CN102181206A - Antifouling paint containing nano oxides - Google Patents
Antifouling paint containing nano oxides Download PDFInfo
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- CN102181206A CN102181206A CN 201110100299 CN201110100299A CN102181206A CN 102181206 A CN102181206 A CN 102181206A CN 201110100299 CN201110100299 CN 201110100299 CN 201110100299 A CN201110100299 A CN 201110100299A CN 102181206 A CN102181206 A CN 102181206A
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Abstract
The invention provides an antifouling paint containing nano oxides. The antifouling paint is prepared from the following raw materials based on a weight ratio: 5-20% of nano oxide, 10-30% of cuprous oxide, 20-30% of chlorine-containing polymer, 3-5% of rosin, 1-7% of polymer dispersant, 3-6% of plasticizer, 2-5% of anti-settling agent and 20-40% of solvent. The preparation method comprises the following steps: proportionally adding chlorine-containing polymer powder to the solvent with equivalent mass, and shearing and stirring at a high speed to obtain a transparent chlorine-containing polymer solution; proportionally adding the polymer dispersant to a certain amount of the solvent, and then adding the nano oxides for high-speed dispersion to obtain nano-oxide slurry; proportionally adding the prepared nano-oxide slurry as well as the cuprous oxide, the rosin, the plasticizer, the anti-settling agent and the like to the chlorine-containing polymer solution under the condition of high-speed stirring or grinding and dispersion; and finally filtering the obtained mixed solution with a sieve mesh or silk cloth to obtain the nano-antifouling paint, sampling, weighing and packaging to obtain the finished product after the sample passes a test.
Description
Technical field
The present invention relates to the whole antifouling paint of the antifouling or submarine at a kind of tidal range district that is applicable to boats and ships and submerged zone position, belong to the marine antifouling field.
Background technology
The surface was subjected to the washing away of the galvanic corrosion of seawater and seawater, the high humidity of marine atmosphere, high mould, high-temperature and high salt fog when boats and ships moved in the ocean, and the erosion of marine microorganism, wherein mould and microorganism are important factors that causes surface corrosion.Especially hull bottom is because long period of soaking among seawater, the adhering to stained even more serious of marine microorganism, directly has influence on reliability that boats and ships use, life-span and to the adaptability of environment.According to estimates, the marine biofouling rate is the twice that 5% o'clock resistance just is equivalent to clean surface, and fuel consumption increases by 10%, makes the ship's speed of 15 nautical miles/hour tjemplons that travel reduce the 0.5-1 joint.For many years, anti-fouling ship paint is one of material of the most special, the investigative technique difficulty maximum of performance in the marine finish always.
For preventing marine organisms adhering to, growing on boats and ships, very long one period countries in the world use always and contain virose material such as compounds such as copper, arsenic, lead, mercury and tin carry out antifouling.Though this can reduce or eliminate halobiontic stained, the release of objectionable impurities has also caused serious harm for ecotope and human health.The early stage compounds such as arsenic, mercury that use of countries such as American and Britain are prepared antifouling paint as stain control agent, because its toxicity is eliminated too greatly and already; After the seventies in 20th century, because the forbidding of stain control agents such as mercury, arsenic, and find that organotin can reach antifouling efficiently purpose under lower concentration, so organo-tin compound becomes representative stain control agent.The eighties, discover that organotin can accumulate in fish, shellfish body, cause heritable variation, but also might enter after the food chain, big quantity research has been made for the toxicity problem of organotin in countries in the world.To the end of the eighties, various countries make laws one after another, forbid or limit the use of the organotin antifouling paint, International Maritime Organizaton (IMO) has passed through " international control boats and ships system's pact of harmful antifouling end " resolution October calendar year 2001, require beginning on January 1st, 2003, all boats and ships must not apply or apply again the antifouling paint that contains tributyl tin compound again, finally forbid organo-tin antifouling paint in 2008 on all boats and ships of the whole world.
At present, prevailing antifouling paint is the cupric antifouling paint of low release rate on the market at home, is the tin-free self-polishing antifouling paint of stain control agent with toxicity less Red copper oxide and heterocyclic sterilization, mould inhibitor etc. promptly.Japan is matrix resin in nineteen ninety-five development and sale with copper propylene vinegar multipolymer, and the non-tin that with Red copper oxide is stain control agent is the hydrolysis-type self polishing copolymer antifouling paint, and its mechanism of action is identical with hydrolysis-type tributyl tin acrylate copolymer.Afterwards, developing a series of again is the self polishing color of base-material with the zinc acrylic copolymer, controls the release rate of cuprous ion by the dissolution rate of control multipolymer.Yet studies show that, use copper separately in stain control agent, invalid to diatom and other algae, must add auxiliary toxic agent, and the toxicity of copper and auxiliary toxic agent almost is equal to organotin.Therefore, be badly in need of environmental protection and the antifouling paint of dependable performance solves the antifouling problem of boats and ships.
Summary of the invention
The purpose of this invention is to provide a kind of antifouling paint that contains nano-oxide.
What the present invention will solve is that existing stain control agent or antifouling paint are preventing halobiontic weak point of adhering to aspect erosion.
For realizing purpose of the present invention, the technical solution used in the present invention is as follows: a kind of antifouling paint that contains nano-oxide, make by following weight ratio raw material: nano-oxide 5-20%; Red copper oxide 10-30%; Chlorine-containing polymer 20-30%; Rosin 3-5%; Macromolecule dispersing agent 1-7%; Softening agent 3-6%; Anti-settling agent 2-5%; Solvent 20-40%.
Nano-oxide is meant that mean particle size by primary particle nano titanium oxide or in the nano zine oxide one or both below 100nm form, and its particle crystal formation is an anatase titanium dioxide, rutile-type or mix crystal formation; Chlorine-containing polymer is chlorinated polyether resin, chlorinated rubber, chlorinated polyvinyl chloride or vinylchlorid vinyl acetate copolymer; Macromolecule dispersing agent is selected from Disperbyk163, the EFKA-4010 of Deuchem Co., Ltd., extra large river chemical industry 5040 or the Sodium hexametaphosphate 99 of German Bi Ke chemical company; Softening agent is one or both in tritolyl phosphate or the clorafin; Anti-settling agent is one or both in organobentonite or the silicon-dioxide; Solvent is one or both in dimethylbenzene, trimethylbenzene or the propyl carbinol.
A kind of preparation method who contains the antifouling paint of nano-oxide, its preparation process is as follows:
In the solvent with quality such as chlorine-containing polymer powder addings, high speed shear stirs (1500r/min) up to obtaining transparent colloidal solution, is chlorine-containing polymer solution at first in proportion;
Then in proportion macromolecule dispersing agent is added in the certain amount of solvent, add nano-oxide then, 400-2000rpm high speed dispersion 5-60 minute; The gained slurry ground in ball mill or sand mill or ball mill 20 minutes-24 hours; Make the nano-oxide slurry;
Again in proportion the nano-oxide slurry for preparing and Red copper oxide, rosin, softening agent, anti-settling agent etc. in high-speed stirring or grind under the dispersive state and join in the chlorine-containing polymer solution, fully disperse this mixture with high speed dispersor or grinding plant, the time is 10 minutes-60 minutes;
Being prepared into nano antifouling coating after filtering with 100-300 purpose screen cloth or silk at last, can weighing and bagging be finished product after sampling and testing is qualified.
Advantage of the present invention: nano titanium oxide or nano zine oxide have photocatalytic, under sun exposure can with multiple organism generation redox reaction, produce the extremely strong hydroxyl free radical (OH of a large amount of oxidation capacities
-) and active oxygen (O
2), most bacterium (microorganism) is killed, sterilizing ability reaches 99.97%; Its extremely strong oxidizing power can also be decomposed into carbonic acid gas and water to the organism that is difficult to remove that sticks on the hull, or other inorganics of very easily removing.And, nano-titanium oxide and base material excellent bonding performance, intensity, wear resistance are good, thereby boats and ships clash into other hard objects under sail or be subjected to wave impact, can not cause coming off of coating and local corrosion takes place.In addition, nano-titanium oxide multilayer complex films (inorganic/organic multilayer composite membrane etc.), composite granule have very strong absorption and dissipation performance to radar wave and mid-infrared light wave band, radar and infrared eye are produced shielding effect, make boats and ships have tangible stealthy function, thereby can provide new material for boats and ships type antiradar coatings.
Therefore, Red copper oxide is combined with nano titanium oxide, under no rayed, suppress the growth of barnacle, reach the long-acting and anti-fouling effect by the slow release of cuprous ion; Under sun exposure, nanoparticle can with multiple organism generation redox reaction, producing extremely strong hydroxyl free radical of a large amount of oxidation capacities and active oxygen kills most of microbe, can also be decomposed into carbonic acid gas and water to the organism that is difficult to remove that sticks on the hull, or other inorganics of very easily removing.
Easy and the organism reaction of nano-oxide, rosin has certain solvability in seawater, and chlorine-containing polymer cooperates the rate of release that can rationally regulate cupric ion in the paint film with nano-oxide, rosiny; Organobentonite has the precipitable effect of improvement, can make paint vehicle after storage for some time, and the precipitation in jar is comparatively soft, stirs easily.Use the prefabricated nanometer slurry of macromolecule dispersing agent preparation nano antifouling coating, the utilising efficiency of nano powder in coating improved, make nano material easier dispersion in coating, coating system is more stable.Antifouling paint of the present invention is used for antifouling or submarine whole antifouling at boats and ships tidal range district and submerged zone position more.
Marine simultaneous test
Nano antifouling coating carries out antifouling varnish model shallow sea soak test, and according to the test method of GB5370 standard code, test is vigorous in marine life growth, carry out on the buoyant raft of seawater trend less than the wooden structures in the marine site, Zhoushan of 2m/s.The test plate (panel) base material is the sandblast mild steel plate, is coated with rust-proofing primer is housed.Rust-inhibiting paint gauge control 250-300 μ m wherein, the antifouling varnish gauge control is about 60-80 μ m.
Marine fouling organism adheres to kind, adhesion amount and breeding degree on the routine observation model, compare with blank model simultaneously, and result evaluation antifouling varnish performance according to the observation.1 year test period, the surperficial stained and paint film physical condition evaluation of test piece all reaches more than 90, and antifouling property is good.
This table is practice simultaneous test table of the present invention (12 months):
Promote the use case:
The crashproof piling bar of the sharp bridge spanning the sea of Zhoushan city Zhu family, application in January, 2010, antifouling property is stable good so far, and length has fragmentary marine life.
The Zhoushan city connects island bridge segmentation steel body caution post, application in April, 2010, and seldom length has marine life so far.
Specific embodiment
Embodiment 1
Determine to be made by following weight ratio raw material: 5% nano titanium oxide, 5% nano zine oxide, 15.5% Red copper oxide, 20% chlorinated polyether resin, 40% xylene solvent, 4% rosin, 1.5% macromolecule dispersing agent EFKA-4010,4% tritolyl phosphate and 5% machine wilkinite are formed.
Dispose 100g according to the following steps:
At first 20g chlorinated polyether resin powder is joined in the 20g xylene solvent, high speed shear stirs (1500r/min) up to obtaining transparent colloidal solution;
Then 1.5g macromolecule dispersing agent EFKA-4010 is joined in the 20g dimethylbenzene, add 5g nano titanium oxide and 5g nano zine oxide then,, ground 2 hours with sand mill then, make nano titanium dioxide paste 2000rpm high speed dispersion 15 minutes.
In proportion the 31.5g nanometer slurry, 15.5g Red copper oxide, 4g rosin and the 4g tritolyl phosphate that prepare and 5g organobentonite are joined under the high-speed stirring state in the above-mentioned chlorinated polyether resin solution of 40g again, under 1000rpm, disperseed this mixture 15 minutes with high speed dispersor.
Be prepared into nano antifouling coating after filtering with 200 order copper mesh more at last, can use after sampling and testing is qualified.
Embodiment 2
Determine to be made by following weight ratio raw material: the dimethylbenzene of 7% nano titanium oxide, 14% Red copper oxide, 23% chlorinated rubber, 40% weight ratio 3:1 and propyl carbinol solvent, 5% rosin, 3% river, macromolecule dispersing agent sea chemical industry 5040,4% tritolyl phosphate and 4% silicon-dioxide are formed.
Dispose 100g according to the following steps:
At first the chlorinated rubber powder with 23g joins in the dimethylbenzene and propyl carbinol solvent of 23g weight ratio 3:1, and high speed shear stirs (1500 r/min) up to obtaining transparent colloidal solution;
Then river, 3g macromolecule dispersing agent sea chemical industry 5040 is joined in the dimethylbenzene and propyl carbinol solvent of 17g weight ratio 3:1, add the 7g nano titanium oxide,, ground 2 hours with sand mill then, make nano titanium dioxide paste 2000rpm high speed dispersion 15 minutes.
In proportion the 27g nanometer slurry, 14g Red copper oxide, 5g rosin and the 4g tritolyl phosphate that prepare and 4g silicon-dioxide are joined in the above-mentioned chlorinated rubber solution of 46g under high-speed stirring or grinding dispersive state again, under 1000rpm, disperseed this mixture 15 minutes with high speed dispersor.
Be prepared into nano antifouling coating after filtering with 200 order copper mesh at last, can use after sampling and testing is qualified.
Claims (8)
1. an antifouling paint that contains nano-oxide is characterized in that: made by following weight ratio raw material: nano-oxide 5-20%; Red copper oxide 10-30%; Chlorine-containing polymer 20-30%; Rosin 3-5%; Macromolecule dispersing agent 1-7%; Softening agent 3-6%; Anti-settling agent 2-5%; Solvent 20-40%.
2. a kind of antifouling paint that contains nano-oxide according to claim 1, it is characterized in that: described nano-oxide is meant that mean particle size by primary particle nano titanium oxide or in the nano zine oxide one or both below 100nm form, its particle crystal formation is an anatase titanium dioxide, rutile-type or mixing crystal formation.
3. a kind of antifouling paint that contains nano-oxide according to claim 1 is characterized in that: described chlorine-containing polymer is chlorinated polyether resin, chlorinated rubber, chlorinated polyvinyl chloride or vinylchlorid vinyl acetate copolymer.
4. a kind of antifouling paint that contains nano-oxide according to claim 1 is characterized in that: described macromolecule dispersing agent is selected from Disperbyk163, the EFKA-4010 of Deuchem Co., Ltd., extra large river chemical industry 5040 or the Sodium hexametaphosphate 99 of German Bi Ke chemical company.
5. a kind of antifouling paint that contains nano-oxide according to claim 1 is characterized in that: described softening agent is one or both in tritolyl phosphate or the clorafin.
6. a kind of antifouling paint that contains nano-oxide according to claim 1 is characterized in that: described anti-settling agent is one or both in organobentonite or the silicon-dioxide.
7. a kind of antifouling paint that contains nano-oxide according to claim 1 is characterized in that: described solvent is one or both in dimethylbenzene, trimethylbenzene or the propyl carbinol.
8. one kind prepares the described a kind of preparation method who contains the antifouling paint of nano-oxide of claim 1-8, it is characterized in that its preparation process is as follows:
In the solvent with quality such as chlorine-containing polymer powder addings, high speed shear stirs (1500r/min) up to obtaining transparent colloidal solution, is chlorine-containing polymer solution at first in proportion;
Then in proportion macromolecule dispersing agent is added in the certain amount of solvent, add nano-oxide then, 400-2000rpm high speed dispersion 5-60 minute; The gained slurry ground in ball mill or sand mill or ball mill 20 minutes-24 hours; Make the nano-oxide slurry;
Again in proportion the nano-oxide slurry for preparing and Red copper oxide, rosin, softening agent, anti-settling agent etc. in high-speed stirring or grind under the dispersive state and join in the chlorine-containing polymer solution, fully disperse this mixture with high speed dispersor or grinding plant, the time is 10 minutes-60 minutes;
Being prepared into nano antifouling coating after filtering with 100-300 purpose screen cloth or silk at last, can weighing and bagging be finished product after sampling and testing is qualified.
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| CN 201110100299 CN102181206A (en) | 2011-04-21 | 2011-04-21 | Antifouling paint containing nano oxides |
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| CN 201110100299 CN102181206A (en) | 2011-04-21 | 2011-04-21 | Antifouling paint containing nano oxides |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408763A (en) * | 2011-11-22 | 2012-04-11 | 吴江市天源塑胶有限公司 | Method for preparing anti-fouling paint for ship bottom |
| CN102511503A (en) * | 2011-12-06 | 2012-06-27 | 海南大学 | Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method |
| CN102690556A (en) * | 2012-06-07 | 2012-09-26 | 海安县国力化工有限公司 | Chlorinated rubber antifouling paint |
| CN103087592A (en) * | 2012-12-26 | 2013-05-08 | 山东鲁蒙防水防腐材料股份有限公司 | Multifunctional nano antiseptic marine paint |
| CN103436171A (en) * | 2013-08-28 | 2013-12-11 | 广西梧州龙鱼漆业有限公司 | Antifouling paint and preparation method thereof |
| CN104817913A (en) * | 2015-05-15 | 2015-08-05 | 上海海悦涂料有限公司 | Long-acting environment-friendly ship bottom antifouling paint, strippable antifouling paint and ship bottom antifouling treatment method |
| CN104974610A (en) * | 2015-06-30 | 2015-10-14 | 韩光泉 | Anticorrosive paint |
| CN105017910A (en) * | 2014-04-17 | 2015-11-04 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating and preparation method thereof |
| CN105778640A (en) * | 2016-05-25 | 2016-07-20 | 南通中国科学院海洋研究所海洋科学与技术研究发展中心 | Nano-TiO2-modified chloric ether resin marine antifouling coating and preparation method and application thereof |
| CN107141905A (en) * | 2017-06-09 | 2017-09-08 | 冯智勇 | A kind of metallic paint protective coating |
| CN107556850A (en) * | 2017-09-21 | 2018-01-09 | 苏州振振好新型建材科技有限公司 | A kind of antifouling elastic coating of ship |
| CN107629495A (en) * | 2017-09-25 | 2018-01-26 | 国网浙江省电力公司电力科学研究院 | A kind of DC fields equipment surface antifouling paint and its preparation method and application |
| CN107964338A (en) * | 2017-12-29 | 2018-04-27 | 安徽科邦树脂科技有限公司 | A kind of anti-fouling type water paint synthetic method |
| CN108034343A (en) * | 2017-12-29 | 2018-05-15 | 安徽科邦树脂科技有限公司 | A kind of anti-fouling type water paint |
| CN110982359A (en) * | 2019-11-13 | 2020-04-10 | 湖北航天化学技术研究所 | Marine antifouling paint |
| CN116396672A (en) * | 2021-12-28 | 2023-07-07 | 中国科学院海洋研究所 | Organosilicon modified polythiourethane/zinc oxide composite marine antifouling paint and preparation and application thereof |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408763A (en) * | 2011-11-22 | 2012-04-11 | 吴江市天源塑胶有限公司 | Method for preparing anti-fouling paint for ship bottom |
| CN102408763B (en) * | 2011-11-22 | 2013-07-03 | 吴江市天源塑胶有限公司 | Method for preparing anti-fouling paint for ship bottom |
| CN102511503A (en) * | 2011-12-06 | 2012-06-27 | 海南大学 | Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method |
| CN102511503B (en) * | 2011-12-06 | 2014-07-02 | 海南大学 | Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method |
| CN102690556A (en) * | 2012-06-07 | 2012-09-26 | 海安县国力化工有限公司 | Chlorinated rubber antifouling paint |
| CN103087592A (en) * | 2012-12-26 | 2013-05-08 | 山东鲁蒙防水防腐材料股份有限公司 | Multifunctional nano antiseptic marine paint |
| CN103087592B (en) * | 2012-12-26 | 2015-06-03 | 姜美青 | Multifunctional nano antiseptic marine paint |
| CN103436171A (en) * | 2013-08-28 | 2013-12-11 | 广西梧州龙鱼漆业有限公司 | Antifouling paint and preparation method thereof |
| CN105017910A (en) * | 2014-04-17 | 2015-11-04 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating and preparation method thereof |
| CN105017910B (en) * | 2014-04-17 | 2018-04-17 | 浙江省海洋开发研究院 | Modified super-hydrophobic marine antifouling coating of one kind and preparation method thereof |
| CN104817913A (en) * | 2015-05-15 | 2015-08-05 | 上海海悦涂料有限公司 | Long-acting environment-friendly ship bottom antifouling paint, strippable antifouling paint and ship bottom antifouling treatment method |
| CN104974610A (en) * | 2015-06-30 | 2015-10-14 | 韩光泉 | Anticorrosive paint |
| CN105778640A (en) * | 2016-05-25 | 2016-07-20 | 南通中国科学院海洋研究所海洋科学与技术研究发展中心 | Nano-TiO2-modified chloric ether resin marine antifouling coating and preparation method and application thereof |
| CN107141905A (en) * | 2017-06-09 | 2017-09-08 | 冯智勇 | A kind of metallic paint protective coating |
| CN107556850A (en) * | 2017-09-21 | 2018-01-09 | 苏州振振好新型建材科技有限公司 | A kind of antifouling elastic coating of ship |
| CN107629495A (en) * | 2017-09-25 | 2018-01-26 | 国网浙江省电力公司电力科学研究院 | A kind of DC fields equipment surface antifouling paint and its preparation method and application |
| CN107629495B (en) * | 2017-09-25 | 2020-03-03 | 国网浙江省电力公司电力科学研究院 | Direct-current field equipment surface antifouling paint and preparation method and application thereof |
| CN107964338A (en) * | 2017-12-29 | 2018-04-27 | 安徽科邦树脂科技有限公司 | A kind of anti-fouling type water paint synthetic method |
| CN108034343A (en) * | 2017-12-29 | 2018-05-15 | 安徽科邦树脂科技有限公司 | A kind of anti-fouling type water paint |
| CN110982359A (en) * | 2019-11-13 | 2020-04-10 | 湖北航天化学技术研究所 | Marine antifouling paint |
| CN116396672A (en) * | 2021-12-28 | 2023-07-07 | 中国科学院海洋研究所 | Organosilicon modified polythiourethane/zinc oxide composite marine antifouling paint and preparation and application thereof |
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Application publication date: 20110914 |