CN114957903A - Preparation method of acrylic acid microgel sphere antifouling resin, acrylic acid microgel sphere antifouling resin and coating - Google Patents
Preparation method of acrylic acid microgel sphere antifouling resin, acrylic acid microgel sphere antifouling resin and coating Download PDFInfo
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- CN114957903A CN114957903A CN202210755834.8A CN202210755834A CN114957903A CN 114957903 A CN114957903 A CN 114957903A CN 202210755834 A CN202210755834 A CN 202210755834A CN 114957903 A CN114957903 A CN 114957903A
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 86
- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 13
- 239000003973 paint Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 12
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229920001225 polyester resin Polymers 0.000 claims description 12
- 239000004645 polyester resin Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007970 homogeneous dispersion Substances 0.000 claims description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 239000002519 antifouling agent Substances 0.000 abstract description 13
- 238000005498 polishing Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000006378 damage Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
Acrylic acid microgel sphere antifouling resin, acrylic acid microgel sphere antifouling resin and a preparation method of a coating. The problems that the existing self-polishing antifouling coating is large in use amount of cuprous oxide and organic antifouling agent, the surface microstructure coating is difficult to construct on the surface of a ship, and the coating is damaged due to the deposition of marine microorganisms and inorganic matters on the surface, so that the antifouling effect is difficult to achieve are mainly solved. The microgel balls are dispersed in the antifouling paint, a microstructure with a convex and smooth surface is formed due to water absorption expansion (the microstructure system contains a large amount of water), the microstructure is continuously regenerated due to polishing of polishing resin, the antifouling effect of the microstructure is continuously exerted, and the microstructure is prevented from being damaged and losing the antifouling effect due to deposition of marine microorganisms and inorganic matters on the surface of the coating due to a complex marine environment.
Description
Technical Field
The utility model belongs to antifouling application field, concretely relates to acrylic acid microgel ball antifouling resin and a preparation method of acrylic acid microgel ball antifouling resin and coating.
Background
Marine fouling refers to the attachment and growth of marine organisms on the surface exposed in seawater, which causes great harm to marine ships and marine facilities, and not only increases the frictional resistance of ships, reduces the speed of navigation, increases the fuel consumption, and causes the aging damage, coating damage and steel corrosion of turbines, but also has the problems of influencing heat transfer, increasing the energy consumption of equipment and the like. According to the statistical analysis of foreign IP companies, marine biofouling can cause the fuel consumption of ships to increase by more than 40%, the total amount of the marine biofouling is about 700 ten thousand tons of fuel consumed in the world every year, the economic loss can reach nearly billions of dollars, and meanwhile, 21000 million tons of carbon dioxide gas emission and 560 million tons of sulfur dioxide gas emission are increased.
The application of antifouling paints is recognized as the most economical and effective method of antifouling. The use of antifouling coatings containing organotin biocides was banned in 2008 around the world, the most prominent alternative being self-polishing antifouling coatings containing copper based antifouling agents. However, the antifouling paint has certain limitations, and a certain amount of inorganic/organic antifouling agent must be used to achieve a good antifouling effect, for example, the dosage of the antifouling agent cuprous oxide is about 40%, and the antifouling agent has certain toxicity, and can damage marine environment and ecology after long-term use. The self-polishing microstructure surface is constructed, the synergistic antifouling effect of the resin/antifouling agent is exerted, the using amount of the antifouling agent is reduced, the harm of the antifouling agent to an environmental system is reduced, and the method is a new solution. The article "preparation and performance study of surface microstructure self-polishing antifouling coating" has indicated that the amount of antifouling agent can be reduced by 50% by the surface microstructure.
The coating of the desorptable elastomer has high cost and poor bonding force with the substrate, and needs an intermediate coating, so the coating is difficult; for coatings with surface microstructures, the deposition of marine microorganisms and minerals on the surface makes the microstructures easily destroyed and lose their antifouling effect due to the complexity of marine environment. Patent CN110684421A also teaches that the micro gel beads and the anti-fouling agent act synergistically to reduce the amount of anti-fouling agent by 50% to 60%. However, in patent CN110684421A, the microgel sphere antifouling resin is complex to prepare, which is not conducive to industrial popularization.
Patent CN101792534A discloses a method for manufacturing a bionic micro-nano structure surface material with a marine antifouling function, the invention utilizes a negative structure template of a high polymer material to simulate the surface micro-nano structure of marine organisms, the structure has the characteristics of low price of the template material and simple batching process, but the structure is difficult to be applied to the existing ship, the microstructure of the surface cannot be regenerated, the clean surface is difficult to be kept in a complex marine environment all the time, and the antifouling period is short.
Disclosure of Invention
In order to overcome the defects of the background art, the invention provides acrylic acid microgel sphere antifouling resin, acrylic acid microgel sphere antifouling resin and a preparation method of a coating, and mainly solves the problems that the existing self-polishing antifouling coating is high in cuprous oxide and organic antifouling agent usage amount, a surface microstructure coating is difficult to construct on the surface of a ship, and the coating is damaged due to the deposition of marine microorganisms and inorganic matters on the surface, so that the antifouling effect is difficult to play.
The technical scheme adopted by the invention is as follows:
the acrylic microgel ball antifouling resin comprises the following components in parts by weight:
acrylic acid microgel balls 70-90 parts
12 to 18 portions of dispersing resin
The balance being the first dispersant.
The first dispersant is span 80.
The preparation method of the acrylic microgel sphere antifouling resin is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparation of acrylic acid microgel balls:
step 1.1, adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersing agent, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butyl alcohol into a flask, introducing nitrogen for 25-35 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour until the solution turns white;
step 1.2 then adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersant, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butanol continuously dropwise into the reaction solution within 6 hours; after the dripping of the mixed solution is finished, continuously carrying out heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel ball solution;
step 2, preparation of dispersion resin:
step 2.1, adding 40-70% xylene solvent into a flask, controlling the stirring speed to be 300 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 90 ℃ and keeping constant nitrogen pressure; then dropwise adding a mixed solution of 10-40% of isobornyl methacrylate, 10-30% of triisopropyl methacrylate silicone grease, 5-15% of butyl acrylate, 5-15% of acrylic acid and 0.1-1% of azobisisovaleronitrile at a constant speed into the solvent, controlling the dropwise adding time to be 3 hours, and after the dropwise adding is finished, continuing to perform heat preservation reaction for 4 hours;
step 3, preparation of dispersing resin
Preparation of acrylic microgel ball antifouling resin: firstly, adding a first dispersing agent into 70-90% of dispersed resin, heating to 80 ℃, dripping 12-18% of microgel balls into a dispersed resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel ball antifouling resin.
The flask is a 500ml four-mouth flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe.
The preparation method of the acrylic microgel sphere antifouling resin coating is characterized by comprising the following steps: the method comprises the following steps:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 23-27 parts of
Organic bentonite: 0.3 to 0.8 portion
Xylene: 13-19 parts
Zinc oxide: 20-24 parts of
Cuprous oxide: 18-20 parts of
Copper pyrithione: 2-4 parts of
Terpene resin: 9-10 parts of
The rest is polyester resin;
then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20-30 minutes until the fineness of the coating reaches below 50 micrometers, and the acrylic microgel ball antifouling coating is obtained.
The polyester resin is J-693 polyester resin.
The invention has the beneficial effects that: in the embodiment of the invention, the microgel balls are dispersed in the antifouling paint, a microstructure with a convex and smooth surface is formed due to water absorption expansion (the microstructure system contains a large amount of water), the microstructure is continuously regenerated due to polishing of the polishing resin, the antifouling effect of the microstructure is continuously exerted, and the microstructure is prevented from being damaged and losing the antifouling effect due to deposition of marine microorganisms and inorganic substances on the surface of the coating caused by a complex marine environment. 500-time observation of an ultra-field depth microscope shows that in the artificial seawater soaking process, the surface of the self-polishing antifouling coating with the surface microstructure always has a raised microstructure along with continuous polishing of the coating, and the size of the microstructure is about 1-2 mu m. An indoor chlorella antifouling performance evaluation test shows that the microstructure and the antifouling agent have a synergistic antifouling effect. According to the self-polishing antifouling coating with the surface microstructure, the cross-linking reaction between the resin and the micro gel balls in the coating enables the coating to form a network structure, so that the water resistance of the coating is improved, and the antifouling period is prolonged.
In the antifouling paint, the dosage of cuprous oxide is generally between 35% and 55%, and the price is 70 yuan/kg. The major source of cost in antifouling coatings is cuprous oxide. The consumption of the cuprous oxide in the invention is less than 20%, and compared with the main stream antifouling paint in the market, the consumption of the cuprous oxide is reduced by 50-60%. The invention is characterized in that the service performance of the antifouling paint is kept, the cost of the antifouling paint is greatly reduced, and the influence of toxic heavy metal ions on the marine environment is reduced, thus being a new application technology with important significance.
Drawings
FIG. 1 is a schematic diagram of the antifouling mechanism of an acrylic microgel sphere antifouling paint.
Detailed Description
The invention will be further described with reference to the accompanying drawings in which: as shown in the figure, the acrylic microgel ball antifouling resin comprises the following components in parts by weight:
acrylic acid microgel balls 70-90 parts
12 to 18 portions of dispersing resin
The balance being the first dispersant.
The first dispersant is span 80.
The preparation method of the acrylic microgel sphere antifouling resin comprises the following steps:
step 1, preparation of acrylic acid microgel balls:
step 1.1, adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersing agent, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butyl alcohol into a flask, introducing nitrogen for 25-35 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour until the solution turns white; all percentages herein are weight percentages and the proportion of step 1.1 is only that percentage of that step;
step 1.2 then adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersant, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butanol continuously dropwise into the reaction solution within 6 hours; after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution; step 2, preparation of dispersion resin:
step 2.1, adding 40-70% xylene solvent into a flask, controlling the stirring speed to be 300 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 90 ℃ and keeping constant nitrogen pressure; then dripping a mixed solution of 10-40% of isobornyl methacrylate, 10-30% of triisopropyl methacrylate silicone grease, 5-15% of butyl acrylate, 5-15% of acrylic acid and 0.1-1% of azobisisovaleronitrile into a solvent at a constant speed, controlling the dripping time to be 3 hours, and continuing to perform heat preservation reaction for 4 hours after finishing dripping;
step 3, preparation of dispersing resin
Preparation of acrylic microgel ball antifouling resin: firstly, adding a first dispersing agent into 70-90% of dispersion resin, heating to 80 ℃, dripping 12-18% of microgel spheres into a dispersion resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel sphere antifouling resin.
The flask is a 500ml four-mouth flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe.
The preparation method of the acrylic microgel sphere antifouling resin coating is characterized by comprising the following steps: the method comprises the following steps:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 23-27 parts of
Organic bentonite: 0.3 to 0.8 portion
Xylene: 13-19 parts
Zinc oxide: 20-24 parts of
Cuprous oxide: 18-20 parts of
Copper pyrithione: 2-4 parts of
Terpene resin: 9-10 parts of
The rest is polyester resin;
then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20-30 minutes until the fineness of the coating reaches below 50 micrometers, and the acrylic microgel ball antifouling coating is obtained.
The polyester resin is J-693 polyester resin.
In the case of the example 1, the following examples are given,
(1) preparation of acrylic acid microgel spheres: adding a mixed solution containing 4.2g of acrylamide, 0.2g of ethylene glycol dimethacrylate, 2.1g of methacrylic acid, 2.4g of methoxyethyl acrylate, 4.2g of a second dispersing agent, 0.2g of azobisisovaleronitrile and 20g of n-butyl alcohol into a 1L four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sample injection device and a vent pipe, introducing nitrogen for 30 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour until the solution turns white; then, a mixed solution containing 32.4g of acrylamide, 1.6g of ethylene glycol dimethacrylate, 19.6g of methacrylic acid, 22.6g of methoxyethyl acrylate, 15.2g of a dispersant, 1.0g of azobisisovaleronitrile and 160g of n-butanol was continuously added dropwise to the reaction solution over 6 hours (a continuous dropwise addition apparatus may be used); after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel spheres is 0.5-0.7 um, and the dispersant used in the step is a ternary random copolymer synthesized by methacrylic acid, methyl methacrylate and vinyl acetate through free radical polymerization;
(2) preparation of dispersion resin: firstly, adding 180g of xylene solvent into a 500m four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, controlling the stirring speed to be 300 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 90 ℃, and keeping constant nitrogen pressure; then, a mixed solution of 100g of isobornyl methacrylate, 40g of triisopropyl methacrylate silicone grease, 10g of butyl acrylate, 2.2g of acrylic acid and 1.3g of azobisisovaleronitrile is uniformly dripped into a solvent (a continuous dripping device can be adopted), the dripping time is controlled to be 3 hours, and after the dripping is finished, the heat preservation reaction is continued for 4 hours;
(3) preparation of acrylic microgel ball antifouling resin: firstly, adding 6g of dispersing agent into 150g of dispersing resin, heating to 80 ℃, dripping 30g of microgel balls into a dispersing resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel ball antifouling resin.
(4) Preparing an acrylic microgel ball antifouling coating:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 250g
Organic bentonite: 5g
Xylene: 160g
Zinc oxide: 220g
Cuprous oxide: 200g
Copper pyrithione: 30g of
Terpene resin: 95g
Polyester resin: 40g of
Then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20 minutes until the fineness of the coating reaches below 50 microns, and the acrylic microgel sphere antifouling coating is obtained.
In the case of the example 2, the following examples are given,
(1) preparation of acrylic acid microgel spheres: adding a mixed solution containing 4g of acrylamide, 0.3g of ethylene glycol dimethacrylate, 2g of methacrylic acid, 2g of methoxyethyl acrylate, 4g of a second dispersing agent, 0.2g of azobisisovaleronitrile and 21g of n-butyl alcohol into a 1L four-neck flask provided with a stirrer, a reflux condenser, a semi-automatic sample introduction device and a vent pipe, introducing nitrogen for 30 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour to turn the solution into white; then, a mixed solution containing 32g of acrylamide, 2g of ethylene glycol dimethacrylate, 20g of methacrylic acid, 22g of methoxyethyl acrylate, 15g of a dispersant, 1g of azobisisovaleronitrile and 165g of n-butanol was continuously added dropwise to the reaction solution over 6 hours (a continuous dropwise addition apparatus may be used); after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel spheres is 0.5-0.7 um, and the dispersant used in the step is a ternary random copolymer synthesized by methacrylic acid, methyl methacrylate and vinyl acetate through free radical polymerization;
(2) preparation of dispersion resin: firstly, 170g of xylene solvent is added into a 500m four-mouth flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, the stirring speed is controlled to be 300 r/min, nitrogen is introduced to remove oxygen for 30 minutes, and then the solvent is heated to 90 ℃ and the constant nitrogen pressure is kept; then, dropwise adding a mixed solution of 90g of isobornyl methacrylate, 30g of triisopropyl methacrylate silicone grease, 15g of butyl acrylate, 2g of acrylic acid and 1.5g of azobisisovaleronitrile into a solvent (a continuous dropwise adding device can be adopted) at a constant speed, controlling the dropwise adding time to be 3 hours, and after the dropwise adding is finished, continuing to perform heat preservation reaction for 4 hours;
(3) preparation of acrylic microgel ball antifouling resin: firstly, adding 5g of dispersing agent into 130g of dispersing resin, heating to 80 ℃, dripping 40g of microgel balls into a dispersing resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel ball antifouling resin.
(4) Preparing an acrylic microgel ball antifouling coating:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 250g
Organic bentonite: 5g
Xylene: 160g
Zinc oxide: 240g
Cuprous oxide: 180g
Copper pyrithione: 30g of
Terpene resin: 95g
J-693 polyester resin: 40g of
Then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20 minutes until the fineness of the coating reaches below 50 microns, and the acrylic microgel sphere antifouling coating is obtained.
In the case of the example 3, the following examples are given,
(1) preparation of acrylic acid microgel spheres: adding a mixed solution containing 4.5g of acrylamide, 0.5g of ethylene glycol dimethacrylate, 2.6g of methacrylic acid, 2.6g of methoxyethyl acrylate, 4.5g of a second dispersing agent, 0.5g of azobisisovaleronitrile and 23g of n-butyl alcohol into a 1L four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sample injection device and a vent pipe, introducing nitrogen for 30 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour to turn the solution into white; then, a mixed solution containing 32.8g of acrylamide, 1.6g of ethylene glycol dimethacrylate, 21g of methacrylic acid, 21.5g of methoxyethyl acrylate, 14g of a dispersant, 0.8g of azobisisovaleronitrile and 155g of n-butanol was continuously added dropwise to the reaction solution over 6 hours (a continuous dropwise addition apparatus may be used); after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel spheres is 0.5-0.7 um, and the dispersant used in the step is a ternary random copolymer synthesized by methacrylic acid, methyl methacrylate and vinyl acetate through free radical polymerization; the micro-gel microsphere is a high-molecular terpolymer, is beneficial to forming a micro-gel sphere structure by hydrophilic resin in a system, and plays a role of a template in the process of forming the micro-gel sphere resin.
(2) Preparation of dispersion resin: firstly, adding 180g of xylene solvent into a 500m four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, controlling the stirring speed to be 300 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 90 ℃, and keeping constant nitrogen pressure; then, a mixed solution of 95g of isobornyl methacrylate, 38g of triisopropyl methacrylate silicone grease, 8g of butyl acrylate, 2.5g of acrylic acid and 1.6g of azobisisovaleronitrile is uniformly dripped into a solvent (a continuous dripping device can be adopted), the dripping time is controlled to be 3 hours, and after the dripping is finished, the heat preservation reaction is continued for 4 hours;
(3) preparation of acrylic microgel ball antifouling resin: firstly, adding 7g of dispersing agent into 160g of dispersing resin, heating to 80 ℃, dripping 20g of microgel balls into a dispersing resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel ball antifouling resin.
(4) Preparing an acrylic microgel ball antifouling coating:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 240g
Organic bentonite: 15g of
Xylene: 170g
Zinc oxide: 230g
Cuprous oxide: 170g
Copper pyrithione: 30g of
Terpene resin: 95g
J-693 polyester resin: 30g of
Then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20 minutes until the fineness of the coating reaches below 50 microns, and the acrylic microgel sphere antifouling coating is obtained.
The basic properties of the assay were as follows:
| inspection item | Actual measurement result | Inspection method |
| Adhesion/grade | 2 | GB/T1720-1979 |
| Impact resistance/(kg. cm) | ≥45 | GB/T1732-1993 |
| Flexibility/mm | ≤2 | GB/T1731-1979 |
| Salt water resistance (Normal temperature, 14 d) | No bubbling, no falling and no change of coating | GB/T10834-2008 |
| Storage stability (50，30d） | Qualified | GB/T6753.3-1986 |
| Storage stability (Room temperature, 9 months) | Qualified | GB/T6753.3-1986 |
| Antifouling performance (12 months) | The marine organism attachment is less than or equal to 10 percent in 12 months | GB/T5370-2007 |
| Type of sample | Conventional formulation 40% Cu2O | Conventional formulation 20% Cu2O | 20% Cu2O of the invention |
| Biological fouling rate (%) | 8 | 40 | 7 |
The embodiments described with reference to the drawings are illustrative and are intended to be illustrative of the invention and should not be construed as limiting the invention. The examples should not be construed as limiting the present invention, but any modifications made based on the spirit of the present invention should be within the scope of protection of the present invention.
Claims (7)
1. An acrylic microgel ball antifouling resin is characterized in that: the paint comprises the following components in parts by weight:
acrylic acid microgel balls 70-90 parts
12 to 18 portions of dispersing resin
The balance of the first dispersant.
2. The acrylic microgel sphere antifouling resin of claim 1, wherein: the first dispersant is span 80.
3. The method for preparing an acrylic microgel sphere antifouling resin as set forth in any one of claims 1 to 2, wherein: the method comprises the following steps:
step 1, preparation of acrylic acid microgel balls:
step 1.1, adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersing agent, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butyl alcohol into a flask, introducing nitrogen for 25-35 minutes to remove residual oxygen in the solution, heating to 80 ℃, and reacting for 1 hour until the solution becomes white;
step 1.2 then adding a mixed solution containing 10-40% of acrylamide, 0.1-1% of ethylene glycol dimethacrylate, 5-15% of methacrylic acid, 5-15% of methoxyethyl acrylate, 1-5% of a second dispersant, 0.1-1% of azobisisovaleronitrile and 50-75% of n-butanol continuously dropwise into the reaction solution within 6 hours; after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution;
step 2, preparation of dispersion resin:
step 2.1, adding 40-70% xylene solvent into a flask, controlling the stirring speed to be 300 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 90 ℃ and keeping constant nitrogen pressure; then dripping a mixed solution of 10-40% of isobornyl methacrylate, 10-30% of triisopropyl methacrylate silicone grease, 5-15% of butyl acrylate, 5-15% of acrylic acid and 0.1-1% of azobisisovaleronitrile into a solvent at a constant speed, controlling the dripping time to be 3 hours, and continuing to perform heat preservation reaction for 4 hours after finishing dripping;
step 3, preparation of dispersing resin
Preparation of acrylic microgel ball antifouling resin: firstly, adding a first dispersing agent into 70-90% of dispersion resin, heating to 80 ℃, dripping 12-18% of microgel spheres into a dispersion resin system under the condition of 600r/min, stirring for 10-20 minutes under the condition of heat preservation, and uniformly dispersing to obtain the acrylic microgel sphere antifouling resin.
4. The method of claim 31, wherein the acrylic microgel sphere antifouling resin comprises: the flask is a 500ml four-mouth flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe.
5. The method for preparing an acrylic microgel sphere antifouling resin coating according to claim 3, wherein: the second dispersing agent is a ternary random copolymer synthesized by free radical polymerization reaction of methacrylic acid, methyl methacrylate and vinyl acetate.
6. The method for preparing an acrylic microgel sphere antifouling resin coating as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
in a high-speed homogeneous dispersion machine, the following components are sequentially added:
acrylic acid microgel sphere antifouling resin: 23-27 parts of
Organic bentonite: 0.3 to 0.8 portion
Xylene: 13-19 parts
Zinc oxide: 20-24 parts of
Cuprous oxide: 18-20 parts of
Copper pyrithione: 2-4 parts of
Terpene resin: 9-10 parts of
The rest is polyester resin;
then, high-speed dispersion is carried out at 3500 rpm for 20-30 minutes, a dispersion head is replaced, a proper amount of glass beads are added, the rotating speed is adjusted to 1000 rpm, grinding is carried out for 20-30 minutes until the fineness of the coating reaches below 50 micrometers, and the acrylic microgel ball antifouling coating is obtained.
7. The method for preparing a coating of an acrylic microgel sphere antifouling resin according to claim 6, wherein: the polyester resin is J-693 polyester resin.
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