CN103122187A - Ionic liquid modified marine antifouling paint - Google Patents
Ionic liquid modified marine antifouling paint Download PDFInfo
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- CN103122187A CN103122187A CN2011103695437A CN201110369543A CN103122187A CN 103122187 A CN103122187 A CN 103122187A CN 2011103695437 A CN2011103695437 A CN 2011103695437A CN 201110369543 A CN201110369543 A CN 201110369543A CN 103122187 A CN103122187 A CN 103122187A
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Abstract
The invention discloses ionic liquid marine antifouling paint, which comprises an antifouling paint matrix resin containing ionic liquid groups, an antifouling agent, a pigment filling material, an aiding agent and an organic solvent. The antifouling paint is mainly applied to the antifouling of a ship. In the ocean, based on the characteristic of the low surface energy of the paint, the adhering of marine organisms is effectively inhibited; an acrylic copolymer on the surface of the coating are hydrolyzed to release organic acid zinc or copper and the antifouling agent, so that the self polishing of the surface of the coating is realized; and the main chain of the hydrolyzed acrylic copolymer contains the ionic liquid groups with bactericidal activities, so that the efficient antifouling activity of the coating is maintained continuously, and the adhering of the marine organisms is prevented. Thus, the antifouling paint provided by the invention has the excellent long-term antifouling performance.
Description
Technical field
The invention belongs to the antifouling paint technical field, relate to a kind of marine antifouling coating, particularly a kind of ionic liquid modification marine antifouling coating, be used for oceangoing vessel antifouling.
Background technology
Ocean environment and mankind's activity are closely bound up, and the marine biofouling problem is the great difficult problem that the restriction marine resources development utilizes always.Marine life adheres to increases ship's navigation friction resistance, affects the speed of a ship or plane, increases energy consumption.Sea marine organism pollution can be accelerated film aging simultaneously, and the corruption of aggravation hull endangers huge.Prevent that the most effective means of biodeterioration are exactly the brushing antifouling paint, thereby various anti-fouling ship paint arises at the historic moment just.In numerous antifouling approach, the self polishing copolymer antifouling paint effect is best, with the fastest developing speed.In the past few decades, the self polishing copolymer antifouling paint that contains organotin (TBT) was once used in a large number.Organotin can reach wide spectrum, efficient antifouling purpose under lower concentration, but these materials are stablized in water and easily accumulation, can cause some organisms deformities, and may enter food chain, become the potential safety hazard that affects human health and ecology.Therefore the Marine Environmental Protection Committee under International Maritime Organizaton (IMO) to have stipulated to contain the final time limit of service of the antifouling paint of organotin be on January 1st, 2008.
In recent years, owing to banning use of TBT, various new antifouling paint system is developed and introduces, and is wherein especially noticeable with Tin-free Spc Anti-fouling Paint and low surface energy anti-fouling paint.At present, on market, widely used Tin-free Spc Anti-fouling Paint is all one group of bactericidal properties antifouling paint imitateing the TBT copolymer coating, and its film forming base-material is linear copolymer, does not but have microbe killing properties with hydrolyzable side group.Its Hydrolytic Mechanism is identical with the TBT multipolymer, thereby makes stain control agent from the coatingsurface controllable release, and making films keeps smooth.Although the Tin-free Spc Anti-fouling Paint excellent performance, having a problem is that static antifouling property is poor, the stain control agent rate of release is little, is not enough to kill the marine life that attempt is attached to hull.Low surface energy anti-fouling paint refers to the low surface energy feature by the anti-fouling material that utilizes its preparation, makes biology be difficult for adhering to.But there are a large amount of low surface energy character compositions that do not have in coating, can reduce the antifouling property of low surface energy anti-fouling paint; It is not firm that simple low surface energy anti-fouling paint often can only make marine organisms adhere to, and needs the cleaning of regularly upper depressed place; In a single day settled organism grows up and removes being difficult to, and scale removal process may be destroyed paint film, in case damage, antifouling property just will reduce greatly.At present, although the domestic low surface energy coatings research that the types such as fluoro-resin and organosilicon are arranged due to starting evening and technical elements, is in elementary development mostly, has no and widely apply report.Although the application of low surface energy elastic coating is abroad arranged, due to its elastomerics, bad mechanical strength, hardness are low, poor adhesive force, and construction is inconvenient, and expensive, causes it to use and has very large limitation.
Ionic liquid (ionic liquids) refers in room temperature or is bordering on be in a liquid state under room temperature, the material that is made of ion fully.General and positively charged ion that volume relatively large asymmetric by structure and the negatively charged ion of volume less are consisted of.In recent years, ionic liquid is subject to extensive concern due to its unique chemical physical property at numerous areas such as mechanical engineering, biotechnology.There are some researches show, ionic liquid has the characteristic that excellent anti-protein adsorption performance, high-efficiency antimicrobial activity and good inhibition marine organisms adhere to, thereby ionic liquid more and more receives publicity in the research aspect anti-biological pollution and antifouling mechanism thereof.But a problem of existence is, ionic liquid is applied in marine antifouling coating as adding as stain control agent with micromolecular form, can cause coating stain control agent rate of release fast, and antifouling phase effect shortens, and has a strong impact on its anti-fouling effect.And ionic liquid if with the form of polymkeric substance by copolymerization, construct in resin film forming base-material, will be the effective way of head it off.
End is got up, simple Tin-free Spc Anti-fouling Paint, and static stain control agent rate of release is little, is not enough to kill the marine life that attempt is attached to hull, need to introduce the efficient sterilizing active group on the resin copolymer main chain, improves and suppresses the marine life adhesive ability; Simple low surface energy anti-fouling paint can only make marine life adhere to not firm, need to could realize final cleaning to some settled organismes by external force.Therefore, need to develop and a kind ofly can effectively make up Tin-free Spc Anti-fouling Paint and low surface energy anti-fouling paint defective separately, the marine antifouling coating that antifouling property is excellent, lasting.
Summary of the invention
The object of the present invention is to provide a kind of ionic liquid modification marine antifouling coating.
The technical problem to be solved in the present invention is that existing low surface energy anti-fouling paint poor adhesive force, antifouling cycle are short, antifouling effect inefficacy is fast and the poor problem of the static antifouling property of Tin-free Spc Anti-fouling Paint, for the problems referred to above, the objective of the invention is to overcome the shortcoming that prior art exists, seek to provide a kind of environmental friendliness, surface can be low, from polishing stable, the lasting marine antifouling coating preparation method of antifouling effect.In seawater, the low surface energy characteristic of this antifouling paint can effectively suppress marine organisms and adhere to, simultaneously, the coatingsurface acrylic copolymer is hydrolyzed, and discharges organic acid zinc or copper and stain control agent, realize that coatingsurface is from polishing, and the main polymer chain after hydrolysis also comprises the ionic liquid group with fungicidal activity, makes coating continue to keep high-efficiency pollution-proof active, suppresses marine organisms and adheres to, thereby realize that number of ways is collaborative antifouling, and show excellent long-acting and anti-fouling performance.
To achieve these goals, the technical solution used in the present invention is: a kind of ionic liquid modification marine antifouling coating, this coating are following component and quality proportioning:
The antifouling paint substrate resin that contains the ionic liquid group: 20%～50%
Stain control agent: 15%～30%
Color stuffing: 5%～15%
Auxiliary agent: 1%～5%
Organic solvent: 10%～40%
Ionic liquid modification marine antifouling coating of the present invention, the wherein said antifouling paint substrate resin structural formula that contains the ionic liquid group is:
Wherein, R
1Be H or CH
3, R
2With R
3Represent that separately carbon number is 1～4 alkyl, R
4Be straight chained alkyl, M is Cu or Zn, and A represents the organic acidic group of perfluoro and the organic acidic group of monovalence, and X is hydrophobic anion.The described preparation method who contains the antifouling paint substrate resin of ionic liquid group is, at first synthesize hydrophobicity ionic liquid monomer, again by free-radical polymerized, acrylic acid or the like soft or hard monomer, hydrophobicity ionic liquid monomer, acrylic or methacrylic acid, unsaturated organosilicon monomer under existing, initiator are carried out copolymerization, obtain containing the acrylic polymer of ionic liquid group, and then obtain containing the antifouling paint substrate resin of ionic liquid group with zinc hydroxide (copper), perfluoro organic acid and monovalence organic acid mixture reaction.
Ionic liquid modification marine antifouling coating of the present invention, wherein said stain control agent is comprised of Red copper oxide and copper pyrithione, and the mass ratio of Red copper oxide and copper pyrithione is 8: 1～10: 1.Described organic solvent is the mixing liquid of dimethylbenzene and butylacetate, and its mass ratio is 1: 0.5-2.
Ionic liquid modification marine antifouling coating of the present invention, wherein said coatings additive(s) is the mixture that contains wetting dispersing agent, flow agent, defoamer, anti-settling agent.Described wetting dispersing agent is one or more in polyether-modified organopolysiloxane, anionic wetting dispersing agent, the unsaturated polycarboxylic acid polymkeric substance of lower molecular weight, as 103,104,161,163 of German BYK series; 903,904 of the modest chemical company limited of moral.Described defoamer is a kind of in BYK051,066.Described flow agent is the Levaslip435 of the modest chemical company limited of moral.Described anti-settling agent is organobentonite, talcous mixture.
Ionic liquid modification marine antifouling coating of the present invention, wherein said color stuffing is at least two kinds in red iron oxide, zinc oxide, titanium dioxide, silicon-dioxide.
Ionic liquid modification marine antifouling coating of the present invention, its preparation method is: antifouling paint substrate resin, wetting dispersing agent and the mixed solvent that will contain the ionic liquid group adds and disperses in cylinder, fully disperse, add successively composite anti-fouling agent, color stuffing, flow agent, defoamer, anti-settling agent, stir, after high speed dispersion, select ball mill to be milled to the coating fineness less than 50 μ m, get marine antifouling coating, at last packing.
Ionic liquid modification marine antifouling coating of the present invention, with coating from polishing characteristic and the effective combination of low surface energy characteristic, the ionic liquid group that will have simultaneously the efficient sterilizing activity is incorporated into copolymer chain, strengthen antifouling phase effect, be a kind of environmental friendliness, surface can be low, from polishing stable, the lasting novel antifouling coating of antifouling effect.In seawater, this coating can realize that number of ways is collaborative antifouling, thereby shows excellent long-acting and anti-fouling performance.Simultaneously, coating and base material adhere to well, and coating surface is smooth, easy construction, and the four seasons all can use.
Ionic liquid modification marine antifouling coating of the present invention, the traditional performance that is sprayed at tinplate is as follows:
1) sticking power: GB1720-79 (drawing the circle method), 1 grade;
2) shock-resistance: GB1732-79,50Kg.cm;
3) hardness: GB6379-86, the 2H level;
4) snappiness: GB1731-79,1mm;
5) coatingsurface energy: less than 25mJm
-2
6) drying varniss time: GB1728-79,16～25 ℃ of room temperatures, surface drying 1 hour, 6 hours actual drying time.
Ionic liquid modification marine antifouling coating of the present invention, can be coated on the mild steel plate of epoxy anticorrosion primer (150 * 250 * 1.5mm) by spraying or brushing mode, the epoxy anticorrosion primer build is about 200 μ m, the antifouling coating gauge control can obtain promising result at 100 μ m～200 μ m.
Antifouling paint is coated on by the spraying means on the mild steel plate of epoxy anticorrosion primer and makes model, after the abundant drying of room temperature, carry out the shallow sea panel experiment.Select simultaneously the international top-brand antifouling varnish, the Seaforce90 that produces as Zuo Dun company is from polishing Wuxi antifouling varnish (honest hereinafter to be referred as assistant) and present domestic antifouling varnish commonly used, as in be coated with the tin-free self-polishing antifouling paint (hereinafter to be referred as domestic) that chemical industry company limited produces, brush on the same size steel plate respectively, brushing thickness is identical with this coating.Select simultaneously same specification steel plate to do blank, a brushing epoxy anticorrosion primer.Be placed in lower 6 meters depths, sea and carry out the extra large link plate dynamic testing of reality being coated with the experiment model that is brushed with various antifouling paints and blank plate.Test period 2011,6～2011,9 (marine life growth most productive periods), test site: ocean research base, Qingdao.Take out the observed and recorded result when being specially respectively at 40 days, 100 days, then put back to rapidly and continue test in seawater.This coating model shallow sea link plate is after 100 days, and paint film is intact, and without bubbling, come off, the model surface is adhered to without marine fouling organism, shows that it has good anti-fouling effect.Experimental result is as shown in table 1:
The marine link plate contrast of table 1. dynamic testing data
Embodiment
Below by embodiment, the present invention is described further
Being prepared as follows of hydrophobicity ionic liquid monomer in the present invention:
With 82 gram N-Methylimidazoles, 165 gram 1-chloro-4-methyl-benzenes, 0.5 gram stopper 2,6-toluene di-tert-butyl phenol (DBMP) adds in a reaction flask.Under nitrogen protection, 35 ℃ of stirrings of constant temperature 24 hours generate little yellow thick liquid, through the ether washing, obtain transparent, thick liquid 1-(4-vinyl benzyl-)-3-Methylimidazole chlorine after room temperature vacuum-drying is spent the night.Join in the mixture of 27.6 gram 1-(4-vinyl benzyl-)-3-Methylimidazole chlorine, 0.2 gram stopper DBMP, 100ml acetone after subsequently 18 gram ammonium hexafluorophosphates or 12.1 gram sodium tetrafluoroborates and 100ml acetone being mixed, 30 ℃ were stirred 24 hours, then filtration treatment, the filtrate decompression distillation, get white waxy solid, crude product stores after washing, ether are washed, and is standby.
The acrylic polymer that contains the ionic liquid group in the present invention is prepared as follows:
Be that toluene and the n-butanol mixed solvent of 4: 1 joins in reaction flask with 32 parts of mass ratioes, drip the mixing solutions of 21 parts of methyl methacrylates, 17 parts of n-butyl acrylates, 6 parts of ethyl propenoates, 9 parts of vinylformic acid, 3 parts of organosilane monomers, 4 parts of hydrophobicity ionic liquid monomers and 0.8 part of Diisopropyl azodicarboxylate, 0.5 part of Dodecyl Mercaptan under 90 ℃ and nitrogen purging, be controlled in 1.5 hours and drip off, and be incubated 2 hours.Add again the residue mixed solvent that is dissolved with 0.2 part of Diisopropyl azodicarboxylate in 0.5 hour, continue insulation 1 hour, obtain containing the acrylic polymer of ionic liquid group.
Embodiment 1
(1) containing the acrylic polymer of ionic liquid group, 5.7 parts of zinc hydroxides, 20 parts of mass ratioes with 46 parts is 1; 1 dimethylbenzene and n-butyl acetate mixed solvent add in reaction flask, 8 parts of Perfluorocaprylic Acids, 4.7 parts of phenylformic acid are dissolved in 15.6 parts of mixed solvents, drip above-mentioned organic acid mixing solutions under 95 ℃ and nitrogen purging, keep reflux state transparent to reaction solution, after be warming up to 125 ℃ of dehydrations, until water is deviate from fully, obtain transparent, the thick antifouling paint substrate resin that contains the ionic liquid group.
(2) above-mentioned antifouling paint substrate resin, wetting dispersing agent and the mixed solvent that contains the ionic liquid group added in the dispersion cylinder, fully disperseed 10 minutes, add successively composite anti-fouling agent, color stuffing, flow agent, defoamer, anti-settling agent, stir, high speed dispersion 30 minutes, the ball milling certain hour, get antifouling paint after inspection viscosity, fineness, at last packing subsequently.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 14 grams, copper pyrithione 1.7 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 2
(1) containing the acrylic polymer of ionic liquid group, 5.5 parts of zinc hydroxides, 20 parts of mass ratioes with 45 parts is 1; 1 dimethylbenzene and n-butyl acetate mixed solvent join in reaction flask, 12.4 parts of Perfluorocaprylic Acids, 3.2 parts of phenylformic acid are dissolved in 14 parts of mixed solvents, drip above-mentioned organic acid mixing solutions under 95 ℃ and nitrogen purging, keep reflux state transparent to reaction solution, after be warming up to 125 ℃ of dehydrations, until water is deviate from fully, obtain transparent, the thick antifouling paint substrate resin that contains the ionic liquid group.
(2) this example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 14 grams, copper pyrithione 1.7 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 3
This example contains antifouling paint substrate resin synthetic identical with embodiment 1 of ionic liquid group.
This example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 10 grams, copper pyrithione 1.2 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Titanium dioxide 1 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 4
This example contains antifouling paint substrate resin synthetic identical with embodiment 2 of ionic liquid group.
This example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 10 grams, copper pyrithione 1.2 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Titanium dioxide 1 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 5
(1) containing the acrylic polymer of ionic liquid group, 5.7 parts of copper hydroxides, 20 parts of mass ratioes with 46 parts is 1; 1 dimethylbenzene and n-butyl acetate mixed solvent join in reaction flask, 8 parts of Perfluorocaprylic Acids, 4.7 parts of phenylformic acid are dissolved in 15.6 parts of mixed solvents, drip above-mentioned organic acid mixing solutions under nitrogen purging at 95 ℃, keep reflux state transparent to reaction solution, after be warming up to 125 ℃ of dehydrations, until water is deviate from fully, obtain transparent, the thick antifouling paint substrate resin that contains the ionic liquid group.
(2) this example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 14 grams, copper pyrithione 1.7 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 6
(1) containing the acrylic polymer of ionic liquid group, 5.5 parts of copper hydroxides, 20 parts of mass ratioes with 45 parts is 1; 1 dimethylbenzene and n-butyl acetate mixed solvent join in reaction flask, 12.4 parts of Perfluorocaprylic Acids, 3.2 parts of phenylformic acid are dissolved in 14 parts of mixed solvents, drip above-mentioned organic acid mixing solutions under nitrogen purging at 95 ℃, keep reflux state transparent to reaction solution, after be warming up to 125 ℃ of dehydrations, until water is deviate from fully, obtain transparent, the thick antifouling paint substrate resin that contains the ionic liquid group.
(2) this example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 14 grams, copper pyrithione 1.7 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: with dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 7
This example contains antifouling paint substrate resin synthetic identical with embodiment 5 of ionic liquid group.
This example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 10 grams, copper pyrithione 1.2 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Titanium dioxide 1 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams
Embodiment 8
This example contains antifouling paint substrate resin synthetic identical with embodiment 6 of ionic liquid group.
This example marine antifouling coating preparation technology is identical with embodiment 1.
This example marine antifouling coating component proportion is as follows:
The antifouling paint substrate resin that contains the ionic liquid group: 30 grams
Composite anti-fouling agent: Red copper oxide 10 grams, copper pyrithione 1.2 grams
Color stuffing: red iron oxide 2 grams, zinc oxide 1.5 grams, nano silicon 0.5 gram
Titanium dioxide 1 gram
Coatings additive(s): wetting dispersing agent (BYK163) 0.7 gram, defoamer (BYK051) 0.2 gram,
Flow agent (Levaslip435) 0.3 gram, anti-settling agent (organobentonite 0.8 gram,
Talcum powder 0.8 gram)
Mixed solvent: dimethylbenzene 8 grams, butylacetate 8 grams.
Claims (7)
1. ionic liquid modification marine antifouling coating is characterized in that coating is following component and quality proportioning:
The antifouling paint substrate resin that contains the ionic liquid group: 20%～50%
Stain control agent: 15%～30%
Color stuffing: 5%～15%
Auxiliary agent: 1%～5%
Organic solvent: 10%～40%.
2. coating according to claim 1 is characterized in that the antifouling paint substrate resin structural formula that contains the ionic liquid group is:
Wherein, R
1Be H or CH
3, R
2With R
3Represent that separately carbon number is 1～4 alkyl, R
4Be straight chained alkyl, M is Cu or Zn, and A represents the organic acidic group of perfluoro and the organic acidic group of monovalence, and X is hydrophobic anion.
3. coating according to claim 1, is characterized in that stain control agent is comprised of Red copper oxide and copper pyrithione, and the mass ratio of Red copper oxide and copper pyrithione is 8: 1～10: 1.
4. coating according to claim 1, is characterized in that color stuffing is at least two kinds in red iron oxide, zinc oxide, titanium dioxide, silicon-dioxide.
5. coating according to claim 1, is characterized in that coatings additive(s) is the mixture that contains wetting dispersing agent, flow agent, defoamer, anti-settling agent.
6. coating according to claim 1, is characterized in that organic solvent is the mixing liquid of dimethylbenzene and butylacetate, and its mass ratio is 1: 0.5-2.
7. the preparation method of ionic liquid modification marine antifouling coating according to claim 1, it is characterized in that: antifouling paint substrate resin, wetting dispersing agent and the mixed solvent that will contain the ionic liquid group adds and disperses in cylinder, fully disperse, add successively composite anti-fouling agent, color stuffing, flow agent, defoamer, anti-settling agent, stir, after high speed dispersion, select ball mill to be milled to the coating fineness less than 50 μ m, obtain marine antifouling coating.
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| CN104761991A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Environmental-protection type multi-element collaborative marine anti-fouling coating |
| CN105255291A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Poly(ionic liquid) broad-spectrum antifouling compound containing environment-friendly marine antifouling coating and preparation process thereof |
| CN105542608A (en) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | Fluoroalkyl modified acrylate-containing low-surface energy, drag reduction and fouling prevention coating and preparation method thereof |
| CN105542607A (en) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | Betaine type zwitterion-modified acrylate-containing self-polishing antifouling coating and preparation method thereof |
| CN104745038B (en) * | 2013-12-31 | 2017-05-31 | 浙江省海洋开发研究院 | A kind of compound super-hydrophobic marine antifouling coating, preparation method and its use |
| CN111138958A (en) * | 2020-01-10 | 2020-05-12 | 中国科学院海洋研究所 | Gel coat coating material with antifouling property and preparation method thereof |
| CN112375494A (en) * | 2020-11-16 | 2021-02-19 | 张建峰 | Silicon-based coating material and preparation method thereof |
| CN115521683A (en) * | 2022-10-21 | 2022-12-27 | 常熟理工学院 | Double-network structure modified organic silicon marine antifouling coating and preparation method thereof |
| CN115584153A (en) * | 2022-10-21 | 2023-01-10 | 常熟理工学院 | Modified organic silicon marine antifouling coating based on ion network and preparation method thereof |
| CN116496680A (en) * | 2023-05-15 | 2023-07-28 | 泰山学院 | Preparation method of alkaline red mud coating for preventing marine organism from adhering |
| US11945973B2 (en) | 2019-05-15 | 2024-04-02 | The Hong Kong University Of Science And Technology | Ionic liquid-based coating and method of making articles coated with the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002173647A (en) * | 2000-12-05 | 2002-06-21 | Kansai Paint Co Ltd | Antifouling coating composition |
| JP3443096B2 (en) * | 2000-01-28 | 2003-09-02 | 大日本塗料株式会社 | Antifouling paint composition |
| CN101287805A (en) * | 2005-09-06 | 2008-10-15 | 诺华丝国际股份有限公司 | Marine antifouling coating compositions |
| CN101550304A (en) * | 2008-04-02 | 2009-10-07 | 上海海悦涂料有限公司 | Environment-friendly marine antifouling coating for finishing boat |
| CN101696340A (en) * | 2009-10-26 | 2010-04-21 | 江苏科技大学 | Strippable anti-fouling paint |
| CN102010639A (en) * | 2010-12-06 | 2011-04-13 | 上海暄洋化工材料科技有限公司 | Environmentally-friendly marine antifouling coating and preparation method thereof |
-
2011
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3443096B2 (en) * | 2000-01-28 | 2003-09-02 | 大日本塗料株式会社 | Antifouling paint composition |
| JP2002173647A (en) * | 2000-12-05 | 2002-06-21 | Kansai Paint Co Ltd | Antifouling coating composition |
| CN101287805A (en) * | 2005-09-06 | 2008-10-15 | 诺华丝国际股份有限公司 | Marine antifouling coating compositions |
| CN101550304A (en) * | 2008-04-02 | 2009-10-07 | 上海海悦涂料有限公司 | Environment-friendly marine antifouling coating for finishing boat |
| CN101696340A (en) * | 2009-10-26 | 2010-04-21 | 江苏科技大学 | Strippable anti-fouling paint |
| CN102010639A (en) * | 2010-12-06 | 2011-04-13 | 上海暄洋化工材料科技有限公司 | Environmentally-friendly marine antifouling coating and preparation method thereof |
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| CN104745038B (en) * | 2013-12-31 | 2017-05-31 | 浙江省海洋开发研究院 | A kind of compound super-hydrophobic marine antifouling coating, preparation method and its use |
| CN104761991B (en) * | 2014-01-07 | 2017-04-26 | 中国科学院兰州化学物理研究所 | Environmental-protection type multi-element collaborative marine anti-fouling coating |
| CN104761991A (en) * | 2014-01-07 | 2015-07-08 | 中国科学院兰州化学物理研究所 | Environmental-protection type multi-element collaborative marine anti-fouling coating |
| CN105255291A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Poly(ionic liquid) broad-spectrum antifouling compound containing environment-friendly marine antifouling coating and preparation process thereof |
| CN105542608A (en) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | Fluoroalkyl modified acrylate-containing low-surface energy, drag reduction and fouling prevention coating and preparation method thereof |
| CN105542607A (en) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | Betaine type zwitterion-modified acrylate-containing self-polishing antifouling coating and preparation method thereof |
| US11945973B2 (en) | 2019-05-15 | 2024-04-02 | The Hong Kong University Of Science And Technology | Ionic liquid-based coating and method of making articles coated with the same |
| CN111138958A (en) * | 2020-01-10 | 2020-05-12 | 中国科学院海洋研究所 | Gel coat coating material with antifouling property and preparation method thereof |
| CN112375494A (en) * | 2020-11-16 | 2021-02-19 | 张建峰 | Silicon-based coating material and preparation method thereof |
| CN115521683A (en) * | 2022-10-21 | 2022-12-27 | 常熟理工学院 | Double-network structure modified organic silicon marine antifouling coating and preparation method thereof |
| CN115584153A (en) * | 2022-10-21 | 2023-01-10 | 常熟理工学院 | Modified organic silicon marine antifouling coating based on ion network and preparation method thereof |
| CN116496680A (en) * | 2023-05-15 | 2023-07-28 | 泰山学院 | Preparation method of alkaline red mud coating for preventing marine organism from adhering |
| CN116496680B (en) * | 2023-05-15 | 2024-03-12 | 泰山学院 | Preparation method of alkaline red mud coating for preventing marine organism from adhering |
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Effective date of registration: 20220519 Address after: 264006 5, R & D building, Yeda Science Park, No. 300, Changjiang Road, Yantai Economic and Technological Development Zone, Shandong Province Patentee after: Yantai Zhongke advanced materials and green chemical industry technology Research Institute Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |