating; meanwhile, the hyperbranched hydrophilic polyurethane resin has a highly branched structure, so that the surface hydrogel layer can be endowed with high strength, the water flow erosion can be slowed down, the water flow erosion is prevented from being consumed too fast, and the antifouling effect of the coating is prolonged.
Further, in steps (a) and (B), the dihydroxyacid includes dihydroxypropionic acid and/or dihydroxybutyric acid.
Preferably, the host resin is a polyaddition resin and/or a polyurethane resin; the monomer of the addition polymerization resin comprises a hydrophilic addition polymerization monomer and a hydrophobic addition polymerization monomer in a mass ratio of 0-1:1; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃; the hydrophilic addition monomer and/or the hydrophobic addition monomer comprise an acrylic monomer; the monomers of the polyurethane resin comprise polyamine and/or polyol and also comprise polyisocyanate.
Further, in the monomer of the polyurethane resin, the ratio of the total molar amount of hydroxyl groups to amino groups to the molar amount of isocyanate groups is 0.7 to 0.95:1.
Further, the hydrophilic addition monomer may further include one or more of vinyl acetate, N-vinylpyrrolidone and acrylonitrile.
In a second aspect, the present invention provides a method for preparing the anti-fouling resin, comprising the steps of: heating the main resin dispersion liquid to 60-70 ℃, adding the micro-nano accelerator dispersion liquid, dropwise adding the auxiliary resin dispersion liquid into the main resin dispersion liquid at the speed of 1.0-2.5 mL/min under stirring, heating to 90-100 ℃ after the dropwise adding is completed, and continuously stirring for 1h to obtain the antifouling resin.
The invention adopts a specific method to prepare the antifouling resin, and can lead the auxiliary resin to be dispersed in the main resin in a micro-nano state, and the specific mechanism is as follows: the polarity of the auxiliary resin is higher than that of the main resin, under the micro-nano accelerator and special process conditions, the auxiliary resin with larger molecular chain flexibility can generate molecular chain deformation, and the auxiliary resin is gathered together through hydrophilic-hydrophobic interaction and molecular secondary valence bond acting force to form a nano or micro structure (the particle size is between 280nm and 1.5 microns), and is dispersed in the main resin to form a hydrophilic micro-nano area in the antifouling resin, and the main resin forms a hydrophobic area with relatively higher hydrophobicity.
Preferably, the solid contents of the main resin dispersion liquid, the auxiliary resin dispersion liquid and the micro-nano accelerator dispersion liquid are 45 to 55wt%, 45 to 55wt% and 65 to 75wt%, respectively; the mass ratio of the main resin dispersion liquid, the auxiliary resin dispersion liquid and the micro-nano accelerator dispersion liquid is 1:0.25-0.50:0.05-0.10.
In a third aspect, the invention provides application of the antifouling resin in a copper-free stable controlled release marine antifouling paint.
Preferably, the copper-free stable controlled release antifouling paint comprises the following components in percentage by weight: 5 to 25 percent of the antifouling resin, 5 to 16 percent of the antifouling agent, 0 to 10 percent of rosin, 0 to 4 percent of tackifier, 0 to 6 percent of pigment, 0 to 40 percent of filler, 0 to 2 percent of plasticizer, 0 to 7 percent of auxiliary agent and the balance of solvent.
Preferably, the auxiliary agent comprises one or more of dispersing agent, leveling agent, anti-settling thixotropic agent and antioxidant.
Preferably, the rosin comprises hydrogenated rosin.
Preferably, the tackifier comprises liquid styrene-butadiene rubber. The liquid polybutadiene rubber can endow the coating with better initial viscosity and flexibility.
Preferably, the filler comprises zinc oxide.
Preferably, the anti-fouling agent comprises bromopyrrocarbonitrile and/or zinc pyrithione.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the main resin with self-polishing capability is matched with the auxiliary resin capable of migrating to the surface of the coating to form the hydrogel layer, so that a better antifouling effect can be exerted, and a longer antifouling period effect is achieved, and thus, the use of an antifouling agent can be reduced;
(2) The auxiliary resin is dispersed in the main resin in a micro-nano state, so that the auxiliary resin is easy to migrate to the surface of the antifouling coating to play a role in preventing adhesion of organisms, and the auxiliary resin is favorable for migrating to the surface of the coating after the coating contacts with water to form a surface hydrogel layer to play a role in antifouling;
(3) By adding the micro-nano accelerator into the antifouling resin, the auxiliary resin can form hydrophilic micro-areas and hydrophobic micro-areas, so that the antifouling effect of the antifouling paint is prolonged, the antifouling effect is better, and the auxiliary resin can form micro-nano states in the main resin;
(4) The hyperbranched hydrophilic polyurethane resin is used as the auxiliary resin, so that the erosion of water flow to the surface hydrogel layer can be slowed down, and when the hydrogel layer on the surface of the coating is damaged, a new surface hydrogel layer can be formed in time, thereby ensuring that the coating has a better long-term antifouling effect.
Detailed Description
The invention is further described below with reference to examples.
General examples
An antifouling resin for marine antifouling paint based on micro-nano hydrogel comprises a main resin, a micro-nano accelerator and an auxiliary resin dispersed in the main resin in a micro-nano state. The auxiliary resin is hydrophilic resin with water swelling property; the main body resin is self-polishing resin; the auxiliary resin has a higher hydrophilicity than the main resin. The mass ratio of the main resin to the auxiliary resin to the micro-nano accelerator is 1:0.2-0.6:0.05-0.15.
The host resin is a polyaddition resin and/or a polyurethane resin.
The monomer of the addition polymerization resin comprises a hydrophilic addition polymerization monomer and a hydrophobic addition polymerization monomer in a mass ratio of 0-1:1; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃. The hydrophilic addition monomer and/or the hydrophobic addition monomer comprise an acrylic monomer; optionally, the hydrophilic addition monomer further comprises one or more of vinyl acetate, N-vinylpyrrolidone and acrylonitrile.
The acrylic monomer can be selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, triisopropyl silicon methacrylate, tributyl silicon acrylate, tributyl silicon methacrylate, trimethyl silicon acrylate, trimethyl silicon methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, hexyl acrylate, hexyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, ethoxyethoxyethoxyethyl acrylate and ethoxyethoxyethoxyethyl methacrylate.
As a specific embodiment, the method for producing the addition polymerization resin comprises the steps of: 200 parts of monomers (including hydrophilic polyaddition monomers and hydrophobic polyaddition monomers with the mass ratio of 0-1:1), 0.9-1.5 parts of Azodiisobutyronitrile (AIBN), 0.3-0.9 part of Azodiisovaleronitrile (AMBN) and 190-210 parts of reaction solvent are mixed according to parts by weight, reacted for 2.5-3.5 hours at 70-90 ℃, then 0.2 part of Tertiary Amyl Peroxyacetate (TAPV) is added, and reacted for 2-3 hours at 80-100 ℃ to obtain polyaddition resin. Optionally, the monomer is tributyl silicon methacrylate, or consists of methyl methacrylate and ethoxyethoxyethyl methacrylate with the mass ratio of 1:0.5-1, or consists of isooctyl methacrylate, vinyl acetate and vinyl pyrrolidone with the mass ratio of 1:0.2-0.3:0.5-0.7, or consists of isooctyl acrylate, trimethyl silicon methacrylate, isodecyl methacrylate and acrylonitrile with the mass ratio of 1:0.5-0.8:0.4-0.6:0.3-0.4.
The monomers of the polyurethane resin comprise polyamine and/or polyol and also comprise polyisocyanate.
The polyisocyanate may be selected from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate. The polyol may be one or more selected from hydroxyl terminated polyesters, hydroxyl terminated polyethers, C2-8 diols, C3-10 triols. The polyamine can be selected from one or more of diamine and triamine.
As a specific embodiment, the preparation method of the polyurethane resin comprises the following steps: mixing polyamine and/or polyol, a reaction solvent, polyisocyanate and a catalyst, reacting at 60-70 ℃ until the mixture is completely reacted, and adding butanediol to chain extend to obtain the polyurethane resin.
As a specific embodiment, the preparation method of the polyurethane resin comprises the following steps: mixing polyamine and/or polyol, a reaction solvent, isophorone diisocyanate (IPDI) and a catalyst, reacting for 3.5-4.5 hours at 60-70 ℃, adding diphenylmethane diisocyanate (MDI), continuously reacting at 60-70 ℃ until the reaction is completed, and adding dihydric alcohol for chain extension to obtain polyurethane resin.
The auxiliary resin is hydrophilic polyaddition resin and/or hydrophilic polyurethane resin.
The hydrophilic polyaddition resin comprises hydrophilic monomers and hydrophobic monomers in a mass ratio of 1:0-0.5; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃. The hydrophilic monomer and/or hydrophobic monomer includes an acrylic monomer; optionally, the hydrophilic monomer further comprises N-vinyl pyrrolidone and/or acrylamide.
The acrylic monomer may be selected from one or more of methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, methoxyethyl acrylate, polyethylene glycol methacrylate, tetrahydrofuran methacrylate, dimethylaminoethyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, isobutyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, and benzyl methacrylate.
As a specific embodiment, the method for preparing the hydrophilic polyaddition resin comprises the following steps: 200 parts of monomers (including hydrophilic polyaddition monomers and hydrophobic polyaddition monomers with the mass ratio of 1:0-0.5), 0.3 part of AIBN, 3 parts of AMBN, 0.5 part of TAPV and 196 parts of reaction solvent are mixed according to parts by weight, reacted for 2.5-3.5 hours at 70-90 ℃, then 0.2 part of Benzoyl Peroxide (BPO) is added, and reacted for 2-3 hours at 100-120 ℃ to obtain the hydrophilic polyaddition resin. Optionally, the monomer consists of vinyl pyrrolidone and methoxyethyl acrylate in a mass ratio of 1:0.8-1.2, or consists of isooctyl methacrylate, vinyl acetate and vinyl pyrrolidone in a mass ratio of 1:0.2-0.3:0.5-0.7, or consists of isobornyl methacrylate, vinyl pyrrolidone and methoxyethyl acrylate in a mass ratio of 0.1-0.3:0.6-0.8:0.9-1.1, or consists of acrylic acid, isobornyl methacrylate, methoxyethyl acrylate and hydroxyethyl acrylate in a mass ratio of 1:1.5-2.0:2.5-2.8:0.8-1.3.
The hydrophilic polyurethane resin is hyperbranched hydrophilic polyurethane resin; the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) Taking polytetrahydrofuran ether glycol and dihydroxyacid with the mass ratio of 1:6-10 as raw materials, and carrying out esterification reaction to obtain hyperbranched polyester;
(B) Taking dihydroxyl acid and diisocyanate with the mass ratio of 1:4.5-5.5:0.8-1.2 and hyperbranched polyester prepared in the step (A) as raw materials to carry out polymerization reaction to prepare the hyperbranched hydrophilic polyurethane resin.
As a specific embodiment, the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) Mixing polytetrahydrofuran ether glycol (PTMG 1000) and dihydroxyic acid in a mass ratio of 1:6-10, reacting for 3-4 hours at 165-175 ℃, heating to 195-205 ℃ to react until the acid value is lower than 3, and immediately cooling after heating to 225-235 ℃ to obtain hyperbranched polyester;
(B) The dihydroxyl acid, diisocyanate and catalyst with the mass ratio of 1:4.5-5.5 are mixed and then react for 50-90 min at 70-80 ℃, then diluent is added, and the reaction is continued to be completed at 70-80 ℃; adding hyperbranched polyester, wherein the mass ratio of the hyperbranched polyester to the 2, 2-dimethylolpropionic acid is 0.8-1.2:1, and continuously reacting at 70-80 ℃ until the reaction is completed; and adding dihydric alcohol to chain extend to obtain the hyperbranched hydrophilic polyurethane resin. Optionally, the diluent is N-methyl pyrrolidone and dimethylbenzene in a mass ratio of 1-2:1, and the mass ratio of the diluent to diisocyanate is 1.6-2.1:1.
The micro-nano accelerator comprises an amphiphilic polymer with the molecular weight of 1000-6000. The monomer of the amphiphilic polymer comprises an anhydride monomer and/or a polybasic acid monomer, and also comprises a polyalcohol monomer; the ratio of the total molar weight of the anhydride monomer and the polybasic acid monomer to the molar weight of the polybasic alcohol monomer is 1.05-1.35:1 or 1:1.1-1.5.
The anhydride monomer can be selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and trimellitic anhydride. The polyacid monomer may be selected from glutaric and/or adipic acid. The polyol monomer may be selected from one or more of ethylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, triethylene glycol and tetraethylene glycol.
As a specific embodiment, the preparation process of the micro-nano accelerator comprises the following steps: 280 to 320 parts of monomer, 50 to 60 parts of reaction solvent and 1.3 to 1.6 parts of catalyst are mixed according to parts by weight, then reacted for 2.5 to 3.5 hours at 155 to 165 ℃, heated to 190 to 210 ℃ and reacted for 2 to 4 hours, then heated to 220 to 240 ℃ and kept for 20 to 40 minutes, and 62 to 81 parts of reaction solvent is added to obtain the micro-nano accelerator.
A method for preparing the anti-fouling resin, comprising the following steps: heating a main resin dispersion liquid with the solid content of 45-55wt% to 60-70 ℃, adding a micro-nano accelerator dispersion liquid with the solid content of 65-75wt%, dripping an auxiliary resin dispersion liquid with the reinforcing content of 45-55wt% into the main resin dispersion liquid at the speed of 1.0-2.5 mL/min under stirring, wherein the mass ratio of the main resin dispersion liquid to the auxiliary resin dispersion liquid to the micro-nano accelerator dispersion liquid is 1:0.25-0.50:0.05-0.10, heating to 90-100 ℃ after dripping, and continuously stirring for 1h to obtain the antifouling resin.
The copper-free stable controlled release marine antifouling paint comprises the following components in percentage by weight: 5 to 25 percent of the antifouling resin, 5 to 16 percent of the antifouling agent, 0 to 10 percent of rosin, 0 to 4 percent of tackifier, 0 to 6 percent of pigment, 0 to 40 percent of filler, 0 to 2 percent of plasticizer, 0 to 7 percent of auxiliary agent and the balance of solvent. The auxiliary agent comprises one or more of dispersing agent, leveling agent, anti-settling thixotropic agent and antioxidant. The rosin comprises hydrogenated rosin. The tackifier comprises liquid styrene butadiene rubber. The filler comprises zinc oxide. The antifouling agent comprises bromopyrrocarbonitrile and/or zinc pyrithione.
As a specific embodiment, the antifouling paint is a marine copper-free stable controlled release marine antifouling paint, which comprises the following components in percentage by weight: 5 to 16 percent of antifouling resin, 5 to 16 percent of antifouling agent, 4 to 10 percent of rosin, 0.5 to 4 percent of tackifier, 0 to 6 percent of pigment, 5 to 40 percent of filler, 0 to 2 percent of plasticizer, 0 to 7 percent of auxiliary agent and the balance of solvent.
As a specific embodiment, the antifouling paint is a copper-free steady controlled release marine antifouling paint for a netting, and comprises the following components: 5 to 22 percent of the antifouling resin, 6 to 16 percent of the antifouling agent, 0.5 to 4 percent of the tackifier, 0 to 6 percent of the pigment, 0 to 2 percent of the plasticizer, 0 to 7 percent of the auxiliary agent and the balance of the solvent.
As a specific embodiment, the antifouling paint is a copper-free stable controlled release marine antifouling paint for offshore platforms, and comprises the following components in percentage by weight: 5 to 16 percent of antifouling resin, 6 to 16 percent of antifouling agent, 4 to 10 percent of rosin, 0.5 to 4 percent of tackifier, 0 to 6 percent of pigment, 5 to 40 percent of filler, 0 to 2 percent of plasticizer, 0 to 7 percent of auxiliary agent and the balance of solvent.
Preparation example 1: synthesis of a Main resin (addition polymerization resin)
(1) Synthesis of the host resin 1A:
200g of tributyl methacrylate, 1.5g of AIBN, 0.3g of AMBN, 178g of xylene and 20g of propylene glycol monomethyl ether are added into a 1L four-necked flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the mixture is kept at 85 ℃ for 3 hours, then 0.2g of TAPV is added, the temperature is raised to 95 ℃ for 2.5 hours, and the mixture is cooled to room temperature, so that a main resin 1A dispersion with a solid content of about 50% is obtained.
(2) Synthesis of the host resin 1B:
into a 1L four-necked flask equipped with a stirrer and a reflux condenser and protected with nitrogen gas were charged 100g of methyl methacrylate, 100g of ethoxyethoxyethyl methacrylate, 1.5g of AIBN, 0.3g of AMBN, 178g of xylene, 20g of ethylene glycol monobutyl ether, and the flask was kept at 70℃for 3 hours, then 0.2g of TAPV was added, and after heating to 80℃for 2.5 hours, the flask was cooled to room temperature to obtain a bulk resin 1B dispersion having a solid content of about 50%.
(3) Synthesis of the host resin 1C:
A1L four-necked flask equipped with a stirrer and a reflux condenser and protected with nitrogen was charged with 100g of isooctyl methacrylate, 30g of vinyl acetate, 70g of vinylpyrrolidone, 0.9g of AIBN, 0.9g of AMBN, 178g of solvent oil, 20g of ethylene glycol monobutyl ether, and the flask was kept at 90℃for 3 hours, then 0.2g of TAPV was added, and the flask was warmed to 100℃and kept at 2.5 hours, and then cooled to room temperature to obtain a bulk resin 1C dispersion having a solid content of about 50%.
(4) Synthesis of the host resin 1D:
A1L four-necked flask equipped with a stirrer and a reflux condenser and protected with nitrogen was charged with 80g of isooctyl acrylate, 50g of trimethylsilyl methacrylate, 40g of isodecyl methacrylate, 30g of acrylonitrile, 0.9g of AIBN, 0.9g of AMBN, 178g of solvent oil and 20g of ethylene glycol monobutyl ether, the mixture was kept at 90℃for 3 hours, then 0.2g of TAPV was added, and the mixture was heated to 100℃for 2.5 hours, and then cooled to room temperature to obtain a 1D dispersion of a main resin having a solid content of about 50%.
Preparation example 2: synthesis of Main resin (polyurethane resin)
(1) Synthesis of the host resin 2A:
under the protection of argon, mixing 200g of dry hydroxyl terminated polyester, 240g N-methylpyrrolidone, 33.4g of MDI and 4 drops of di-n-butyltin dilaurate (DBTDL), continuously reacting at 65 ℃ until NCO reaches a theoretical value (di-n-butylamine titration method), adding 1.8g of butanediol to chain extend for 3 hours, and cooling to obtain a target product, namely a main resin 2A dispersion liquid with the solid content of about 50 percent.
(2) Synthesis of the host resin 2B:
under the protection of argon, mixing 100g of dry hydroxyl terminated polyester, 100g of hydroxyl terminated polyether, 235g N-methyl pyrrolidone, 30g of IPDI and 4 drops of DBTDL, continuously reacting at 65 ℃ until NCO reaches a theoretical value, adding 1.8g of butanediol to chain extend for 3 hours, and cooling to obtain a target product, namely a main resin 2B dispersion liquid with the solid content of about 50%.
(3) Synthesis of the host resin 2C:
under the protection of argon, mixing 100g of dry hydroxyl terminated polyester, 100g of hydroxyl terminated polyether, 237. 237g N-methyl pyrrolidone, 22.2g of IPDI and 4 drops of DBTDL, reacting for 4 hours at 65 ℃, adding 8.3g of MDI, continuing to react at 65 ℃ until NCO reaches a theoretical value, adding 1.8g of butanediol, extending for 3 hours, and cooling to obtain a target product, namely a main resin 2C dispersion liquid with the solid content of about 50 percent.
Preparation example 3: synthesis of auxiliary resin (hydrophilic addition polymerization resin)
(1) Synthesis of auxiliary resin 3A:
100g of vinylpyrrolidone, 100g of methoxyethyl acrylate, 0.3g of AIBN, 3.0g of AMBN, 0.5g of TAPV, 176g of solvent oil and 20g of propylene glycol monomethyl ether are added into a 1L four-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the mixture is kept at 100 ℃ for 3 hours, then 0.2g of BPO is added, the mixture is kept at 110 ℃ for 2.5 hours, and the mixture is cooled to room temperature to obtain an auxiliary resin 3A dispersion with a solid content of about 50%.
(2) Synthesis of auxiliary resin 3B:
into a 1L four-necked flask equipped with a stirrer and a reflux condenser and protected with nitrogen gas were added 30g of isobornyl methacrylate, 70g of vinylpyrrolidone, 100g of methoxyethyl acrylate, 0.3g of AIBN, 3.0g of AMBN, 0.5g of TAPV, 176g of xylene, 20g of propylene glycol monomethyl ether, the mixture was kept at 100℃for 3 hours, then 0.2g of BPO was added, the mixture was kept at 110℃for 2.5 hours, and the mixture was cooled to room temperature to obtain an auxiliary resin 3B dispersion having a solid content of about 50%.
(3) Synthesis of auxiliary resin 3C:
30g of acrylic acid, 60g of isobornyl methacrylate, 80g of methoxyethyl acrylate, 30g of hydroxyethyl acrylate, 0.3g of AIBN, 3.0g of AMBN, 0.5g of TAPV, 146g of dimethylbenzene and 50g of propylene glycol monomethyl ether are added into a 1L four-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the mixture is kept at 100 ℃ for 3 hours, then 0.2g of BPO is added, the mixture is heated to 110 ℃ for 2.5 hours, then cooled to 60 ℃, 36g of triethylamine is added, the mixture is cooled to room temperature after 0.5 hour of reaction, and the reaction is completed to obtain the auxiliary resin 3C dispersion with the solid content of about 50%.
Preparation example 4: synthesis of auxiliary resin (hyperbranched hydrophilic polyurethane resin)
(1) Synthesis of hyperbranched polyester HO-HB-OH:
100g of PTMG1000 and 600g of dihydroxypropionic acid (DMPA) were added to the reactor under nitrogen. After stirring uniformly, slowly heating to 170 ℃, maintaining the temperature for 3h, continuously heating to 200 ℃ (during the whole process, continuously blowing nitrogen), reacting until the acid value is lower than 3, and immediately cooling after heating to 230 ℃. When the temperature is reduced to 100 ℃, the pressure is reduced, the water is removed for 1h, and then the temperature is reduced to room temperature, so that the hyperbranched polyester HO-HB-OH is obtained.
(2) Synthesis of auxiliary resin 4A:
mixing 100g of DMPA, 498g of IPDI and 6 drops of catalyst DBTDL under the protection of high-purity nitrogen, reacting for 1h at 70 ℃, adding 500g of dry N-methylpyrrolidone and 400g of dry dimethylbenzene, and continuing to react until NCO reaches a theoretical value; then adding 100g of hyperbranched polyester HO-HB-OH, and continuing to react until NCO reaches a theoretical value; then, 96g of triethylene glycol (TEG) was added thereto, and after completion of the reaction, 67g of Triethylamine (TEA) was used for neutralization to obtain a dispersion of the auxiliary resin 4A having a solid content of about 50%.
The hyperbranched polyester HO-HB-OH and the auxiliary resin 4A were prepared as follows:
Figure BDA0003661691840000111
(3) Synthesis of auxiliary resin 4B:
Mixing dried 110g of dimethylolbutanoic acid (DMBA), 390g of Hexamethylene Diisocyanate (HDI) and 6 drops of catalyst DBTDL under the protection of high-purity nitrogen, reacting for 1h at 70 ℃, adding 500g of dried N-methylpyrrolidone and 300g of dried xylene, and continuing to react until NCO reaches a theoretical value; then adding 100g of hyperbranched polyester HO-HB-OH, and continuing to react until NCO reaches a theoretical value; 99g of tetraethylene glycol was then added, and after completion of the reaction, 60g of TEA was used to neutralize the mixture, thereby obtaining a dispersion of auxiliary resin 4B having a solids content of about 50%.
(4) Synthesis of auxiliary resin 4C:
mixing dried 110g DMBA, 560 g 4,4' -dicyclohexylmethane diisocyanate (HMDI) and 7 drops of catalyst DBTDL under the protection of high-purity nitrogen, reacting for 1h at 70 ℃, adding 600g dried N-methylpyrrolidone and 400g dried xylene, and continuing to react until NCO reaches a theoretical value; then adding 100g of hyperbranched polyester HO-HB-OH, and continuing to react until NCO reaches a theoretical value; 99g of tetraethylene glycol was then added, and after completion of the reaction, the mixture was neutralized with 66g of Diethanolamine (DEA) to obtain a dispersion of 4C as an auxiliary resin having a solid content of about 50%.
Preparation example 5: synthesis of auxiliary resin (hydrophilic polyurethane resin)
Mixing 100g of DMPA, 498g of IPDI and a certain amount of catalyst DBTDL under the protection of high-purity nitrogen, reacting for 1h at 70 ℃, adding 500g of dry N-methylpyrrolidone and 400g of dry xylene, and continuing to react until NCO reaches a theoretical value; then 100g of PTMG1000 is added, and the reaction is continued until NCO reaches a theoretical value; then, 96g of triethylene glycol (TEG) was added thereto, and after completion of the reaction, 67g of Triethylamine (TEA) was used for neutralization to obtain a dispersion of the auxiliary resin 5A having a solid content of about 50%.
Preparation example 6: synthesis of micro-nano accelerator
(1) Synthesis of micro-nano accelerator 6A:
180g of phthalic anhydride, 80g of ethylene glycol, 40g of hexanediol, 60g of dimethylbenzene and 1.5g of C-94 catalyst are taken, mixed and heated to 160 ℃, maintained for 3 hours, heated to 200 ℃, maintained for 2.5 hours, continuously heated to 230 ℃, maintained for 0.5 hour, cooled to 90 ℃, added with 71g of dimethylbenzene, and reacted to obtain the micro-nano accelerator 6A dispersion with the solid content of about 70% and the number average molecular weight of 2846.
(2) Synthesis of micro-nano accelerator 6B:
110g of phthalic anhydride, 90g of trimellitic anhydride, 80g of ethylene glycol, 40g of hexanediol, 60g of dimethylbenzene and 1.6g of C-94 catalyst are taken, the mixture is heated to 155 ℃, maintained for 2.5h, heated to 200 ℃, maintained for 2h, continuously heated to 230 ℃, maintained for 0.5h, cooled to 90 ℃, 81g of dimethylbenzene is added, and the reaction is finished to obtain a micro-nano accelerator 6B dispersion with the solid content of about 70% and the number average molecular weight of 1473.
(3) Synthesis of micro-nano accelerator 6C:
110g of phthalic anhydride, 90g of trimellitic anhydride, 50g of ethylene glycol, 30g of hexanediol, 50g of dimethylbenzene and 1.3g of C-94 catalyst are taken, mixed and heated to 165 ℃, maintained for 3.5h, heated to 210 ℃, maintained for 4h, continuously heated to 230 ℃, maintained for 0.5h, cooled to 90 ℃, added with 62g of dimethylbenzene, and finally reacted to obtain the micro-nano accelerator 6C dispersion with the solid content of about 70% and the number average molecular weight of 5695.
Examples 1 to 9 and comparative examples 1 to 4: copper-free stable controlled release antifouling paint for ship
(1) Preparation of an antifouling resin dispersion:
examples 1 to 9: the main resin dispersion (obtained in preparation example 1) was heated to 60 ℃, a micro-nano accelerator 6A dispersion (obtained in preparation example 6) corresponding to 6% of the mass of the main resin dispersion was added, an auxiliary resin dispersion (obtained in preparation example 3) corresponding to 25% of the mass of the main resin dispersion was slowly dropped thereto at a rate of 1.0mL/min under 3500r/min dispersion conditions, the temperature was raised to 90 ℃ after the dropping was completed, and the dispersion was kept for 1 hour under 3500r/min dispersion conditions, and then cooled down to obtain an antifouling resin dispersion.
In examples 1 to 9, the main resin and the auxiliary resin used are shown in table 1, respectively.
TABLE 1
Resin numbering 1A 1B 1C
3A Example 1 Example 4 Example 7
3B Example 2 Example 5 Example 8
3C Example 3 Example 6 Example 9
Comparative example 1 differs from example 1 only in that no auxiliary resin dispersion was added during the preparation of the anti-fouling resin dispersion.
Comparative example 2 differs from example 1 only in that in the preparation of the antifouling resin dispersion, the main resin 1A dispersion was changed to a commercial M133 resin dispersion (styrene-methyl methacrylate-butyl acrylate terpolymer, which could not be polished in seawater) of equal mass and the same solid content.
Comparative example 3 differs from example 1 only in that the micro-nano accelerator dispersion was not added during the preparation of the anti-fouling resin dispersion.
Comparative example 4: the main resin 1A dispersion (obtained in production example 1) was heated to 60 ℃, and a micro-nano accelerator 6A dispersion (obtained in production example 6) corresponding to 6% by mass of the main resin 1A dispersion and an auxiliary resin 3A dispersion (obtained in production example 3) corresponding to 25% by mass of the main resin 1A dispersion were added, and the mixture was heated to 90 ℃, maintained at 3500r/min dispersion for 2.5 hours, and then cooled to obtain an antifouling resin dispersion.
(2) Preparation of a copper-free stable controlled release antifouling paint for a ship:
According to the formulations of tables 2 and 3 (the amounts of the respective raw materials were in mass percent), after all the raw materials were uniformly mixed, the copper-free stable controlled release antifouling paints for ship of examples 1 to 9 and comparative examples 1 to 3 were prepared (in comparative examples 1 and 3, the solid content of the antifouling paint was controlled by changing the amounts of the antifouling resin dispersion liquid, xylene and propylene glycol monomethyl ether, as in example 1).
(3) One year antifouling evaluation:
the copper-free stable controlled release antifouling paints for ship of examples 1 to 9 were respectively applied to the surfaces of the sample plates to form antifouling coatings having a thickness of 100. Mu.m. According to the method of GB/T7789-2007, the solid sea-hanging plate test was conducted in the sea area of Zhejiang Zhoushan screw, and the 1-year evaluation of the amount of bioadhesion (bioadhesion area) was preferably less than 5%, the evaluation of 5 to 10% (including 5% and not including 10%) was good, the evaluation of 10 to 20% (including 10% and not including 20%) was general, and the evaluation of 20% or more was poor. The results are shown in Table 2.
TABLE 2
Figure BDA0003661691840000131
Figure BDA0003661691840000141
TABLE 3 Table 3
Raw materials Comparative example 1 Comparative example 2 ComparisonExample 3 Comparative example 4
Antifouling resin dispersion/% 25.6 25.8 26.7 25.8
Hydrogenated rosin/% 9 9 9 9
Liquid styrene butadiene rubber/% 2 2 2 2
Bromopyrrocarbonitrile/% 3 3 3 3
Zinc pyrithione/% 2 2 2 2
Iron oxide red/% 3 3 3 3
Zinc oxide/% 40 40 40 40
Dioctyl phthalate/% 1 1 1 1
Polyether silicon ET102/% 0.7 0.7 0.7 0.7
Xylene/% 10.1 10 9.3 10
Propylene glycol monomethyl ether/% 3.6 3.5 3.3 3.5
One year anti-fouling evaluation Difference of difference In general In general In general
(4) Data analysis:
from table 2, it can be seen that the annual organism adhesion amounts in examples 1 to 9 are all less than 10%, which indicates that the copper-free stable controlled release antifouling paint for ship obtained by the method of the present invention can achieve better long-term antifouling effect without adding cuprous oxide and with the addition amount of the organic small molecule auxiliary antifouling agent being only 5%.
As can be seen from tables 2 and 3, the one-year antifouling effect of examples 1 to 3 is significantly better than that of comparative example 1, indicating that the antifouling effect of the antifouling paint can be improved by adding the auxiliary resin to the antifouling resin. The reason is that: after the auxiliary resin is contacted with seawater, the auxiliary resin with stronger hydrophilicity gradually migrates to the surface of the coating, and continuously absorbs water and swells in the migration process, and finally a smooth hydrogel film is formed on the surface of the coating, so that the effect of preventing the adhesion of organisms is exerted.
As can be seen from tables 2 and 3, the one-year antifouling effect of examples 1, 4 and 7 is significantly better than that of comparative example 2, indicating that the use of the main resin of the present invention can impart a better antifouling effect to the antifouling paint than the commercially available M133 resin. The reason is that: in the course of long-term contact with seawater, the surface hydrogel film formed of the auxiliary resin is gradually degraded, and the antifouling effect is deteriorated. The main resin adopted by the invention has self-polishing capability, and the main resin on the surface layer can be degraded and fall off under the action of seawater, so that the auxiliary resin in the coating is further released, and a new hydrogel film is formed on the surface of the coating; however, the commercial M133 resin cannot be self-polished in seawater, and in the long-term use process, the release rate of the auxiliary resin is greatly reduced, and when the surface hydrogel film formed of the auxiliary resin is damaged, it is difficult to form a new hydrogel film in time, so that the long-term antifouling effect of the antifouling paint is poor.
As can be seen from tables 2 and 3, the one-year antifouling effect of example 1 is significantly better than that of comparative example 3, indicating that the antifouling effect of the antifouling paint can be improved by adding the micro-nano accelerator to the antifouling resin. The reason is that: the micro-nano accelerator can promote the formation of hydrophilic micro-areas and hydrophobic micro-areas inside auxiliary resin, and the hydrophilic micro-areas can absorb water and swell in the process of transferring the auxiliary resin to the surface of main resin, so that a hydrogel layer is finally formed on the surface of the coating layer, and the lubrication and anti-fouling effects are exerted; the molecular chains in the hydrogel layer are not connected through covalent bonds, so that the hydrogel layer is easy to polish and abrade when contacted with water, and the hydrophobic micro-areas are less in contact with water and have slower polishing speed, so that the hydrogel layer can be prevented from being polished too fast, and the antifouling period of the coating is prolonged; in addition, the amphipathy of the micro-nano accelerator is utilized, and the hydrophilic-hydrophobic difference of the auxiliary resin and the main resin is matched, so that the auxiliary resin forms a micro-nano state in the main resin in the preparation process of the anti-fouling resin, and the auxiliary resin is beneficial to migration to the surface of the anti-fouling coating after the anti-fouling coating is contacted with water. In this way, the micro-nano accelerator can give the antifouling paint a better long-term antifouling effect.
As can be seen from tables 2 and 3, the one-year antifouling effect of example 1 is significantly better than that of comparative example 4, indicating that the preparation of the antifouling resin dispersion by the method of the present invention is useful for improving the antifouling effect of the antifouling paint, compared to the direct blending of the main resin dispersion, the auxiliary resin dispersion, and the micro-nano accelerator dispersion. The reason is that: in the antifouling resin obtained by the method, the auxiliary resin can exist in the main resin in a micro-nano state, has less molecular chain entanglement with the main resin, is beneficial to migration of the auxiliary resin to the surface of the coating to form a hydrogel layer, and further plays a role in preventing biological adhesion.
Examples 10 to 18: copper-free stable controlled release antifouling paint for netting
(1) Preparation of an antifouling resin dispersion:
the main resin (obtained in preparation example 2) was heated to 60 ℃, a micro-nano accelerator 6B (obtained in preparation example 6) corresponding to 6% by mass of the main resin was added, an auxiliary resin (obtained in preparation example 4) corresponding to 50% by mass of the main resin was slowly added dropwise thereto at a rate of 1.0mL/min under 3500r/min dispersion conditions, the temperature was raised to 90 ℃ after the completion of the dropwise addition, and the cooling was continued after maintaining for 1 hour under 3500r/min dispersion conditions, whereby an antifouling resin dispersion was obtained.
In examples 10 to 18, the main resin and the auxiliary resin used are shown in Table 4, respectively.
TABLE 4 Table 4
Resin numbering 2A 2B 2C
4A Example 10 Example 13 Example 16
4B Example 11 Example 14 Example 17
4C Example 12 Example 15 Example 18
(2) Preparation of copper-free stable controlled release antifouling paint for netting:
according to the formulation of table 5 (the amounts of the raw materials are all mass percent), all the raw materials are uniformly mixed to prepare the copper-free stable controlled release antifouling paint for the netting of examples 10 to 18.
(3) Evaluation of 6 months of antifouling:
the netting of examples 10 to 18 was coated with copper-free controlled release antifouling paint to the surface of the sample plate to form an antifouling coating layer having a thickness of 100. Mu.m. According to the method of GB/T7789-2007, the solid sea-hanging plate test was carried out in the sea area of Zhejiang Zhoushan screw gate, and the 6-month biological adhesion amount was rated as 5% or less, 5 to 10% (including 5% and not including 10%) was rated as good, 10 to 20% (including 10% and not including 20%) was rated as normal, and 20% or more was rated as bad. The results are shown in Table 5.
TABLE 5
Figure BDA0003661691840000161
(4) Data analysis:
as can be seen from Table 5, the annual organism adhesion amounts in examples 10 to 18 are all less than 10%, which shows that the copper-free stable controlled release antifouling paint for netting obtained by the method of the present invention can achieve a better long-term antifouling effect without adding cuprous oxide and with the addition amount of the organic small molecule auxiliary antifouling agent being only 10%.
Examples 19 to 27: copper-free stable controlled release antifouling paint for offshore platform
(1) Preparation of an antifouling resin dispersion:
the main resin (obtained in preparation example 1) was heated to 60 ℃, a micro-nano accelerator 6C (obtained in preparation example 6) corresponding to 6% by mass of the main resin was added, an auxiliary resin (obtained in preparation example 4) corresponding to 50% by mass of the main resin was slowly dropped thereto at a rate of 2.5mL/min under 3500r/min dispersion conditions, the temperature was raised to 90 ℃ after the dropping was completed, and the cooling was continued after maintaining for 1 hour under 3500r/min dispersion conditions, thereby obtaining an antifouling resin dispersion.
In examples 19 to 27, the main resin and the auxiliary resin used are shown in Table 6, respectively. In example 28, the main resin used was 1A and the auxiliary resin was 5A.
TABLE 6
Resin numbering 1A 1B 1C
4A Example 19 Example 22 Example 25
4B Example 20 Example 23 Example 26
4C Example 21 Example 24 Example 27
(2) Preparation of copper-free stable controlled release antifouling paint for netting:
according to the formulation of Table 7 (the amounts of the respective raw materials are mass percent), all the raw materials were uniformly mixed to prepare copper-free stable controlled release antifouling paints for netting of examples 19 to 27.
(3) One year antifouling evaluation:
the coatings of examples 19 to 27 were each coated with a copper-free controlled release antifouling coating on the surface of a sample plate to form an antifouling coating having a thickness of 100. Mu.m. According to the method of GB/T7789-2007, the solid sea-hanging plate test is carried out in the sea area of Zhejiang Zhoushan screw gate, the biological attachment amount of less than 5% is rated as good in one year, 5-10% (including 5% and not including 10%) is rated as good, and 10-20% (including 10% and not including 20%) is rated as normal, and 20% or more is rated as bad. The results are shown in Table 7.
TABLE 7
Figure BDA0003661691840000171
(4) Data analysis:
as can be seen from Table 7, the annual organism adhesion amounts in examples 19 to 27 are all less than 10%, which indicates that the copper-free stable controlled release antifouling paint for offshore platforms obtained by the method of the present invention can achieve a better long-term antifouling effect without adding cuprous oxide and with an organic small molecule auxiliary antifouling agent added in an amount of only 10%.
As can be seen from table 7, the one-year antifouling effect of examples 19 to 21 is significantly better than that of example 28, indicating that the antifouling effect of the antifouling paint can be improved by using the hyperbranched hydrophilic polyurethane resin as the auxiliary resin as compared with the linear hydrophilic polyurethane resin. The reason is that: the hyperbranched hydrophilic polyurethane resin has a highly branched structure, can endow the surface hydrogel layer with higher strength, can slow down water erosion, and can prevent the water erosion from being consumed too quickly, thereby prolonging the antifouling effect of the coating.
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 (7)

1. An antifouling resin for marine antifouling paint based on micro-nano hydrogel is characterized by comprising a main resin, an auxiliary resin dispersed in the main resin in a micro-nano state, and a micro-nano accelerator; the auxiliary resin is hydrophilic resin with water swelling property; the main body resin is self-polishing resin; the auxiliary resin has higher hydrophilicity than the main resin;
the micro-nano accelerator is an amphiphilic polymer with the number average molecular weight of 1000-6000; the amphiphilic polymer is a reactant of an anhydride monomer and/or a polybasic acid monomer and a polyalcohol monomer; the anhydride monomer is one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and trimellitic anhydride; the polybasic acid monomer is glutaric acid and/or adipic acid; the polyalcohol monomer is one or more of ethylene glycol, butanediol, hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, triethylene glycol and tetraethylene glycol;
the auxiliary resin is hydrophilic polyaddition resin and/or hydrophilic polyurethane resin; the hydrophilic polyurethane resin is hyperbranched hydrophilic polyurethane resin; the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) Taking polytetrahydrofuran ether glycol and dihydroxyacid with the mass ratio of 1:6-10 as raw materials, and carrying out esterification reaction to obtain hyperbranched polyester;
(B) Taking dihydroxyl acid and diisocyanate with the mass ratio of 1:4.5-5.5:0.8-1.2 and hyperbranched polyester prepared in the step (A) as raw materials, and carrying out polymerization reaction to prepare hyperbranched hydrophilic polyurethane resin;
the preparation method of the antifouling resin comprises the following steps: heating the main resin dispersion liquid, adding the micro-nano accelerator dispersion liquid, dropwise adding the auxiliary resin dispersion liquid into the main resin dispersion liquid under stirring, and heating to continuously stir after the dropwise adding is finished to obtain the anti-fouling resin.
2. The antifouling resin according to claim 1, wherein the mass ratio of the main resin, the auxiliary resin and the micro-nano accelerator is 1:0.2 to 0.6:0.05 to 0.15.
3. The antifouling resin according to claim 1, wherein the monomers of the hydrophilic addition polymerization resin comprise a hydrophilic monomer and a hydrophobic monomer in a mass ratio of 1:0 to 0.5; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃; the hydrophilic and/or hydrophobic monomers include acrylic monomers.
4. An antifouling resin according to claim 1 or 3, wherein said host resin is a polyaddition resin and/or a polyurethane resin; the monomer of the addition polymerization resin comprises a hydrophilic addition polymerization monomer and a hydrophobic addition polymerization monomer in a mass ratio of 0-1:1; the hydrophilic monomer is a monomer with the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer is a monomer with the solubility in water of less than 10g/L at 20 ℃; the hydrophilic addition monomer and/or the hydrophobic addition monomer comprise an acrylic monomer; the monomers of the polyurethane resin comprise polyamine and/or polyol and also comprise polyisocyanate.
5. The antifouling resin according to claim 1, wherein said method for producing said antifouling resin comprises the steps of: and heating the main resin dispersion liquid to 60-70 ℃, adding the micro-nano accelerator dispersion liquid, dropwise adding the auxiliary resin dispersion liquid into the main resin dispersion liquid at the speed of 1.0-2.5 mL/min under stirring, heating to 90-100 ℃ after the dropwise adding is completed, and continuously stirring for 1h to obtain the antifouling resin.
6. The use of an antifouling resin according to any of claims 1 to 5 in a copper-free controlled release marine antifouling paint.
7. The use according to claim 6, characterized in that it comprises the following components in weight percent: 5-25% of antifouling resin, 5-16% of antifouling agent, 0-10% of rosin, 0-4% of tackifier, 0-6% of pigment, 0-40% of filler, 0-2% of plasticizer, 0-7% of auxiliary agent and the balance of solvent.
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