CN101967316B - Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint - Google Patents
Nontoxic antifouling paint for oceanographic ship and facilities and method for preparing paint Download PDFInfo
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Abstract
The invention discloses a nontoxic antifouling paint for an oceanographic ship and facilities and a method for preparing the paint. The paint consists of the following components in percentage by weight: 15 to 55 percent of base material, 0.01 to 10 percent of antifouling agent, 10 to 30 percent of filler, 0.3 to 25 percent of pigment, 2 to 8 percent of auxiliary agent and 3 to 55 percent of solvent, wherein the antifouling agent is silver grains with average grain diameter of between 1 and 200nm. The paint does not contain toxic agents, such as dichloro-diphenyl-trichloroethane, organic tin, cuprous oxide and the like, at all while effectively suppressing corrosion of marine biological attachments, meets the related regulations of international maritime organization and future development trend of the antifouling paint, realizes non-toxicity and environmental friendliness of the marine antifouling technology, and can be widely applied to the facilities and the fields, such as ships, floating piers, marine oil platforms, submarine cables, cooling pipes of power plant near the sea, sea water culture net cage and the like.
Description
Technical field
The invention belongs to technical field of coatings, particularly a kind of nontoxic antifouling paint for marine ship and facility.
Background technology
One of matter of utmost importance that offshore operation runs into is exactly the part marine organisms adhering to stained various maritime facilitieies such as boats and ships and offshore drilling platform, buoy, net cage for sea farming, hydrospace detection instruments.Tentatively verify at present marine organisms and reach more than 20 ten thousand kinds, wherein settled organism reaches thousands of kinds.These class marine organisms mainly are attached to the position of hull and maritime facilities underwater, can bring very big harm and considerable financial loss to offshore operation, prevent that harm and disadvantageous effect that marine attaching organism brings boats and ships and maritime facilities from being the focus that people pay close attention to always.
Statistics shows, adheres to relevant material damage with marine organisms and accounts for losing efficacy the 70%-80% that relates to extra large total amount of material, effectively stops microorganism significant on the impact of material adherent corrosion.The application antifouling paint is a kind of not only economy but also efficient terms of settlement that prevents marine biofouling, the approach that it discharges with certain speed by the marine life toxic agent by comprised suppresses halobiontic and adheres to and grow, thereby the smooth and coating of maintenance boats and ships and Offshore Units outside surface is intact.Middle and later periods in last century is the organo-tin compound stain control agents such as widespread use tributyltin oxide, three fourths and Tin tetrafluoride., fentin chloride, triphenyl tin fluoride once.Although organotin stain control agent consumption is low, efficiency is high, there is broad spectrum, yet this class organo-tin compound has teratogenecity, at marine life, as in fish, body of shellfish, cumulative function arranged, not only can cause marine life heritable variation, also food chain be can enter, heredity and the existence of the mankind and other biological had a strong impact on, thereby later stage in last century various countries' forbidding organotin antifouling paint of making laws one after another.International Maritime Organizaton (IMO) from 1 day January in 2008 total ban use this series products at boats and ships.After the organic tin antifouling paint is prohibited from using, its surrogate mainly be take the product that Red copper oxide adds other auxiliary antifouling chemical agents to form as main stain control agent, more exactly.80% marine antifouling coating adopts Red copper oxide as stain control agent now.Although its direct injury to human body is still uncertain at present, the toxicity index of some fish and whale is greater than to 24h.Can not be ignored simultaneously, the copper compounds separate out in a large number and be deposited in seabed, growth and the downstream food chain thereof of algae brought to great threat, will inevitably bring permanent injury and pollution to ocean environment.Therefore, International Maritime Organizaton will start to limit in 2012 the use of Red copper oxide, and Chinese environmental protection general bureau also classifies Red copper oxide as excessive risk, high pollution list, and plans to ban use of in 2012.In view of this, the exploitation of Novel non-toxic antifouling coating material is extremely urgent.
China Patent No. discloses a kind of fluorine and/or siloxanes low surface energy anti-fouling paint for No. CN98812901.The shortcoming of low surface energy coatings maximum is that the coating that brings of low surface free energy is poor to sticking power and the sticking power between coat layer of base material, and recoatability is bad, gives the construction of coating and repairs and can cause difficulty.China Patent No. CN200510081683 discloses a kind of zinc acrylate resin that contains Capsaicin functional group or resin of copper and preparation method thereof.But regrettably, this class coating is subject to the restriction of processing condition, and also exists suitable distance between practical application, its large-scale production also is difficult to realize at present.The suitable growth environment of marine fouling organism is the slight alkalinity seawater that the pH value is 7.5-8.0, all is difficult for existence in highly basic or highly acid environment.China Patent No. CN97121813 discloses a kind of nontoxic antifouling paint that silicate is stain control agent of take.But study, show, the effective antifouling life of alkaline silicate antifouling paint is not long, and physicochemical property is poor, and actual application prospect is also uncertain.
Summary of the invention
The object of the invention is to overcome existing antifouling paint deficiency, a kind of novel non-toxic anti-pollution paint for sea is provided; Another object of the present invention is to provide the preparation method of this coating.
The objective of the invention is to be achieved through the following technical solutions:
A kind of nontoxic antifouling paint for marine ship and facility, by base-material, stain control agent, filler, pigment, auxiliary agent and solvent composition, the weight percent of described each component is:
Base-material 15～55%,
Stain control agent 0.01～10%,
Filler 10～30%,
Pigment 0.3～25%,
Auxiliary agent 2～8%,
Solvent 3～55%.
Described stain control agent is the silver-colored particle of median size at 1～200 interior rice.
In above-mentioned antifouling paint, described base-material is at least one in acrylic resin, ethenoid resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, pitch, poly divinyl acetylene resin, resol, urea-formaldehyde resin, melamine resin, urethane, epoxy resin, Synolac, silicone resin, organic fluorine or subsilicate.
In above-mentioned antifouling paint, described filler is at least one in calcium carbonate, barium carbonate, silicon-dioxide, talcum powder, graphite, zinc oxide, diatomite, glass microsphere, ground barium sulfate, wilkinite, organic pottery clay, china clay, zeolite powder or mica.
In above-mentioned antifouling paint, described pigment is at least one in red iron oxide, laterite, iron oxide yellow, carbon black, titanium dioxide, zinc sulfide white, magnesium oxide, barba hispanica, ultramarine, diarylide yellow, calcium phosphate, trimagnesium phosphate or barium metaborate.
In above-mentioned antifouling paint, described auxiliary agent is at least one in dispersion agent, defoamer, flow agent, film coalescence aid, wetting agent, softening agent, siccative, pH adjusting agent, sanitas, anti-settling and thixotropic thickening agent;
Above-mentioned auxiliary agent can be selected from but be not limited to following kind:
Dispersion agent: Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, Zinic stearas, Yelkin TTS, Disper BYK series;
Defoamer: tributyl phosphate, dimethyl polysiloxane, polyether-modified methyl polysiloxane, aluminum stearate;
Flow agent: polymethyl acrylate, PSI, polyester modification polydimethyl silane;
Film coalescence aid: alcohol ester 12, Texanol, ethylene glycol, sherwood oil, diisobutyl adipic acid ester;
Wetting agent: vinyltriethoxysilane, vinyltriacetoxy silane, dimethyl silicone oil;
Softening agent: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, Viscotrol C, clorafin;
Siccative: cobalt naphthenate, manganese naphthenate, calcium iso-octoate, zirconium iso-octoate, diethyl are with sour cobalt;
Sanitas: Sodium Benzoate, isothiazolinone, BIT (BIT);
PH adjusting agent: ammoniacal liquor, aqueous sodium hydroxide solution, acetic acid;
Anti-settling and thixotropic thickening agent: organobentonite, aluminium octoate, calcium stearate, polyethylene wax, zinc ricinate.
In above-mentioned antifouling paint, described solvent is ketone, for example acetone, pimelinketone, butanone or ester class, for example ethyl acetate, butylacetate or jasmal; Alcohols, for example methyl alcohol, ethanol, Virahol, isopropylcarbinol, ethylene glycol or propylene glycol; Ethers, for example ethylene glycol ethyl ether, butyl glycol ether or propylene-glycol ethyl ether; Fat hydrocarbon, for example normal hexane, hexanaphthene, Skellysolve A, octane or heptane; Arene, for example at least one in toluene, dimethylbenzene, trimethylbenzene or water.
A kind of method for preparing above-mentioned antifouling paint, it carries out according to the following steps:
Under the condition of room temperature to 80 ℃, base-material is added in solvent and dissolved, add successively stain control agent, pigment, filler and auxiliary agent, after being stirred, disperse, grind 2～6 hours with the rotating speed of 1500～5000r/min, make antifouling paint.
The present invention utilizes silver-colored particle to have no side effect, have broad spectrum antibacterial and eco-friendly characteristics to human body and other organism, development is for the nontoxic antifouling paint of marine ship and facility, when effectively suppressing the marine organisms adherent corrosion, do not contain the toxic agent such as dichlorodiphenyl trichloroethane (DDT), organotin (TBT), Red copper oxide fully, the future developing trend that meets International Maritime Organizaton's (IMO) relevant regulations and antifouling paint, realized that the nothing of marine anti-pollution technology poisons and greenization.
Compared with prior art, the present invention has following outstanding advantages:
1. the silver-colored particle that yardstick is 1～200 nanometer is for the preparation of Marine Paints, and antifouling property is remarkable, under lower concentration, be the tool anti-fouling effect, and cost performance is high;
2. antifouling paint of the present invention has the antifouling usefulness of wide spectrum to adhering to marine organisms;
3. antifouling paint of the present invention in use, can not discharge toxic substance, environmental protection in seawater;
4. antifouling paint of the present invention can be widely used in boats and ships, floating terminal, offshore platform, undersea cable, border on the sea facility and the fields such as power station cooling duct and net cage for sea farming.
Embodiment
Below in conjunction with embodiment, technology of the present invention and characteristics are described further.
Embodiment 1
Each component is joined in multi-functional dispersion machine material-compound tank by following formula, and mixture remains under 50 ℃, with the rotating speed of 2000r/min, stirs, disperses, grinds 4 hours, makes 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) acrylic resin 500.00g,
(2) zinc oxide 187.43g,
(3) red iron oxide 124.95g,
(4) talcum powder 62.57g,
(5) dimethylbenzene 124.95g,
(6) silver-colored particle 0.10g,
The median size of described silver-colored particle is 15nm.
Embodiment 2
(1) water soluble acrylic resin's base-material and water are mixed into to the water soluble resin aqueous solution, then in the water soluble resin aqueous solution, add organo-silicon coupling agent vinyltriethoxysilane and dimethyl-silicon oil assistant;
(2), under 55 ℃ of conditions, superfine silicon dioxide, titanium dioxide, zinc oxide, light magnesium oxide, water glass and stain control agent are added in multi-functional dispersion machine material-compound tank successively; Rotating speed with 3500r/min stirs, disperses, grinds 2 hours, makes the 1kg non-toxic anti-pollution paint for sea.
In formula, each composition weight is respectively:
(1) water soluble acrylic resin 392.04g,
(2) deionized water 417.00g,
(3) vinyltriethoxysilane 6.58g,
(4) dimethyl silicone oil 16.06g,
(5) superfine silicon dioxide 22.94g,
(6) titanium dioxide 13.28g,
(7) zinc oxide 45.96g,
(8) light magnesium oxide 32.70g,
(9) water glass 52.44g,
(10) silver-colored particle 1.00g,
The median size of described silver-colored particle is about 1nm.
Embodiment 3
Each component is joined in multi-functional dispersion machine material-compound tank by following formula, and mixture keeps at room temperature, with the rotating speed of 1500r/min, stirs, disperses, grinds 6 hours, makes 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) coal coke asphalt liquid 90.82g,
(2) rosin 208.58g,
(3) zinc oxide 159.68g,
(4) laterite 211.58g,
(5) talcum powder 93.81g,
(6) heavy benzene 233.53g,
(7) silver-colored particle 2.00g,
The median size of described silver-colored particle is 22nm.
Embodiment 4
Each component is joined in multi-functional dispersion machine material-compound tank by following formula, and mixture remains under 40 ℃, with the rotating speed of 5000r/min, stirs, disperses, grinds 3 hours, makes 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) ethenoid resin 149.25g
(2) tributyl phosphate 27.26g,
(3) rosin 113.76g,
(4) epoxy resin 3.28g,
(5) laterite 236.91g,
(6) zinc oxide 165.87g,
(7) talcum powder 94.72g,
(8) organic pottery clay 11.84g,
(9) pimelinketone 85.57g,
(10) trimethylbenzene 106.57g,
(11) silver-colored particle 4.97g,
The median size of described silver-colored particle is 45nm.
Embodiment 5
Each component is joined in multi-functional dispersion machine material-compound tank by following formula, and mixture remains under 80 ℃, with the rotating speed of 4000r/min, stirs, disperses, grinds 2 hours, makes 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) 35% chlorinated rubber liquid 99.58g,
(2) clorafin 28.96g,
(3) 50% carboxylic ester 34.77g,
(4) rosin 104.32g,
(5) laterite 231.77g,
(6) zinc oxide 162.23g,
(7) talcum powder 92.69g,
(8) organic pottery clay 11.62g,
(9) barium meta carbonate 11.62g,
(10) dimethylbenzene 214.94g,
(11) silver-colored particle 7.50g,
The median size of described silver-colored particle is 64nm.
Embodiment 6
Each component is joined in multi-functional dispersion machine material-compound tank according to this by following formula, and mixture remains under 50 ℃, with the rotating speed of 2500r/min, stirs, disperses, grinds 4 hours, and regulating the pH value with sodium hydroxide is 8.Make 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) organosilicon crylic acid latex 554.26g,
(2) Sodium hexametaphosphate 99 27.74g,
(3) zinc oxide 269.50g,
(4) Natvosol 13.77g,
(5) tributyl phosphate 1.36g,
(6) Sodium Benzoate 2.82g,
(7) ethylene glycol 27.74g,
(8) propylene glycol 2.81g,
(9) silver-colored particle 100.00g,
The median size of described silver-colored particle is 78nm.
Embodiment 7
Acrylic resin is dissolved in mixed solvent, adds successively silver-colored particle, dispersion agent, pigment, filler etc., remain under 35 ℃, with the 3000r/min rotating speed, stir, disperse, grind 2.5 hours, make 1kg non-toxic anti-pollution paint for sea finished product.
In formula, each composition weight is respectively:
(1) acrylic resin 435.86g,
(2) talcum powder 43.51g,
(3) zinc oxide 145.26g,
(4) phthalocyanine blue 2.94g,
(5)Disper BYK 102 2.94g，
(6) organobentonite 32.07g,
(7) dimethylbenzene 226.84g,
(8) butylacetate 72.58g,
(9) silver-colored particle 38.00g,
The median size of described silver-colored particle is 126nm.
Embodiment 8
Modified organic silicon is dissolved in organic solvent, add successively again auxiliary agent, silver-colored particles such as clorafin, zinc oxide, dimethyl silicone oil, fluorocarbon surfactants, remain under 65 ℃, stir, disperse, grind 3.5 hours with the 1800r/min rotating speed, become low surface energy non-toxic anti-pollution paint for sea A component.At room temperature, low molecular polyamides is dissolved in mixed solvent and makes antifouling paint B component.Before use A, two components of B are mixed.
In formula, each composition weight is respectively:
The A component:
(1) modified organic silicon 287.40g,
(2) clorafin 67.06g,
(3) zinc oxide 38.32g,
(4) fluorocarbon surfactant 2.50g,
(5) dimethyl silicone oil 3.25g,
(5) mixed solvent 496.24g,
(6) silver-colored particle 42.00g,
The B component:
(1) low molecular polyamides 5.75g,
(2) mixed solvent 57.48g,
The mixture that described mixed solvent is toluene, dimethylbenzene, propyl carbinol, isopropylcarbinol and Virahol.
The median size of described silver-colored particle is 200nm.
The above is only the preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, can also make some improvement and change and also should be considered within the scope of protection of the present invention.
Claims (7)
1. the nontoxic antifouling paint for marine ship and facility, it is by base-material, stain control agent, filler, pigment, auxiliary agent and solvent composition, it is characterized in that, described stain control agent is the silver-colored particle of median size in 1～200 nanometer, and the weight percent of described each component is:
Base-material 15～55 %,
Stain control agent 0.01～10 %,
Filler 10～30 %,
Pigment 0.3～25 %,
Auxiliary agent 2～8 %,
Solvent 3～55 %.
2. nontoxic antifouling paint according to claim 1, it is characterized in that, described base-material is at least one in acrylic resin, ethenoid resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, pitch, poly divinyl acetylene resin, resol, urea-formaldehyde resin, melamine resin, urethane, epoxy resin, Synolac, silicone resin, organic fluorine or subsilicate.
3. nontoxic antifouling paint according to claim 2, it is characterized in that, described filler is at least one in calcium carbonate, barium carbonate, silicon-dioxide, talcum powder, graphite, zinc oxide, diatomite, glass microsphere, ground barium sulfate, wilkinite, organic pottery clay, china clay, laterite, zeolite powder or mica.
4. nontoxic antifouling paint according to claim 3, it is characterized in that, described pigment is at least one in red iron oxide, iron oxide yellow, carbon black, titanium oxide, zinc sulfide white, magnesium oxide, barba hispanica, ultramarine, diarylide yellow, calcium phosphate, trimagnesium phosphate or barium metaborate.
5. nontoxic antifouling paint according to claim 4, it is characterized in that, described auxiliary agent is at least one in dispersion agent, defoamer, flow agent, film coalescence aid, wetting agent, softening agent, siccative, pH adjusting agent, sanitas or anti-settling and thixotropic thickening agent; Wherein,
Described dispersion agent is: Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, Zinic stearas, Yelkin TTS;
Described defoamer is: tributyl phosphate, dimethyl polysiloxane, polyether-modified methyl polysiloxane, aluminum stearate;
Described flow agent is: polymethyl acrylate, PSI, polyester modification polydimethyl silane;
Described film coalescence aid is: alcohol ester 12, Texanol, ethylene glycol, sherwood oil, diisobutyl adipic acid ester;
Described wetting agent is: vinyltriethoxysilane, vinyltriacetoxy silane, dimethyl silicone oil;
Described softening agent is: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, Viscotrol C;
Described siccative is: cobalt naphthenate, manganese naphthenate, calcium iso-octoate, zirconium iso-octoate;
Described sanitas is: Sodium Benzoate, isothiazolinone, BIT;
Described pH adjusting agent is: ammoniacal liquor, aqueous sodium hydroxide solution, acetic acid;
Described anti-settling and thixotropic thickening agent are: organobentonite, aluminium octoate, calcium stearate, polyethylene wax, zinc ricinate.
6. nontoxic antifouling paint according to claim 5, it is characterized in that, described solvent is at least one in acetone, pimelinketone, butanone, ethyl acetate, butylacetate, jasmal, methyl alcohol, ethanol, Virahol, isopropylcarbinol, ethylene glycol, propylene glycol, ethylene glycol ethyl ether, butyl glycol ether, propylene-glycol ethyl ether, normal hexane, hexanaphthene, Skellysolve A, octane, heptane, toluene, dimethylbenzene, trimethylbenzene or water.
One kind prepare as described in claim 1,2,3,4,5 or 6 for the method for the nontoxic antifouling paint of marine ship and facility, it is characterized in that, it carries out according to the following steps:
In room temperature to 80
under the condition of C, base-material is added in solvent and dissolved, add successively stain control agent, pigment, filler and auxiliary agent, after being stirred, disperse, grind 2～6 hours with the rotating speed of 1500～5000 r/min, make described nontoxic antifouling paint.
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