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CN101967316A - 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 PDF

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CN101967316A
CN101967316A CN 201010275187 CN201010275187A CN101967316A CN 101967316 A CN101967316 A CN 101967316A CN 201010275187 CN201010275187 CN 201010275187 CN 201010275187 A CN201010275187 A CN 201010275187A CN 101967316 A CN101967316 A CN 101967316A
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agent
antifouling
percent
resin
paint
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CN101967316B (en
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邹竞
王虹
吕丽云
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CHINA LUCKY GROUP Corp
Tianjin University
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Tianjin University
China Lucky Film Group Corp
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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

Nontoxic antifouling paint for marine ships and facilities and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a nontoxic antifouling coating for marine ships and facilities.
Background
One of the primary problems encountered in offshore operations is the adhesion and fouling of some marine organisms to various marine facilities such as ships, offshore drilling platforms, buoys, mariculture net cages, marine detection instruments and the like. At present, it has been preliminarily ascertained that the number of marine organisms is 20 or more and thousands of the fouling organisms are present. The marine organisms are mainly attached to the ship body and the part below the waterline of the marine facility, great harm and considerable economic loss are brought to marine operation, and the focus of people on preventing the harm and adverse effect of the marine organisms on ships and the marine facility is always concerned.
Statistics show that the material damage and failure related to marine organism adhesion accounts for 70-80% of the total amount of the marine material, and the effective prevention of the influence of microorganisms on material adhesion corrosion is of great significance. The application of antifouling paints is an economical and efficient solution to prevent fouling by marine organisms by inhibiting the attachment and growth of marine organisms by releasing the marine organisms contained at a rate that maintains the smoothness of the outer surface and the integrity of the coating on ships and offshore structures. In the middle and later stages of the last century, organotin compound antifouling agents such as tributyltin oxide, tin fluoride, triphenyltin chloride and triphenyltin fluoride have been widely used. Although the organic tin antifouling agent has low dosage, high efficiency and broad spectrum, the organic tin compound has teratogenicity and has cumulative effect in marine organisms such as fish and shellfish, which not only causes the genetic variation of the marine organisms, but also can enter a food chain to seriously affect the heredity and survival of human beings and other organisms, so that the organic tin antifouling paint is forbidden by various legislations in the later period of the last century. The International Maritime Organization (IMO) has completely banned the use of such products on ships since 1 month 1 of 2008. After the organic tin antifouling paint is forbidden to be used, the substitute is mainly a product which is formed by taking cuprous oxide as a main antifouling agent and adding other auxiliary antifouling chemical agents. Currently 80% marine antifouling paints use cuprous oxide as the antifouling agent. Although the direct injury to the human body is not clear at present, the toxicity index to some fishes and whales is more than 24 h. Meanwhile, a large amount of copper compounds are separated out and deposited on the seabed, so that the growth of algae and the downstream food chain belts thereof are greatly threatened, and permanent damage and pollution to the marine environment are inevitably brought. Therefore, the international maritime organization will start to limit the use of cuprous oxide in 2012, and the chinese environmental protection agency will list cuprous oxide as a high risk, high pollution list and plan to ban the use in 2012. In view of this, the development of new nontoxic antifouling coating materials is urgent.
Chinese patent No. CN98812901 discloses a fluorine and/or siloxane low surface energy antifouling paint. The most important defects of the low surface energy coating are that the adhesion of the coating to a base material and the adhesion between coating layers are poor due to low surface free energy, the recoatability is poor, and the construction and repair of the coating are difficult. Chinese patent No. CN200510081683 discloses zinc acrylate or copper resin containing a capsaicin functional group and a preparation method thereof. Unfortunately, the coating is limited by the process conditions, and has a considerable distance from the practical application, and the scale production of the coating is difficult to realize at present. The suitable growth environment of the marine fouling organisms is slightly alkaline seawater with the pH value of 7.5-8.0, and the marine fouling organisms are not easy to survive in strong alkali or strong acid environment. Chinese patent No. CN97121813 discloses a nontoxic antifouling paint using silicate as an antifouling agent. However, researches show that the alkali silicate antifouling paint has short effective antifouling period, poor physical and chemical properties and unclear practical application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the existing antifouling paint and provide a novel non-toxic marine antifouling paint; it is a further object of the present invention to provide a process for the preparation of such coatings.
The purpose of the invention is realized by the following technical scheme:
a non-toxic antifouling paint for marine ships and facilities comprises a base material, an antifouling agent, a filler, a pigment, an auxiliary agent and a solvent, wherein the components in percentage by weight are as follows:
15 to 55 percent of base material,
0.01 to 10% of an antifouling agent,
10 to 30 percent of filler,
0.3 to 25 percent of pigment,
2 to 8 percent of auxiliary agent,
3-55% of a solvent.
The antifouling agent is silver particles with the average particle size of 1-200 nm.
In the antifouling paint, the base material is at least one of acrylic resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, asphalt, polydivinyl acetylene resin, phenolic resin, urea resin, melamine resin, polyurethane, epoxy resin, alkyd resin, organic silicon resin, organic fluorine resin or alkali silicate.
In the antifouling paint, the filler is at least one of calcium carbonate, barium carbonate, silicon dioxide, talcum powder, graphite, zinc oxide, diatomite, glass microspheres, barite powder, bentonite, organic argil, porcelain clay, zeolite powder or mica.
In the antifouling paint, the pigment is at least one of red iron oxide, red earth, yellow iron oxide, carbon black, titanium dioxide, lithopone, magnesium oxide, iron blue, ultramarine, benzidine yellow, calcium phosphate, magnesium phosphate or barium metaborate.
In the antifouling paint, the auxiliary agent is at least one of a dispersing agent, a defoaming agent, a flatting agent, a film-forming auxiliary agent, a wetting agent, a plasticizer, a drier, a pH regulator, a preservative, an anti-settling agent and a thixotropic thickener;
the above-mentioned auxiliary agents can be selected from, but not limited to, the following species:
dispersing agent: sodium hexametaphosphate, sodium dodecyl benzene sulfonate, zinc stearate, lecithin and Disper BYK series;
defoaming agent: tributyl phosphate, dimethyl polysiloxane, polyether modified methyl polysiloxane and aluminum stearate;
leveling agent: polymethyl acrylate, polymethylphenylsiloxane, polyester-modified polydimethylsilane;
film-forming auxiliary agent: alcohol ester dodeca, Texanol, ethylene glycol, petroleum ether, diisobutyl adipate;
wetting agent: vinyl triethoxysilane, vinyl triacetoxysilane, dimethicone;
plasticizer: tributyl phosphate, dibutyl phthalate, epoxy linseed oil, castor oil and chlorinated paraffin;
a drier: cobalt naphthenate, manganese naphthenate, calcium isooctanoate, zirconium isooctanoate, cobalt diethyloleate;
preservative: sodium benzoate, isothiazolinone, Benzisothiazolinone (BIT);
pH regulator: ammonia water, sodium hydroxide aqueous solution, acetic acid;
anti-settling thixotropic thickener: organic bentonite, aluminum octoate, calcium stearate, polyethylene wax and zinc ricinoleate.
In the above antifouling paint, the solvent is a ketone such as acetone, cyclohexanone, methyl ethyl ketone or an ester such as ethyl acetate, butyl acetate or benzyl acetate; alcohols such as methanol, ethanol, isopropanol, isobutanol, ethylene glycol or propylene glycol; ethers such as ethylene glycol ethyl ether, ethylene glycol butyl ether or propylene glycol ethyl ether; aliphatic hydrocarbons such as n-hexane, cyclohexane, n-pentane, octane or heptane; aromatic hydrocarbons such as at least one of toluene, xylene, trimethylbenzene or water.
A method for preparing the antifouling paint comprises the following steps:
and (2) adding the base material into a solvent to dissolve at the temperature of between room temperature and 80 ℃, sequentially adding the antifouling agent, the pigment, the filler and the auxiliary agent, stirring at the rotating speed of 1500-5000 r/min, dispersing and grinding for 2-6 hours to obtain the antifouling paint.
The invention develops the nontoxic antifouling paint for marine ships and facilities by utilizing the characteristics that silver particles have no toxic or side effect on human bodies and other organisms, have broad-spectrum antibacterial property and are environment-friendly, effectively inhibits the adhesion corrosion of marine organisms, completely does not contain toxic agents such as DDT (DDT), organotin (TBT), cuprous oxide and the like, accords with the relevant regulations of the International Maritime Organization (IMO) and the future development trend of antifouling paint, and realizes the non-toxicity and greening of the marine antifouling technology.
Compared with the prior art, the invention has the following outstanding advantages:
1. the silver particles with the size of 1-200 nanometers are used for preparing the marine coating, have remarkable antifouling performance, have antifouling effect under low concentration and have high cost performance;
2. the antifouling paint has broad-spectrum antifouling effect on attached marine organisms;
3. the antifouling paint disclosed by the invention does not release toxic substances into seawater in the using process, and is green and environment-friendly;
4. the antifouling paint can be widely applied to facilities and fields of ships, floating docks, offshore oil platforms, submarine cables, cooling pipelines of offshore power plants, mariculture net cages and the like.
Detailed Description
The techniques and features of the present invention are further described below in conjunction with the following detailed description.
Example 1
The components are added into a multifunctional dispersion machine batching tank according to the following formula, the mixture is kept at 50 ℃, and stirring, dispersion and grinding are carried out for 4 hours at the rotating speed of 2000r/min, so as to prepare 1kg of a finished nontoxic marine antifouling paint product.
The weight of each component in the formula is respectively as follows:
(1) 500.00g of acrylic resin was added to the reaction mixture,
(2) 187.43g of zinc oxide, namely,
(3) 124.95g of iron oxide red (iron oxide red),
(4) 62.57g of talcum powder, 62.57g,
(5) 124.95g of xylene (a total of 124.95 g),
(6) 0.10g of silver particles was added,
the average particle diameter of the silver particles is 15 nm.
Example 2
(1) Mixing a water-soluble acrylic resin base material with water to obtain a water-soluble resin aqueous solution, and then adding an organic silicon coupling agent vinyl triethoxysilane and a dimethyl silicone oil auxiliary agent into the water-soluble resin aqueous solution;
(2) sequentially adding superfine silicon dioxide, titanium dioxide, zinc oxide, light magnesium oxide, sodium silicate and an antifouling agent into a multifunctional disperser batching tank at 55 ℃; stirring, dispersing and grinding at the rotating speed of 3500r/min for 2 hours to prepare 1kg of nontoxic marine antifouling paint.
The weight of each component in the formula is respectively as follows:
(1) 392.04g of a water-soluble acrylic resin,
(2) 417.00g of deionized water was added to the solution,
(3) 6.58g of vinyl triethoxysilane,
(4) 16.06g of dimethyl silicone oil,
(5) 22.94g of ultra-fine silicon dioxide,
(6) 13.28g of titanium dioxide was added,
(7) 45.96g of zinc oxide, namely,
(8) 32.70g of light-weight magnesium oxide,
(9) 52.44g of sodium silicate, 52.44g,
(10) the amount of silver particles was 1.00g,
the silver particles have an average particle size of about 1 nm.
Example 3
The components are added into a multifunctional dispersion machine batching tank according to the following formula, the mixture is kept at room temperature, and stirring, dispersion and grinding are carried out at the rotating speed of 1500r/min for 6 hours, so as to prepare 1kg of finished nontoxic marine antifouling paint.
The weight of each component in the formula is respectively as follows:
(1) 90.82g of coal tar pitch liquid,
(2) 208.58g of rosin, namely 208.58g,
(3) 159.68g of zinc oxide, namely,
(4) 211.58g of red mud,
(5) 93.81g of talcum powder, 93.81g,
(6) 233.53g of heavy benzene, namely 233.53g,
(7) the amount of silver particles was 2.00g,
the average particle diameter of the silver particles is 22 nm.
Example 4
The components are added into a multifunctional dispersion machine batching tank according to the following formula, the mixture is kept at 40 ℃, and stirring, dispersion and grinding are carried out for 3 hours at the rotating speed of 5000r/min, so as to obtain 1kg of a finished nontoxic marine antifouling paint product.
The weight of each component in the formula is respectively as follows:
(1) ethylene resin 149.25g
(2) 27.26g of tributyl phosphate,
(3) 113.76g of rosin, namely 113.76g,
(4) 3.28g of epoxy resin was added to the reaction mixture,
(5) 236.91g of red mud,
(6) 165.87g of zinc oxide, namely,
(7) 94.72g of talcum powder, 94.72g,
(8) 11.84g of organic argil,
(9) 85.57g of cyclohexanone is added into the mixture,
(10) 106.57g of trimethylbenzene, namely 106.57g,
(11) the amount of the silver particles was 4.97g,
the average particle diameter of the silver particles is 45 nm.
Example 5
The components are added into a multifunctional dispersion machine batching tank according to the following formula, the mixture is kept at 80 ℃, and stirring, dispersion and grinding are carried out for 2 hours at the rotating speed of 4000r/min, so as to prepare 1kg of a finished nontoxic marine antifouling paint product.
The weight of each component in the formula is respectively as follows:
(1) 99.58g of 35% chlorinated rubber solution,
(2) 28.96g of chlorinated paraffin is added,
(3) 34.77g of 50 percent alcohol acid ester,
(4) 104.32g of rosin, namely 104.32g,
(5) the red soil is 231.77g,
(6) 162.23g of zinc oxide, namely,
(7) 92.69g of talcum powder,
(8) 11.62g of organic argil,
(9) the content of the low-barium carbonate is 11.62g,
(10) 214.94g of xylene (a total of 214.94 g),
(11) the amount of the silver particles was 7.50g,
the average particle diameter of the silver particles is 64 nm.
Example 6
The components are added into a multifunctional disperser batching tank according to the following formula, the mixture is kept at 50 ℃, stirred, dispersed and ground for 4 hours at the rotating speed of 2500r/min, and the pH value is adjusted to 8 by sodium hydroxide. 1kg of nontoxic marine antifouling paint finished product is prepared.
The weight of each component in the formula is respectively as follows:
(1) 554.26g of silicone-acrylic emulsion,
(2) 27.74g of sodium hexametaphosphate,
(3) 269.50g of zinc oxide, namely,
(4) 13.77g of hydroxyethyl cellulose, and the like,
(5) 1.36g of tributyl phosphate,
(6) 2.82g of sodium benzoate, namely,
(7) 27.74g of ethylene glycol,
(8) 2.81g of propylene glycol,
(9) 100.00g of silver particles were used,
the average particle diameter of the silver particles was 78 nm.
Example 7
Dissolving acrylic resin in a mixed solvent, sequentially adding silver particles, a dispersing agent, a pigment, a filler and the like, keeping the temperature at 35 ℃, stirring, dispersing and grinding at the rotating speed of 3000r/min for 2.5 hours to prepare 1kg of a finished nontoxic marine antifouling paint product.
The weight of each component in the formula is respectively as follows:
(1) 435.86g of acrylic resin, 435.86g,
(2) 43.51g of talcum powder,
(3) 145.26g of zinc oxide, namely,
(4) 2.94g of phthalocyanine blue is added,
(5)Disper BYK 102 2.94g，
(6) 32.07g of organic bentonite, namely 32.07g,
(7) 226.84g of xylene (a total of 226.84 g),
(8) 72.58g of butyl acetate, and a total amount of butyl acetate,
(9) the amount of the silver particles was 38.00g,
the average particle diameter of the silver particles is 126 nm.
Example 8
Dissolving modified organic silicon in an organic solvent, sequentially adding assistants such as chlorinated paraffin, zinc oxide, dimethyl silicone oil, fluorocarbon surfactant and the like and silver particles, keeping at 65 ℃, stirring, dispersing and grinding at the rotating speed of 1800r/min for 3.5 hours to obtain the component A of the low-surface-energy nontoxic marine antifouling paint. And dissolving the low molecular weight polyamide in the mixed solvent at room temperature to prepare the component B of the antifouling paint. A, B the two components are mixed well before use.
The weight of each component in the formula is respectively as follows:
the component A comprises:
(1) 287.40g of modified organic silicon,
(2) 67.06g of chlorinated paraffin was added,
(3) 38.32g of zinc oxide was added to the solution,
(4) 2.50g of fluorocarbon surfactant is added,
(5) 3.25g of dimethyl silicone oil,
(5) 496.24g of a mixed solvent is added,
(6) the amount of the silver particles was 42.00g,
the component B comprises:
(1) 5.75g of low-molecular polyamide,
(2) 57.48g of the mixed solvent was added,
the mixed solvent is a mixture of toluene, xylene, n-butanol, isobutanol and isopropanol.
The average particle diameter of the silver particles is 200 nm.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the inventive concept, and it should be considered as within the scope of the present invention.

Claims (7)

1. A non-toxic antifouling paint for marine ships and facilities comprises a base material, an antifouling agent, a filler, a pigment, an auxiliary agent and a solvent, and is characterized in that the antifouling agent is silver particles with the average particle size of 1-200 nm, and the components in percentage by weight are as follows:
15 to 55 percent of base material,
0.01 to 10% of an antifouling agent,
10 to 30 percent of filler,
0.3 to 25 percent of pigment,
2 to 8 percent of auxiliary agent,
3-55% of a solvent.
2. The nontoxic antifouling paint of claim 1, wherein the binder is at least one of acrylic resin, vinyl chloride resin, vinyl acetate resin, chlorinated rubber, rosin, asphalt, polydivinyl acetylene resin, phenol resin, urea resin, melamine resin, polyurethane, epoxy resin, alkyd resin, silicone resin, organic fluorine resin, or alkali silicate.
3. The nontoxic and antifouling paint according to claim 2, wherein the filler is at least one of calcium carbonate, barium carbonate, silica, talc, graphite, zinc oxide, diatomaceous earth, glass microspheres, barite powder, bentonite, organo clay, china clay, laterite, zeolite powder or mica.
4. The non-toxic antifouling paint of claim 3, wherein the pigment is at least one of red iron oxide, yellow iron oxide, carbon black, titanium oxide, lithopone, magnesium oxide, iron blue, ultramarine, benzidine yellow, calcium phosphate, magnesium phosphate, or barium metaborate.
5. The nontoxic antifouling paint of claim 4, wherein the adjuvant is at least one of a dispersant, a defoamer, a leveling agent, a film forming adjuvant, a wetting agent, a plasticizer, a drier, a pH regulator, a preservative, or an anti-settling thixotropic thickener; wherein,
the dispersing agent is: sodium hexametaphosphate, sodium dodecyl benzene sulfonate, zinc stearate and lecithin;
the defoaming agent is: tributyl phosphate, dimethyl polysiloxane, polyether modified methyl polysiloxane and aluminum stearate;
the leveling agent is: polymethyl acrylate, polymethylphenylsiloxane, polyester-modified polydimethylsilane;
the film-forming auxiliary agent is as follows: alcohol ester dodeca, Texanol, ethylene glycol, petroleum ether, diisobutyl adipate;
the wetting agent is: vinyl triethoxysilane, vinyl triacetoxysilane, dimethicone;
the plasticizer is as follows: tributyl phosphate, dibutyl phthalate, epoxy linseed oil and castor oil;
the drier comprises the following components: cobalt naphthenate, manganese naphthenate, calcium isooctanoate, zirconium isooctanoate, cobalt diethyloleate;
the preservative is as follows: sodium benzoate, isothiazolinone, Benzisothiazolinone (BIT);
the pH regulator is as follows: ammonia water, sodium hydroxide aqueous solution, acetic acid;
the anti-settling thixotropic thickener comprises the following components: organic bentonite, aluminum octoate, calcium stearate, polyethylene wax and zinc ricinoleate.
6. A non-toxic antifouling paint according to claim 5, wherein the solvent is a ketone, in particular: acetone, cyclohexanone, butanone; esters, in particular: ethyl acetate, butyl acetate, benzyl acetate; alcohols, in particular: methanol, ethanol, isopropanol, isobutanol, ethylene glycol, propylene glycol; ethers, in particular: ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether; aliphatic hydrocarbons, in particular: n-hexane, cyclohexane, n-pentane, octane, heptane; aromatic hydrocarbons, in particular: at least one of toluene, xylene, trimethylbenzene or water.
7. A process for preparing a non-toxic antifouling paint for marine vessels and facilities according to claim 1, 2, 3, 4, 5 or 6, characterized in that it is carried out by the following steps:
and (2) adding the base material into a solvent to dissolve at the temperature of between room temperature and 80 ℃, sequentially adding the antifouling agent, the pigment, the filler and the auxiliary agent, stirring, dispersing and grinding at the rotating speed of 1500-5000 r/min for 2-6 hours to prepare the nontoxic antifouling paint.
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