CN114907740A - Micro-nano hydrogel-based antifouling resin for marine antifouling paint and preparation method thereof - Google Patents

Micro-nano hydrogel-based antifouling resin for marine antifouling paint and preparation method thereof Download PDF

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CN114907740A
CN114907740A CN202210579242.5A CN202210579242A CN114907740A CN 114907740 A CN114907740 A CN 114907740A CN 202210579242 A CN202210579242 A CN 202210579242A CN 114907740 A CN114907740 A CN 114907740A
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resin
antifouling
monomer
hydrophilic
micro
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CN114907740B (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 a micro-nano hydrogel-based antifouling resin for a marine antifouling paint 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 absorption swelling property; the main body resin is self-polishing resin; the auxiliary resin has higher hydrophilicity than the main resin. The invention combines the main resin with self-polishing ability and the auxiliary resin which can migrate to the surface of the coating to form a hydrogel layer, can exert better antifouling effect and has longer antifouling period, thereby reducing the use of antifouling agent.

Description

Micro-nano hydrogel-based antifouling resin for marine antifouling paint and preparation method thereof
Technical Field
The invention relates to the technical field of marine antifouling, in particular to a micro-nano hydrogel-based antifouling resin for a marine antifouling paint and a preparation method thereof.
Background
The problem of marine biofouling continues to plague people in the course of the development of marine economy and the marine industry. Marine biofouling not only increases the resistance of ships to travel and the consumption of fuel, accelerates the corrosion and degradation of hull materials, but also destroys the ecological balance of the water area. British international paint company has made statistics on fouling of the ship bottom and increased consumption of fuel: if the bottom of the ship is polluted by 5%, the fuel consumption is increased by 10%; if the fouling of the ship bottom is more than 50%, the fuel consumption is increased by more than 40%.
After the organotin antifouling paint of the special effect weapon is completely forbidden from 1/2008, a mainstream paint compound system which takes copper acrylate/zinc/silicon resin as a carrier, cuprous oxide as a main antifouling agent and organic micromolecule antifouling agent as an auxiliary antifouling agent is gradually formed. However, in such an antifouling system, the antifouling effect of the carrier itself is poor, and a large amount of antifouling agent needs to be added, and the toxicity of the antifouling agent may destroy 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 antifouling paint, 18-24 parts by weight of resin, 50-55 parts by weight of antifouling agent, 0.5-1.5 parts by weight of graphene nanoplatelets, 3-6 parts by weight of pigment and filler, 1-2 parts by weight of dispersant, 1-2 parts by weight of organobentonite, and the balance of organic solvent; 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-isothiazoline-3-ketone, cuprous oxide and zinc oxide. Although the antifouling paint avoids the use of organic tin, the dosage of the organic micromolecule auxiliary antifouling agent is 6 percent, and the dosage of the main antifouling agent cuprous oxide is up to 30-35 percent, so that the antifouling paint still can damage the marine ecological environment and is difficult to meet the development requirement of environment-friendly antifouling paint in new environment.
Disclosure of Invention
The invention provides a micro-nano hydrogel-based antifouling resin for a marine antifouling paint and a preparation method thereof, aiming at solving the technical problem of overlarge using amount of an antifouling agent in the existing marine antifouling paint. The invention combines the main resin with self-polishing ability and the auxiliary resin which can migrate to the surface of the coating to form a hydrogel layer, can exert better antifouling effect and has longer antifouling period, thereby reducing the use of antifouling agent.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a micro-nano hydrogel-based antifouling resin for a marine antifouling paint, which comprises a main body resin and an auxiliary resin dispersed in the main body resin in a micro-nano state; the auxiliary resin is hydrophilic resin with water absorption swelling property; the main body resin is self-polishing resin; the auxiliary resin has higher hydrophilicity than the main resin.
In the antifouling coating formed by coating the marine antifouling paint, main resin forms the main structure of the coating, and auxiliary resin is dispersed in the coating in a micro-nano state. After contacting with seawater, the micro-nano auxiliary resin with strong hydrophilicity gradually migrates to the surface of the coating, continuously absorbs water in the migration process to swell to form micro-nano hydrogel, and finally a smooth hydrogel film is formed on the surface of the coating to play a role in preventing biological adhesion. 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 long-term contact with seawater, and the self-polishing resin is adopted in the invention, under the action of seawater, 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, 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 disclosed by the invention can play a better antifouling effect, has a longer antifouling period, and can reduce the using amount of the antifouling agent in the marine antifouling paint, so that the damage of the antifouling agent to the marine environment and the ecology is reduced. Tests prove that when the antifouling resin is used in a marine antifouling paint, cuprous oxide is not required to be added into the paint, and only 5-14 wt% of organic micromolecular auxiliary antifouling agent is added, so that a good antifouling effect can be achieved.
In addition, in the antifouling resin of the invention, the auxiliary resin exists in the main resin in a micro-nano state, so that molecular chain entanglement with the main resin is less, the auxiliary resin is favorable for migrating to the coating surface, and water is absorbed to form a surface hydrogel layer so as to play a role in preventing biological adhesion.
Preferably, the antifouling resin further comprises a micro-nano accelerator; the micro-nano accelerator is an amphiphilic molecule.
The micro-nano accelerant can promote the auxiliary resin to form hydrophilic micro-areas and hydrophobic micro-areas inside, so that the coating has a better antifouling effect, and the specific mechanism is as follows: in the process that the auxiliary resin is transferred to the surface of the main resin, the hydrophilic micro-area can absorb water and swell, and finally a hydrogel layer is formed on the surface of the coating to play a role in lubrication and antifouling; molecular chains in the hydrogel layer are not connected through covalent bonds and are easily polished and abraded when the hydrogel layer is contacted with water, and the hydrophobic micro-area is less contacted with water and has a lower 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 difference of the hydrophilicity and the hydrophobicity of the auxiliary resin and the main resin is matched, so that the auxiliary resin can form a micro-nano state in the main resin in the preparation process of the antifouling resin, and the auxiliary resin can be favorably migrated to the surface of the coating after the antifouling coating is contacted with water.
Preferably, the mass ratio of the main resin, the auxiliary resin and the micro-nano accelerant is 1: 0.2-0.6: 0.05-0.15.
Preferably, 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.
Further, the ratio of the total molar amount of the acid anhydride monomer and the polybasic acid monomer to the molar amount of the polyalcohol monomer is 1.05-1.35: 1 or 1: 1.1-1.5.
Preferably, the auxiliary resin is a hydrophilic polyaddition resin and/or a hydrophilic polyurethane resin; the monomer of the hydrophilic addition polymerization resin comprises a hydrophilic monomer and a hydrophobic monomer in a mass ratio of 1: 0-0.5; the hydrophilic monomer has the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has the solubility in water of less than 10g/L at 20 ℃; the hydrophilic monomer and/or the hydrophobic monomer include an acrylic monomer.
Further, the hydrophilic monomer also comprises 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 dihydroxy acid in a mass ratio of 1: 6-10 as raw materials, and performing esterification reaction to obtain hyperbranched polyester;
(B) carrying out polymerization reaction on dihydroxy acid, diisocyanate and the hyperbranched polyester prepared in the step (A) serving as raw materials in a mass ratio of 1: 4.5-5.5: 0.8-1.2 to prepare the hyperbranched hydrophilic polyurethane resin.
Compared with non-hyperbranched hydrophilic polyurethane resin, the hyperbranched hydrophilic polyurethane resin has a proper degradation speed, and is beneficial to the paint to play a better long-term antifouling effect, specifically: the hyperbranched hydrophilic polyurethane resin can be self-degraded, so that after a surface hydrogel layer formed by the auxiliary resin is damaged, the main resin on the surface layer can be timely degraded and the internal auxiliary resin can be released to form a new surface hydrogel layer, thereby endowing the coating with a better antifouling effect; meanwhile, the hyperbranched hydrophilic polyurethane resin has a highly branched structure, so that the surface hydrogel layer has higher strength, water flow erosion can be slowed down, and the coating is prevented from being consumed too fast, so that the antifouling period of the coating is prolonged.
Further, in steps (a) and (B), the dihydroxy acid comprises dihydroxypropionic acid and/or dihydroxybutyric acid.
Preferably, the main 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 has the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has the solubility in water of less than 10g/L at 20 ℃; the hydrophilic addition polymerization monomer and/or the hydrophobic addition polymerization monomer comprise acrylate monomers; the monomer of the polyurethane resin comprises polyamine and/or polyol, and also comprises polyisocyanate.
Further, in the monomer of the polyurethane resin, the ratio of the total molar amount of hydroxyl groups and amino groups to the molar amount of isocyanate groups is 0.7-0.95: 1.
Further, the hydrophilic addition polymerization monomer further includes one or more of vinyl acetate, N-vinylpyrrolidone and acrylonitrile.
In a second aspect, the present invention provides a method for preparing the antifouling resin, comprising the steps of: heating the main resin dispersion liquid to 60-70 ℃, adding the micro-nano accelerant dispersion liquid, dropwise adding the auxiliary resin dispersion liquid at the speed of 1.0-2.5 mL/min while stirring, heating to 90-100 ℃ after dropwise adding, and continuously stirring for 1h to obtain the antifouling resin.
The antifouling resin prepared by the specific method can disperse the auxiliary resin 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, the auxiliary resin with larger molecular chain flexibility can generate molecular chain deformation under the conditions of the micro-nano accelerant and special process conditions, a nano or micron structure (the particle size is between 280nm and 1.5 microns) is formed by gathering together of hydrophilic-hydrophobic interaction and molecular secondary valence bond acting force, the nano or micron structure 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 accelerant dispersion liquid are 45-55 wt%, 45-55 wt% and 65-75 wt% respectively; the mass ratio of the main resin dispersion liquid to the auxiliary resin dispersion liquid to the micro-nano promoter 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: 5-25% 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 assistant and the balance of solvent.
Preferably, the auxiliary agent comprises one or more of a dispersing agent, a leveling agent, an anti-settling thixotropic agent and an 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 antifouling agent comprises bromopyrrolecarbonitrile 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 a hydrogel layer, so that a better antifouling effect can be exerted, and a longer antifouling period is achieved, thus the use of antifouling agents 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 biological adhesion, and the auxiliary resin is favorable to migrate to the surface of the coating after the coating is contacted with water to form a surface hydrogel layer to play an antifouling role;
(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 period of the antifouling paint is prolonged, a better antifouling effect is given to the antifouling paint, and the auxiliary resin can form a micro-nano state in the main resin;
(4) the hyperbranched hydrophilic polyurethane resin is adopted as auxiliary resin, so that the erosion of water flow to the surface hydrogel layer can be slowed down, and a new surface hydrogel layer can be formed in time when the hydrogel layer on the surface of the coating is damaged, so that the coating has a good long-term antifouling effect.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The antifouling resin for the marine antifouling paint based on the 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 absorption swelling property; the main body resin is self-polishing resin; the auxiliary resin has higher hydrophilicity than the main resin. The mass ratio of the main resin to the auxiliary resin to the micro-nano accelerant is 1: 0.2-0.6: 0.05-0.15.
The main body resin is polyaddition resin and/or 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 has a solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has a solubility in water of less than 10g/L at 20 ℃. The hydrophilic addition polymerization monomer and/or the hydrophobic addition polymerization monomer comprise acrylate monomers; optionally, the hydrophilic addition polymerization monomer further comprises one or more of vinyl acetate, N-vinyl pyrrolidone, and acrylonitrile.
The acrylate monomer can be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, triisopropyl silicate, tributyl silicate and trimethyl silicate, one or more of trimethylsilyl 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 ethoxyethoxyethyl methacrylate.
As a specific embodiment, the method for preparing the addition polymerization resin comprises the steps of: mixing 200 parts by weight of monomers (including a hydrophilic addition polymerization monomer and a hydrophobic addition polymerization monomer in a mass ratio of 0-1: 1), 0.9-1.5 parts by weight of Azobisisobutyronitrile (AIBN), 0.3-0.9 part by weight of Azobisisovaleronitrile (AMBN) and 190-210 parts by weight of a reaction solvent, reacting for 2.5-3.5 hours at 70-90 ℃, adding 0.2 part by weight of tert-amyl peroxyacetate (TAPV), and reacting for 2-3 hours at 80-100 ℃ to obtain the addition polymerization resin. Optionally, the monomer is tributyl silicon methacrylate, or consists of methyl methacrylate and ethoxyethoxyethyl methacrylate in a mass ratio of 1: 0.5-1, 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 isooctyl acrylate, trimethylsilyl methacrylate, isodecyl methacrylate and acrylonitrile in a mass ratio of 1: 0.5-0.8: 0.4-0.6: 0.3-0.4.
The monomer of the polyurethane resin comprises polyamine and/or polyol, and also comprises polyisocyanate.
The polyisocyanate may be selected from one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate. The polyol can be selected from one or more of hydroxyl-terminated polyester, hydroxyl-terminated polyether, dihydric alcohol of C2-8 and trihydric alcohol of C3-10. The polyamine can be selected from one or more of diamine and triamine.
As a specific embodiment, the preparation method of the polyurethane resin includes the steps of: mixing polyamine and/or polyol, a reaction solvent, polyisocyanate and a catalyst, reacting at 60-70 ℃ until the reaction is complete, and adding butanediol for chain extension to obtain the polyurethane resin.
As a specific embodiment, the preparation method of the polyurethane resin includes the steps of: mixing polyamine and/or polyol, a reaction solvent, isophorone diisocyanate (IPDI) and a catalyst, reacting for 3.5-4.5 h at 60-70 ℃, adding diphenylmethane diisocyanate (MDI), continuously reacting at 60-70 ℃ until the reaction is complete, and then adding dihydric alcohol for chain extension to obtain the polyurethane resin.
The auxiliary resin is hydrophilic polyaddition resin and/or hydrophilic polyurethane resin.
The monomer of the hydrophilic addition polymerization resin comprises a hydrophilic monomer and a hydrophobic monomer in a mass ratio of 1: 0-0.5; the hydrophilic monomer has a solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has a solubility in water of less than 10g/L at 20 ℃. The hydrophilic monomer and/or hydrophobic monomer comprises 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 process for producing the hydrophilic polyaddition resin comprises the steps of: mixing 200 parts by weight of monomers (including a hydrophilic addition polymerization monomer and a hydrophobic addition polymerization monomer in a 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, reacting at 70-90 ℃ for 2.5-3.5 h, adding 0.2 part of Benzoyl Peroxide (BPO), and reacting at 100-120 ℃ for 2-3 h to obtain the hydrophilic addition polymerization resin. Optionally, the monomer consists of 1: 0.8-1.2 mass ratio of vinyl pyrrolidone and methoxyethyl acrylate, or consists of 1: 0.2-0.3: 0.5-0.7 mass ratio of isooctyl methacrylate, vinyl acetate and vinyl pyrrolidone, or consists of 0.1-0.3: 0.6-0.8: 0.9-1.1 mass ratio of isobornyl methacrylate, vinyl pyrrolidone and methoxyethyl acrylate, or consists of 1: 1.5-2.0: 2.5-2.8: 0.8-1.3 mass ratio of acrylic acid, isobornyl methacrylate, methoxyethyl acrylate and hydroxyethyl acrylate.
The hydrophilic polyurethane resin is hyperbranched hydrophilic polyurethane resin; the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) carrying out esterification reaction on polytetrahydrofuran ether glycol and dihydroxy acid which are used as raw materials in a mass ratio of 1: 6-10 to prepare hyperbranched polyester;
(B) carrying out polymerization reaction on dihydroxy acid, diisocyanate and the hyperbranched polyester prepared in the step (A) serving as raw materials in a mass ratio of 1: 4.5-5.5: 0.8-1.2 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 (PTMG1000) and dihydroxy acid in a mass ratio of 1: 6-10, reacting at 165-175 ℃ for 3-4 h, heating to 195-205 ℃ for reaction until the acid value is lower than 3, heating to 225-235 ℃, and immediately cooling to prepare hyperbranched polyester;
(B) mixing dihydroxy acid, diisocyanate and a catalyst in a mass ratio of 1: 4.5-5.5, reacting at 70-80 ℃ for 50-90 min, adding a diluent, and continuously reacting at 70-80 ℃ until the reaction is complete; 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 complete; and then adding dihydric alcohol for chain extension to obtain the hyperbranched hydrophilic polyurethane resin. Optionally, the diluent is N-methyl pyrrolidone and xylene 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 acid 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 acid anhydride monomer may be selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride. The polyacid monomers may be selected from glutaric acid and/or adipic acid. The polyol monomer may be selected from one or more of ethylene glycol, butanediol, hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, triethylene glycol and tetraethylene glycol.
As a specific implementation mode, the preparation process of the micro-nano accelerant comprises the following steps: mixing 280-320 parts of monomer, 50-60 parts of reaction solvent and 1.3-1.6 parts of catalyst according to parts by weight, reacting for 2.5-3.5 hours at 155-165 ℃, heating to 190-210 ℃, reacting for 2-4 hours, heating to 220-240 ℃, keeping for 20-40 min, and adding 62-81 parts of reaction solvent to obtain the micro-nano accelerator.
A preparation method of the antifouling resin comprises the following steps: heating a main resin dispersion liquid with a solid content of 45-55 wt% to 60-70 ℃, adding a micro-nano accelerant dispersion liquid with a solid content of 65-75 wt%, dropwise adding an auxiliary resin dispersion liquid with a solid content of 45-55 wt% into the main resin dispersion liquid at a 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 accelerant dispersion liquid is 1: 0.25-0.50: 0.05-0.10, heating to 90-100 ℃ after dropwise adding, 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: 5-25% 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 assistant and the balance of solvent. The auxiliary agent comprises one or more of a dispersing agent, a flatting agent, an anti-settling thixotropic agent and an antioxidant. The rosin comprises hydrogenated rosin. The tackifier comprises liquid styrene-butadiene rubber. The filler comprises zinc oxide. The antifouling agent comprises bromopyrrole carbonitrile and/or zinc pyrithione.
As a specific embodiment, the marine copper-free stable controlled release marine antifouling paint comprises the following components in percentage by weight: 5-16% of antifouling resin, 5-16% of antifouling agent, 4-10% of rosin, 0.5-4% of tackifier, 0-6% of pigment, 5-40% of filler, 0-2% of plasticizer, 0-7% of assistant and the balance of solvent.
As a specific embodiment, the antifouling paint is a copper-free stable controlled release marine antifouling paint for netting, and comprises the following components: 5-22% of antifouling resin, 6-16% of antifouling agent, 0.5-4% of tackifier, 0-6% of pigment, 0-2% of plasticizer, 0-7% of assistant and the balance of solvent.
As a specific embodiment, the antifouling paint is a copper-free stable controlled release marine antifouling paint for an offshore platform, and comprises the following components in percentage by weight: 5-16% of antifouling resin, 6-16% of antifouling agent, 4-10% of rosin, 0.5-4% of tackifier, 0-6% of pigment, 5-40% of filler, 0-2% of plasticizer, 0-7% of assistant and the balance of solvent.
Preparation example 1: synthesis of host resin (polyaddition resin)
(1) Synthesis of host resin 1A:
200g of tributyl silicon 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-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the temperature is kept at 85 ℃ for 3h, then 0.2g of TAPV is added, the temperature is raised to 95 ℃ and kept for 2.5h, and the mixture is cooled to room temperature, so that the main body resin 1A dispersion liquid with the solid content of about 50 percent is obtained.
(2) Synthesis of host resin 1B:
100g of methyl methacrylate, 100g of ethoxyethoxyethyl methacrylate, 1.5g of AIBN, 0.3g of AMBN, 178g of xylene and 20g of ethylene glycol monobutyl ether are added into a 1L four-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the temperature is kept at 70 ℃ for 3h, then 0.2g of TAPV is added, the temperature is raised to 80 ℃ and kept for 2.5h, and the mixture is cooled to room temperature, so that the main body resin 1B dispersion liquid with the solid content of about 50 percent is obtained.
(3) Synthesis of host resin 1C:
100g of isooctyl methacrylate, 30g of vinyl acetate, 70g of vinyl pyrrolidone, 0.9g of AIBN, 0.9g of AMBN, 178g of solvent oil and 20g of ethylene glycol monobutyl ether are added into a 1L four-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the temperature is kept for 3 hours at 90 ℃, then 0.2g of TAPV is added, the temperature is raised to 100 ℃, the temperature is kept for 2.5 hours, and the mixture is cooled to the room temperature, so that the main body resin 1C dispersion liquid with the solid content of about 50 percent is obtained.
(4) Synthesis of host resin 1D:
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 are added into a 1L four-neck flask which is provided with a stirrer and a reflux condenser and protected by nitrogen, the temperature is kept for 3 hours at 90 ℃, then 0.2g of TAPV is added, the temperature is raised to 100 ℃, the temperature is kept for 2.5 hours, and then the mixture is cooled to the room temperature, so that the main body resin 1D dispersion liquid with the solid content of about 50 percent is obtained.
Preparation example 2: synthesis of host resin (polyurethane resin)
(1) Synthesis of host resin 2A:
under the protection of argon, 200g of dry hydroxyl-terminated polyester, 240g N-methyl pyrrolidone, 33.4g of MDI and 4 drops of di-n-butyltin dilaurate (DBTDL) are mixed, the mixture is continuously reacted at 65 ℃ until NCO reaches a theoretical value (di-n-butylamine titration method), then 1.8g of butanediol is added for chain extension for 3 hours, and a target product, namely a main body resin 2A dispersion liquid with solid content of about 50%, is obtained after cooling.
(2) Synthesis of host resin 2B:
under the protection of argon, 100g of dry hydroxyl-terminated polyester, 100g of hydroxyl-terminated polyether, 235g N-methyl pyrrolidone, 30g of IPDI and 4 drops of DBTDL are mixed, and continuously reacted at 65 ℃ until NCO reaches a theoretical value, then 1.8g of butanediol is added for chain extension for 3 hours, and after cooling, a target product, namely a main body resin 2B dispersion liquid with the solid content of about 50%, is obtained.
(3) Synthesis of host resin 2C:
under the protection of argon, 100g of dry hydroxyl-terminated polyester, 100g of hydroxyl-terminated polyether, 237g N-methylpyrrolidone, 22.2g of IPDI and 4 drops of DBTDL are mixed, reacted at 65 ℃ for 4 hours, 8.3g of MDI is added, the reaction is continued at 65 ℃ until NCO reaches a theoretical value, then 1.8g of butanediol is added for chain extension for 3 hours, and a target product, namely a main body resin 2C dispersion liquid with the solid content of about 50%, is obtained after cooling.
Preparation example 3: synthesis of support resin (hydrophilic polyaddition resin)
(1) Synthesis of support resin 3A:
100g of vinyl pyrrolidone, 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 temperature is kept for 3 hours at 100 ℃, then 0.2g of BPO is added, the temperature is raised to 110 ℃, the temperature is kept for 2.5 hours, and the mixture is cooled to the room temperature, so that the auxiliary resin 3A dispersion liquid with the solid content of about 50 percent is obtained.
(2) Synthesis of support resin 3B:
30g of isobornyl methacrylate, 70g of vinyl pyrrolidone, 100g of methoxyethyl acrylate, 0.3g of AIBN, 3.0g of AMBN, 0.5g of TAPV, 176g of xylene 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 temperature is kept for 3 hours at 100 ℃, then 0.2g of BPO is added, the temperature is raised to 110 ℃, the temperature is kept for 2.5 hours, and then the mixture is cooled to the room temperature, so that the auxiliary resin 3B dispersion liquid with the solid content of about 50 percent is obtained.
(3) Synthesis of support 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 xylene 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 temperature is kept for 3 hours at 100 ℃, 0.2g of BPO is added, the temperature is raised to 110 ℃ and kept for 2.5 hours, then the temperature is cooled to 60 ℃, 36g of triethylamine is added, the mixture is cooled to room temperature after being reacted for 0.5 hour, and the reaction is finished to obtain the auxiliary resin 3C dispersion liquid with the solid content of about 50 percent.
Preparation example 4: synthesis of auxiliary resin (hyperbranched hydrophilic polyurethane resin)
(1) Synthesis of hyperbranched polyester HO-HB-OH:
100g PTMG1000 and 600g dihydroxypropionic acid (DMPA) were charged to the reactor under nitrogen blanketing. After stirring uniformly, slowly heating to 170 ℃, maintaining the temperature for 3h, continuously heating to 200 ℃ (during the whole process, continuously blowing nitrogen gas), reacting until the acid value is lower than 3, heating to 230 ℃, and immediately cooling. When the temperature is reduced to 100 ℃, reducing the pressure to remove water for 1h, and then reducing the temperature to room temperature to obtain the hyperbranched polyester HO-HB-OH.
(2) Synthesis of support resin 4A:
under the protection of high-purity nitrogen, mixing 100g of dry DMPA, 498g of IPDI and 6 drops of catalyst DBTDL, reacting for 1 hour at 70 ℃, adding 500g of dry N-methylpyrrolidone and 400g of dry xylene, and continuously reacting 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, and after completion of the reaction, the reaction mixture was neutralized with 67g of Triethylamine (TEA) to obtain a dispersion of the support resin 4A having a solid content of about 50%.
The preparation route of the hyperbranched polyester HO-HB-OH and the auxiliary resin 4A is as follows:
Figure BDA0003661691840000111
(3) synthesis of support resin 4B:
under the protection of high-purity nitrogen, mixing dried 110g of dimethylolbutyric acid (DMBA), 390g of Hexamethylene Diisocyanate (HDI) and 6 drops of catalyst DBTDL, reacting at 70 ℃ for 1h, 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; then 99g of tetraethylene glycol was added, and after completion of the reaction, the reaction mixture was neutralized with 60g of TEA to obtain an auxiliary resin 4B dispersion having a solid content of about 50%.
(4) Synthesis of support resin 4C:
under the protection of high-purity nitrogen, mixing dried 110g of DMBA, 590g of 4,4' -dicyclohexylmethane diisocyanate (HMDI) and 7 drops of catalyst DBTDL, reacting at 70 ℃ for 1 hour, adding 600g of dried N-methylpyrrolidone and 400g 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; then 99g of tetraethylene glycol was added, and after completion of the reaction, the reaction mixture was neutralized with 66g of Diethanolamine (DEA) to obtain an auxiliary resin 4C dispersion having a solid content of about 50%.
Preparation example 5: synthesis of support resin (hydrophilic polyurethane resin)
Under the protection of high-purity nitrogen, mixing 100g of dry DMPA, 498g of IPDI and a certain amount of catalyst DBTDL, reacting at 70 ℃ for 1h, adding 500g of dry N-methylpyrrolidone and 400g of dry xylene, and continuing to react until NCO reaches a theoretical value; then adding 100g of PTMG1000, and continuing to react until NCO reaches a theoretical value; then, 96g of triethylene glycol (TEG) was added, and after completion of the reaction, the reaction mixture was neutralized with 67g of Triethylamine (TEA) to obtain a dispersion of auxiliary resin 5A having a solid content of about 50%.
Preparation example 6: synthesis of micro-nano accelerator
(1) Synthesizing a micro-nano accelerator 6A:
taking 180g of phthalic anhydride, 80g of ethylene glycol, 40g of hexanediol, 60g of xylene and 1.5g of C-94 catalyst, mixing, heating to 160 ℃, maintaining for 3h, heating to 200 ℃, maintaining for 2.5h, continuing heating to 230 ℃, maintaining for 0.5h, cooling to 90 ℃, adding 71g of xylene, finishing the reaction, and obtaining the micro-nano accelerator 6A dispersion liquid with the solid content of about 70% and the number average molecular weight of 2846.
(2) Synthesizing a micro-nano accelerator 6B:
taking 110g of phthalic anhydride, 90g of trimellitic anhydride, 80g of ethylene glycol, 40g of hexanediol, 60g of xylene and 1.6g of C-94 catalyst, mixing, heating to 155 ℃, maintaining for 2.5h, heating to 200 ℃, maintaining for 2h, continuing heating to 230 ℃, maintaining for 0.5h, cooling to 90 ℃, adding 81g of xylene, and finishing the reaction to obtain the micro-nano accelerator 6B dispersion liquid with the solid content of about 70% and the number average molecular weight of 1473.
(3) Synthesizing a micro-nano accelerator 6C:
taking 110g of phthalic anhydride, 90g of trimellitic anhydride, 50g of ethylene glycol, 30g of hexanediol, 50g of xylene and 1.3g of C-94 catalyst, mixing, heating to 165 ℃, maintaining for 3.5h, heating to 210 ℃, maintaining for 4h, continuing heating to 230 ℃, maintaining for 0.5h, cooling to 90 ℃, adding 62g of xylene, and finishing the reaction to obtain the micro-nano accelerator 6C dispersion liquid 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 coating for ship
(1) Preparation of antifouling resin dispersion:
examples 1 to 9: heating a main resin dispersion liquid (obtained from preparation example 1) to 60 ℃, adding a micro-nano accelerator 6A dispersion liquid (obtained from preparation example 6) corresponding to 6% of the mass of the main resin dispersion liquid, slowly dripping an auxiliary resin dispersion liquid (obtained from preparation example 3) corresponding to 25% of the mass of the main resin dispersion liquid into the main resin dispersion liquid at a speed of 1.0mL/min under the 3500r/min dispersion condition, heating to 90 ℃ after finishing dripping, continuously maintaining for 1h under the 3500r/min dispersion condition, and then cooling to obtain the antifouling resin dispersion liquid.
In examples 1 to 9, the main resin and the auxiliary resin used are shown in table 1.
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 is added during the preparation of the antifouling 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 of the same mass and same solid content (styrene-methyl methacrylate-butyl acrylate terpolymer, which cannot be polished in seawater).
Comparative example 3 differs from example 1 only in that the micro-nano accelerator dispersion liquid is not added during the preparation of the antifouling resin dispersion liquid.
Comparative example 4: the dispersion liquid of the main resin 1A (obtained from the preparation example 1) is heated to 60 ℃, the dispersion liquid of the micro-nano accelerator 6A (obtained from the preparation example 6) corresponding to 6% of the mass of the dispersion liquid of the main resin 1A and the dispersion liquid of the auxiliary resin 3A (obtained from the preparation example 3) corresponding to 25% of the mass of the dispersion liquid of the main resin 1A are added, the temperature is raised to 90 ℃, and the mixture is maintained for 2.5 hours under the dispersion condition of 3500r/min and then cooled to obtain the dispersion liquid of the antifouling resin.
(2) Preparation of the copper-free stable controlled release antifouling coating for the ship:
according to the formulations shown in tables 2 and 3 (the amounts of the raw materials are all mass percent), the copper-free stable controlled-release antifouling paint for ships of examples 1 to 9 and comparative examples 1 to 3 is prepared after uniformly mixing all the raw materials (in comparative examples 1 and 3, the solid content of the antifouling paint is controlled to be the same as that in example 1 by changing the amounts of the antifouling resin dispersion liquid and xylene and propylene glycol monomethyl ether).
(3) One-year antifouling evaluation:
the marine copper-free controlled-release antifouling paints of examples 1 to 9 were applied to the surface of the sample plate to form an antifouling coating layer having a thickness of 100 μm. According to the method in GB/T7789-2007, the sea-plate test is carried out in the sea area of Zhoushan Oncomelania at Zhejiang, the assessment of the biological attachment (biological attachment area) is excellent when the attachment amount is less than 5%, the assessment is good when the attachment amount is 5-10% (including 5% and not 10%), the assessment is normal when the attachment amount is 10-20% (including 10% and not 20%), and the assessment is poor when the attachment amount is greater than or equal to 20%. The results are shown in Table 2.
TABLE 2
Figure BDA0003661691840000131
Figure BDA0003661691840000141
TABLE 3
Raw materials Comparative example 1 Comparative example 2 Comparative example 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
Bromo-pyrrolesNitrile/%) 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 ET 102/%) 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 antifouling evaluation Difference (D) In general In general In general terms
(4) And (3) data analysis:
as can be seen from table 2, the annual biofouling amount in examples 1 to 9 is less than 10%, which shows that the marine copper-free stable controlled release antifouling paint obtained by the method of the present invention can achieve a good long-term antifouling effect under the condition that no cuprous oxide is added and the addition amount of the organic small-molecule auxiliary antifouling agent is only 5%.
As can be seen from tables 2 and 3, the antifouling effect of examples 1 to 3 is significantly superior to that of comparative example 1 for one year, and it is demonstrated 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 contacting with seawater, the auxiliary resin with strong hydrophilicity gradually migrates to the surface of the coating, continuously absorbs water and swells in the migration process, and finally forms a smooth hydrogel film on the surface of the coating to play a role in preventing biological adhesion.
As can be seen from tables 2 and 3, the antifouling effects of examples 1,4 and 7 for one year are significantly superior to those of comparative example 2, and it is demonstrated that the use of the host resin in 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 by the auxiliary resin will be gradually degraded, and the antifouling effect will be deteriorated. The main body resin adopted by the invention has self-polishing capability, and the main body 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 commercially available M133 resin cannot be self-polished in seawater, and the release rate of the auxiliary resin is greatly reduced during long-term use, and when the surface hydrogel film formed by the auxiliary resin is damaged, it is difficult to form a new hydrogel film in time, which results in poor long-term antifouling effect of the antifouling paint.
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, which shows 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 auxiliary resin to form hydrophilic micro-areas and hydrophobic micro-areas, and the hydrophilic micro-areas can absorb water and swell in the process that the auxiliary resin migrates to the surface of the main resin, so that a hydrogel layer is finally formed on the surface of the coating to play a role in lubrication and antifouling; molecular chains in the hydrogel layer are not connected through covalent bonds and are easily polished and abraded when the hydrogel layer is contacted with water, and the hydrophobic micro-area is less contacted with water and has 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 difference of the hydrophilicity and the hydrophobicity of the auxiliary resin and the main resin is matched, so that the auxiliary resin can form a micro-nano state in the main resin in the preparation process of the antifouling resin, and the auxiliary resin can migrate to the surface of the coating after the antifouling coating is contacted with water. By the method, the micro-nano accelerator can endow the antifouling paint with a good 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, which shows that the antifouling resin dispersion prepared by the method of the present invention is more effective in improving the antifouling effect of the antifouling paint than 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, and is less entangled with molecular chains between the main resin, so that the auxiliary resin is favorably migrated to the surface of the coating to form a hydrogel layer, and the function of preventing biological adhesion is further exerted.
Examples 10 to 18: copper-free stable controlled release antifouling paint for net clothes
(1) Preparation of antifouling resin dispersion:
heating a main resin (obtained from preparation example 2) to 60 ℃, adding a micro-nano accelerator 6B (obtained from preparation example 6) which is 6 percent of the mass of the main resin, slowly dripping an auxiliary resin (obtained from preparation example 4) which is 50 percent of the mass of the main resin at a speed of 1.0mL/min under 3500r/min dispersion condition, heating to 90 ℃, continuously maintaining for 1h under 3500r/min dispersion condition, and cooling to obtain an antifouling resin dispersion liquid.
In examples 10 to 18, the main resin and the auxiliary resin used are shown in 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) The preparation of the copper-free stable controlled release antifouling paint for the net coat comprises the following steps:
according to the formula (the use amount of each raw material is mass percent) of table 5, all the raw materials are uniformly mixed to prepare the copper-free stable controlled-release antifouling paint for the net clothes of the embodiments 10-18.
(3) Evaluation of antifouling at 6 months:
the copper-free controlled-release antifouling paints for the net clothes of examples 10 to 18 were applied to the surface of a sample plate, respectively, to form an antifouling coating layer having a thickness of 100 μm. According to the method in GB/T7789-2007, the sea-suspending board test is carried out in the sea area of Zhoushan Oncomelania at Zhejiang, the assessment that the biological attachment amount is less than 5% is excellent in 6 months, the assessment that the biological attachment amount is 5-10% (containing 5% and not containing 10%) is good, the assessment that the biological attachment amount is 10-20% (containing 10% and not containing 20%) is general, and the assessment that the biological attachment amount is greater than or equal to 20% is poor. The results are shown in Table 5.
TABLE 5
Figure BDA0003661691840000161
(4) And (3) data analysis:
as can be seen from table 5, the annual biofouling amount in examples 10 to 18 is 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 good 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 antifouling resin dispersion:
heating a main resin (obtained from preparation example 1) to 60 ℃, adding a micro-nano accelerator 6C (obtained from preparation example 6) which is 6% of the mass of the main resin, slowly dripping an auxiliary resin (obtained from preparation example 4) which is 50% of the mass of the main resin at a speed of 2.5mL/min under 3500r/min dispersion conditions, heating to 90 ℃, continuously maintaining for 1h under 3500r/min dispersion conditions, and cooling to obtain an antifouling resin dispersion liquid.
In examples 19 to 27, the main resin and the auxiliary resin used are shown in Table 6. 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) The preparation of the copper-free stable controlled release antifouling paint for the net coat comprises the following steps:
according to the formula of table 7 (the amount of each raw material is mass percent), all the raw materials are uniformly mixed to obtain the copper-free stable controlled release antifouling paint for netting of examples 19-27.
(3) One-year antifouling evaluation:
the copper-free controlled-release antifouling paints for netting of examples 19 to 27 were applied to the surface of a sample plate to form an antifouling coating layer having a thickness of 100 μm. According to the method in GB/T7789-2007, the sea-plate test is carried out in the sea area of Zhoushan Oncomelania of Zhejiang, the annual biological attachment is evaluated as excellent when the attachment is less than 5%, the annual biological attachment is evaluated as good when the attachment is 5-10% (including 5% and not including 10%), the annual attachment is evaluated as good when the attachment is 10-20% (including 10% and not including 20%) and the annual attachment is evaluated as poor when the attachment is more than 20%. The results are shown in Table 7.
TABLE 7
Figure BDA0003661691840000171
(4) And (3) data analysis:
as can be seen from table 7, the annual biofouling amount in examples 19 to 27 is less than 10%, which shows that the copper-free stable controlled-release antifouling paint for offshore platforms obtained by the method of the present invention can achieve a good long-term antifouling effect without adding cuprous oxide and with the addition amount of the organic small-molecule auxiliary antifouling agent being 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, which shows that the antifouling effect of the antifouling paint can be improved by using the hyperbranched hydrophilic polyurethane resin as the auxiliary resin compared to the linear hydrophilic polyurethane resin. The reason is that: the hyperbranched hydrophilic polyurethane resin has a highly branched structure, so that the surface hydrogel layer has higher strength, water erosion can be slowed down, and the coating is prevented from being consumed too fast, so that the antifouling period of the coating is prolonged.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The antifouling resin for the marine antifouling paint based on the micro-nano hydrogel is characterized by 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 absorption swelling property; the main body resin is self-polishing resin; the auxiliary resin has higher hydrophilicity than the main resin.
2. The antifouling resin of claim 1, further comprising a micro-nano accelerator; the micro-nano accelerator is an amphiphilic molecule.
3. The antifouling resin as claimed in claim 2, wherein the mass ratio of the main resin, the auxiliary resin and the micro-nano accelerator is 1: 0.2-0.6: 0.05-0.15.
4. The antifouling resin as claimed in claim 2, wherein the micro-nano accelerator comprises an amphiphilic polymer having a molecular weight of 1000 to 6000; the monomer of the amphiphilic polymer comprises an anhydride monomer and/or a polybasic acid monomer and also comprises a polyalcohol monomer.
5. The antifouling resin according to claim 1, wherein the auxiliary resin is a hydrophilic polyaddition resin and/or a hydrophilic polyurethane resin; the monomer of the hydrophilic addition polymerization resin comprises a hydrophilic monomer and a hydrophobic monomer in a mass ratio of 1: 0-0.5; the hydrophilic monomer has the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has the solubility in water of less than 10g/L at 20 ℃; the hydrophilic monomer and/or the hydrophobic monomer include an acrylic monomer.
6. The antifouling resin of claim 1, wherein the hydrophilic polyurethane resin is a hyperbranched hydrophilic polyurethane resin; the preparation method of the hyperbranched hydrophilic polyurethane resin comprises the following steps:
(A) carrying out esterification reaction on polytetrahydrofuran ether glycol and dihydroxy acid which are used as raw materials in a mass ratio of 1: 6-10 to prepare hyperbranched polyester;
(B) carrying out polymerization reaction on dihydroxy acid, diisocyanate and the hyperbranched polyester prepared in the step (A) serving as raw materials in a mass ratio of 1: 4.5-5.5: 0.8-1.2 to prepare the hyperbranched hydrophilic polyurethane resin.
7. The antifouling resin according to claim 1 or 5, wherein 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 has the solubility in water of not less than 10g/L at 20 ℃, and the hydrophobic monomer has the solubility in water of less than 10g/L at 20 ℃; the hydrophilic addition polymerization monomer and/or the hydrophobic addition polymerization monomer comprise acrylate monomers; the monomer of the polyurethane resin comprises polyamine and/or polyol, and also comprises polyisocyanate.
8. A method for producing the antifouling resin according to any one of claims 1 to 7, comprising the steps of: heating the main resin dispersion liquid to 60-70 ℃, adding the micro-nano accelerant 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 dropwise adding, and continuously stirring for 1h to obtain the antifouling resin.
9. Use of the antifouling resin according to any one of claims 1 to 7 in a copper-free stable controlled release marine antifouling paint.
10. The use according to claim 9, comprising 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 assistant and the balance of solvent.
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