CN103160205A - Ionic liquid marine antifouling coating - Google Patents
Ionic liquid marine antifouling coating Download PDFInfo
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- CN103160205A CN103160205A CN2011104253570A CN201110425357A CN103160205A CN 103160205 A CN103160205 A CN 103160205A CN 2011104253570 A CN2011104253570 A CN 2011104253570A CN 201110425357 A CN201110425357 A CN 201110425357A CN 103160205 A CN103160205 A CN 103160205A
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Abstract
The invention discloses an ionic liquid marine antifouling coating. The ionic liquid marine antifouling coating is composed of 5 to 15 parts of ionic liquid, 30 to 45 parts of polyurethane, 0.1 to 1 part of titanium dioxide powder, 0.2 to 1 part of zinc oxide powder and 0.1 to 1 part of promoter and 40 to 55 parts of diluent. The ionic liquid marine antifouling coating can be used for marine organism pollution resistance on surfaces of ships and marine monitoring instruments.
Description
Technical field
The present invention relates to a kind of ionic liquid coating with anti-marine biological polution function.
Background technology
In developing the ocean, utilizing the historical progress of ocean, the mankind are faced with the problem of preventing and kill off marine attaching organism always.Be attached to the marine organisms on the various facilities surface in hull bottom and ocean and microorganism and caused huge harm to the exploration of sea transport and oceanic resources, exploitation, utilization etc.For reduce harm that marime fouling causes, save the energy and expenditure, the operational efficiency of the maritime facilitieies such as protection of the environment and raising naval vessel; taked in the world many effective measures, existing antifouling paint comprises traditional antifouling paint and nontoxic antifouling paint.Traditional antifouling paint is to utilize the copper that discharges in coating, tin, mercury and the poison such as plumbous is expected and organotin kills marine life.Although but that this material can reduce or eliminate is halobiontic stained, the release of objectionable impurities has also caused serious harm to ecotope and human health.Gao Junmin etc. are once in ocean science, and 2006,30 (5): reported organotin on 65-70 to halobiontic pollution, also research found that organotin can accumulate, and caused heritable variation, but also might enter food chain in fish, body of shellfish afterwards.Forbade thoroughly that boats and ships use the antifoulant that contains organotin on January 1st, 2008.Therefore developing low toxicity, nontoxic or environmentally friendly antifouling paint has become and has been badly in need of in the world one of important topic that solves marine biofouling.
Can extract a series of nontoxic, natural products that have antifouling activity from marine plant, marine animal (being mainly marine invertebrate) and marine microorganism, as Denys R et al etc. at Biofouling, 1995 (8): the 259-271 report series of secondary meta-bolites halogenated furan ketone that separation and purification obtains from red algae can effectively suppress line barnacle, large-scale algae sea lettuce and marine bacteria, but purification process is complicated, production cost is high, limits the popularization of its practical application.
Summary of the invention
The object of the present invention is to provide a kind of ionic liquid marine antifouling coating.
The ionic liquid preparation method is simple, and the advantages such as pollution-free because having, difficult volatilization, good thermostability and chemical stability are widely used in the every field of chemical research.Our recent research finds that ionic liquid is a kind of material of antibiotic anti-protein adsorption efficiently, therefore the present invention adds it it to coating in, can obtain marine antifouling coating in addition.This coating can be used for the anti-marine biological polution on boats and ships and Marine monitoring instrument surface.
A kind of ionic liquid marine antifouling coating, it is characterized in that each component of this coating according to the weight part meter, formed by ionic liquid 5-15 part, urethane 30-45 part, titania powder 0.1-1 part, Zinc oxide powder 0.2-1 part, auxiliary agent 0.1-1 part and thinner 40-55 part; Wherein ionic liquid is selected from a kind of in 1-methyl 3-hexyl imidazoles phosphofluoric acid, 1-methyl 3-dodecyl imidazoles trifluoromethane sulfonic acid and 1-methyl 3-hexyl imidazoles two trimethyl fluoride sulfonyl ammoniums; Auxiliary agent is comprised of wetting dispersing agent and anti-settling agent, wetting dispersing agent 0.05-0.5 part wherein, and wetting dispersing agent is selected the polyaminoamide solution of cationic unsaturated polycarboxylic acid; Anti-settling agent 0.05-0.5 part, anti-settling agent is selected organobentonite; Thinner is comprised of the mixed solvent of acetone and dimethylbenzene or N-BUTYL ACETATE.
The synthetic method reference of ionic liquid of the present invention: Huddleston et al, GreenChemistry, 2001 (3): 156-164.
Urethane of the present invention is the castor oil modified base polyurethane prepolymer for use as of alcoholysis, and isocyanate content is 5-8%, and number-average molecular weight is 3500, and its structural formula is:
Titania powder particle diameter of the present invention is 10nm-100nm.
Zinc oxide powder particle diameter of the present invention is 200nm-1 μ m.
The mass ratio of acetone of the present invention and dimethylbenzene or N-BUTYL ACETATE is 1: 0.5-3.
Wetting dispersing agent of the present invention is selected the polyaminoamide solution of cationic unsaturated polycarboxylic acid, BYK (130) the type dispersion agent that preferably adopts German BYK company to produce.
Coating of the present invention prepares by the following method:
First urethane, ionic liquid, titanium dioxide, zinc oxide, auxiliary agent are joined the thinner dispersion grinding to the coating fineness less than 50 μ m, obtain marine antifouling coating.
The coating method of coating of the present invention has two kinds:
The first for the spraying: under 0.25-0.5MPa pressure, with paint spay-coating to base material.
The second is for brushing: first up and then down according to the brushing direction with painting brush, from left to right carry out application.
After spraying or brushing, wet film self-vulcanizing 24 hours.
Ionic liquid marine antifouling coating of the present invention sprays to the performance test of tinplate surface coating.Performance is as follows:
Drying varniss time: GB1728-79,16～25 ℃ of room temperatures, surface drying 10 hours was done solid work 24 hours;
Sticking power: GB1720-79 (drawing the circle method), 1 grade;
Shock-resistance: GB1732-79,50Kgcm just recoils;
Snappiness: GB1731-79,1mm;
The gauge control of coating is at 30 μ m-100 μ m.
Ionic liquid marine antifouling coating of the present invention, the mild steel plate that sprays to sandblasting carries out the ocean panel experiment: will be coated with the experiment model that is brushed with various antifouling paints and blank plate and be placed in lower 6 meters depths, sea and carry out the extra large link plate dynamic testing of reality.Test period year June in June, 2010 to 2011, test site: ocean research base, Qingdao.This coating model shallow sea link plate is after 1 year, and paint film is intact, and without bubbling, coming off, model surface marine fouling organism adheres to few, shows that it has good anti-fouling effect.
Coating of the present invention can be used for the anti-marine biological polution on boats and ships and Marine monitoring instrument surface.
Embodiment
Embodiment 1
Formulation for coating material: 40 parts of urethane, 5 parts of 1-methyl 3-hexyl imidazoles phosphofluoric acids, 0.5 part of titanium dioxide, 1 part, zinc oxide, (130) 0.25 parts of BYK, 0.25 part of organobentonite, 53 parts of the mixed solvents of acetone and dimethylbenzene (mass ratio of acetone and dimethylbenzene is 1: 1).
Embodiment 2
Formulation for coating material: 40 parts of urethane, 10 parts of 1-methyl 3-hexyl imidazoles phosphofluoric acids, 1 part of titanium dioxide, 0.5 part, zinc oxide, (130) 0.25 parts of BYK, 0.25 part of organobentonite, 48 parts of the mixed solvents of acetone and N-BUTYL ACETATE (mass ratio of acetone and N-BUTYL ACETATE is 1: 3).
Embodiment 3
Formulation for coating material: 40 parts of urethane, 15 parts of 1-methyl 3-hexyl imidazoles phosphofluoric acids, 0.5 part of titanium dioxide, 1 part, zinc oxide, (130) 0.25 parts of BYK, 0.25 part of organobentonite, 43 parts (mass ratio of acetone and N-BUTYL ACETATE is 1: 0.5) of the mixed solvent of acetone and N-BUTYL ACETATE.
Embodiment 4
Formulation for coating material: 40 parts of urethane, 10 parts of 1-methyl 3-dodecyl imidazoles trifluoromethane sulfonic acids, 0.5 part of titanium dioxide, 0.5 part, zinc oxide, (130) 0.25 parts of BYK, 0.25 part of organobentonite, 48 parts of the mixed solvents of acetone and dimethylbenzene (mass ratio of acetone and dimethylbenzene is 1: 0.5).
Embodiment 5
Formulation for coating material: 30 parts of urethane, 10 parts of 1-methyl 3-hexyl imidazoles two trimethyl fluoride sulfonyl ammoniums, 1 part, zinc oxide, (130) 0.25 parts of BYK, 0.25 part of organobentonite, 53 parts of the mixed solvents of acetone and dimethylbenzene (mass ratio of acetone and dimethylbenzene is 1: 3).
According to above-mentioned formula with coating after, adopt the method for spraying to obtain antifouling coating.In embodiment related coating shallow sea, Qingdao lacing film after 1 year antifouling property as shown in table 1.
Table 1. antifouling coating shallow sea hanging test
* blank model: do not add ionic liquid in coating, other form with embodiment 1.
* be coated with the tin-free self-polishing antifouling paint that chemical industry company limited produces in.
Claims (6)
1. ionic liquid marine antifouling coating, it is characterized in that each component of this coating according to the weight part meter, formed by ionic liquid 5-15 part, urethane 30-45 part, titania powder 0.1-1 part, Zinc oxide powder 0.2-1 part, auxiliary agent 0.1-1 part and thinner 40-55 part; Wherein ionic liquid is selected from a kind of in 1-methyl 3-hexyl imidazoles phosphofluoric acid, 1-methyl 3-dodecyl imidazoles trifluoromethane sulfonic acid and 1-methyl 3-hexyl imidazoles two trimethyl fluoride sulfonyl ammoniums; Auxiliary agent is comprised of wetting dispersing agent and anti-settling agent, wetting dispersing agent 0.05-0.5 part wherein, and wetting dispersing agent is selected the polyaminoamide solution of cationic unsaturated polycarboxylic acid; Anti-settling agent 0.05-0.5 part, anti-settling agent is selected organobentonite; Thinner is comprised of the mixed solvent of acetone and dimethylbenzene or N-BUTYL ACETATE.
2. coating as claimed in claim 1, is characterized in that urethane is the castor oil modified base polyurethane prepolymer for use as of alcoholysis, and isocyanate content is 5-8%, and number-average molecular weight is 3500, and its structural formula is:
3. coating as claimed in claim 1, is characterized in that the titania powder particle diameter is 10nm-100nm.
4. coating as claimed in claim 1, is characterized in that the Zinc oxide powder particle diameter is 200nm-1 μ m.
5. coating as claimed in claim 1, the mass ratio that it is characterized in that acetone and dimethylbenzene or N-BUTYL ACETATE is 1: 0.5-3.
6. coating as claimed in claim 1 is characterized in that BYK (130) the type dispersion agent that wetting dispersing agent adopts German BYK company to produce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104253570A CN103160205A (en) | 2011-12-16 | 2011-12-16 | Ionic liquid marine antifouling coating |
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| CN2011104253570A CN103160205A (en) | 2011-12-16 | 2011-12-16 | Ionic liquid marine antifouling coating |
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| CN103160205A true CN103160205A (en) | 2013-06-19 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629600A (en) * | 2015-01-20 | 2015-05-20 | 扬州豪扬新型建筑材料有限公司 | Aqueous polyurethane antiseptic and waterproof coating with high cohesiveness and preparation method of coating |
| CN104710895A (en) * | 2015-03-24 | 2015-06-17 | 湖州国信物资有限公司 | Novel phenolic aldehyde epoxy building coating and preparation method thereof |
| 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 |
| CN109897517A (en) * | 2019-01-30 | 2019-06-18 | 广州精点高分子材料制品有限公司 | A kind of polyurethane enhancing pliability |
| CN111672489A (en) * | 2020-06-01 | 2020-09-18 | 中国科学院兰州化学物理研究所 | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil |
| CN111944407A (en) * | 2020-08-20 | 2020-11-17 | 中山大学 | Polyurethane-based ionic liquid perfusion coating prefabricated liquid, preparation method thereof and ionic liquid perfusion coating |
| CN113004752A (en) * | 2021-04-02 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Transparent marine antifouling paint and preparation method and application thereof |
| CN118440585A (en) * | 2024-07-08 | 2024-08-06 | 山东孚日宣威新材料科技有限公司 | Antifouling paint for marine application facilities and preparation method thereof |
Citations (4)
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| JP2008248058A (en) * | 2007-03-30 | 2008-10-16 | Shin Etsu Chem Co Ltd | Underwater antifouling paint and subaqua structure |
| CN101333348A (en) * | 2008-07-02 | 2008-12-31 | 大连海事大学 | Non-toxic anti-pollution paint for sea and method for preparing same |
| WO2009011227A1 (en) * | 2007-07-18 | 2009-01-22 | Jsr Corporation | Antifouling composition, surface protective film and method for protecting surface of polarizing plate |
| CN101967316A (en) * | 2010-09-08 | 2011-02-09 | 中国乐凯胶片集团公司 | Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint |
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2011
- 2011-12-16 CN CN2011104253570A patent/CN103160205A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008248058A (en) * | 2007-03-30 | 2008-10-16 | Shin Etsu Chem Co Ltd | Underwater antifouling paint and subaqua structure |
| WO2009011227A1 (en) * | 2007-07-18 | 2009-01-22 | Jsr Corporation | Antifouling composition, surface protective film and method for protecting surface of polarizing plate |
| CN101333348A (en) * | 2008-07-02 | 2008-12-31 | 大连海事大学 | Non-toxic anti-pollution paint for sea and method for preparing same |
| CN101967316A (en) * | 2010-09-08 | 2011-02-09 | 中国乐凯胶片集团公司 | Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629600A (en) * | 2015-01-20 | 2015-05-20 | 扬州豪扬新型建筑材料有限公司 | Aqueous polyurethane antiseptic and waterproof coating with high cohesiveness and preparation method of coating |
| CN104710895A (en) * | 2015-03-24 | 2015-06-17 | 湖州国信物资有限公司 | Novel phenolic aldehyde epoxy building coating and preparation method thereof |
| 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 |
| CN109897517A (en) * | 2019-01-30 | 2019-06-18 | 广州精点高分子材料制品有限公司 | A kind of polyurethane enhancing pliability |
| CN111672489A (en) * | 2020-06-01 | 2020-09-18 | 中国科学院兰州化学物理研究所 | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil |
| CN111944407A (en) * | 2020-08-20 | 2020-11-17 | 中山大学 | Polyurethane-based ionic liquid perfusion coating prefabricated liquid, preparation method thereof and ionic liquid perfusion coating |
| CN113004752A (en) * | 2021-04-02 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Transparent marine antifouling paint and preparation method and application thereof |
| CN118440585A (en) * | 2024-07-08 | 2024-08-06 | 山东孚日宣威新材料科技有限公司 | Antifouling paint for marine application facilities and preparation method thereof |
| CN118440585B (en) * | 2024-07-08 | 2024-09-03 | 山东孚日宣威新材料科技有限公司 | Antifouling paint for marine application facilities and preparation method thereof |
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Application publication date: 20130619 |