CN1238447C - Bionic poisonless anti-pollution paint for ship and its preducing method - Google Patents
Bionic poisonless anti-pollution paint for ship and its preducing method Download PDFInfo
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- CN1238447C CN1238447C CN 02132491 CN02132491A CN1238447C CN 1238447 C CN1238447 C CN 1238447C CN 02132491 CN02132491 CN 02132491 CN 02132491 A CN02132491 A CN 02132491A CN 1238447 C CN1238447 C CN 1238447C
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- fluoride
- alkaloid
- resin
- solvent
- butanols
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Abstract
The present invention relates to bionic poisonless anti-pollution paint for ships. The paint is prepared from fluororesin, modified fluororesin, alkaloid, a peptide compound, solvent, ionized water, a levelling agent, stuffing, pigment and an assistant. The modified fluororesin is formed by means that substituent fluoric thiofuran, polyfluoroethylene, a fluoric ethylene monomer and solvent which react under the action of an initiator. The alkaloid is extracted from seaweed in the sea, and the peptide compound is extracted from sponge organisms. The anti-pollution paint becomes a paint film on the bottom of the ship. Under the action of seawater, crosslinking density in the surface layer of the paint film is high, and bonding performance is reduced. Natural products, such as the alkaloid and peptide, are exuded to prevent marine organisms from being attached. The paint can be used for the surface treatment of submarine drilling platforms, submarine pipelines, valves and other facilities.
Description
Technical field:
The present invention relates to a kind of fluoro-containing coating, is a kind of fluorine-containing olefin copolymer and marine organism extract, and the antifouling paint that constitutes of solvent, auxiliary agent.
Background technology:
Because marine organisms one are the parasitism and the breeding of shell one bottom, naval vessel on the ocean especially, make the ship navigation burden increase, promptly influence its route speed and load to weight ratio.The parasitism that how to prevent these biologies has become important topic, through big quantity research, has found the coating made from the organic compound of tin, can effectively suppress and prevent the growth of these biologies.Through use for many years, because this class organic tin coating toxicity is bigger, seriously polluted to the marine eco-environment, influenced balance of nature to a certain extent, destroyed the living environment of some aquatic organisms, particularly the marine organisms with important ecology and economic worth have been constituted serious harm, other marine organisms have also been had chronic influence.In addition, enter food chain, final entail dangers to human beings'health by fish, shellfish etc.Along with the prolongation of duration of service of organotin coating, this potential environmental pollution is serious day by day along with the increase of marine ships.International Maritime Organizaton (IMO), Maritime Environment Protection Committee (MEPL) announce in the diplomatic conference of IMO in October calendar year 2001: all use the ship of stanniferous coating to forbid marine the operation after on January 2nd, 2003.
Arrival along with the date that begins to forbid organotin coating, each state has all set about studying the substitute of organotin, in recent years, developed country is bringing into use nontoxic antifouling paint, as using on 3000 ships from the ECOLOFLEN of polishing technology RANGE OFTBT-FREE SYSTEM with vinylformic acid copper of IP company and Japanese NPMC company's cooperative development.Wherein the trade mark is that INTERSMOOTH360 also uses at naval vessels.The Seavictor50 of You Dun company is adopted by silent service, HEMPEL company simultaneously, JOTUN company, SIGMA company also successively introduce the nontoxic antifouling paint of oneself to the market, very fast U.S. army just has 70 warships and over one hundred merchant ship to adopt this antifouling varnish, and its anti-fouling effect can reach more than 3 years.
China National Bureau of Oceanography also classifies developmental research non-toxic anticorrosion technology as the emphasis schedule in the new millennium agenda of formulating.
Citing document:
(1) Zhou Chenliang China coating 1998 № 6
(2)Todd.J T，Zimmerman R C Crews P，et al.
The anti-fouling activity of natural and synthetic phenolic acidsulphate eaters.
Phytochemistry，1993，34(2)：401-404
(3)Chem week，1973，112(18)，32 JP03-239766
Summary of the invention:
The purpose of this invention is to provide a kind of with natural biological effective extract and high molecular polymer be combined into, hull is had strong bonding force, can prevent sea-water corrosion the parasite that marine organisms are adhered to have the toxicological harmless of stronger resistance ability, free of contamination coating again.
Data show that the adhesion strength on fluoropolymer surface can reduce to 25mj/m under seawater eroding
2Below, even it is lower, if, then have more stronger anti-adhesive in that to be equipped with natural biological activator crosslinked.Bioadhesion power is 23-25mj/m under critical surface tension
2Polymkeric substance on minimum.Yet unusual is, halobionticly is stained with different selections, and for example barnacle is 30-35mj/m to free energy
2The easiest adhesion in surface, polyzoan is 15-30mj/m to free energy then
2Surface adhesion the strongest.Therefore, separate out fluorinated surfactant, from water medium at air to the liquid surface independent assortment.When losing solvent and heating, the tensio-active agent polymerization forms covalently cross-linked structure and loses electric charge.Because the cross-linking density height in the deep layer, orientation Rf base is tightly fixed, so infiltration that often can the anti-adhesive molecule can prevent the molecular transposition that bur causes again.During biological attachment, can biology and paint film be repelled mutually, if surface energy is lower than 3 * 10 by means of suitable coating surface free energy
-4N/cm
2, then glycoprotein in the seawater and polysaccharose substance just can not be adsorbed on this surface.Like this, bacterium, marine organisms can not adhere to.Fluorochemical is the low-surface-energy material that is in daily use.Simultaneously fluoropolymer chemical resistance, corrosion-resistant, ageing-resistant better performances are to be used for the comparatively superior veriety of coating at present, and be also very favourable for the protection of naval vessel base material.
The solution of the present invention is the antifouling paint of making in two steps: at first be preparation modified fluoride-containing resin, then use fluorine resin, the natural goods of the alkaloid of extraction and peptide class, auxiliary agent, solvent and make coating.
One. producing of modified fluoride-containing resin.Main raw material is a 4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide, contains fluoroethylene polymer, contains fluoride monomers and solvent reaction forms.Its raw materials used proportioning (W%) is:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8-20
Contain fluoroethylene polymer 20-53
Contain fluoride monomers 15-25
Solvent 17-35
Wherein containing fluoroethylene polymer is fluorinated ethylene propylene, poly-just, inclined to one side two or trifluoro-ethylene, two kinds and two or more combination in voltalef, the tetrafluoroethylene; Containing fluoride monomers is a vinyl fluoride, just or inclined to one side two, trifluoro-ethylene, and trifluorochloroethylene, a kind of and more than one combinations in the tetrafluoroethylene; Solvent is butanols and butanone, and its proportioning is that butanols accounts for 64.0-70.0%.
Initiator-the organo-peroxide or the azo-compound that also need add in addition, above-mentioned total amount 2-6%.
The preparation technology of modified fluoride-containing resin is: heating is being housed, the butanol solution that adds fluoride monomers in the reactor of reflux successively, be heated into liquid voltalef and initiator, stir 210-240 ℃ of heating down, drop into the raw material except that tetrafluoroethylene more successively, tetrafluoroethylene and propyl carbinol, under this temperature, keep 0.5-3h then, be cooled to 180-200 ℃ and add butanone, in 180-230 ℃ of back flow reaction stopped reaction when acid number is 13.0-14.0mgKOH/g, cooling, adding ionized water adjusts viscosity (being coated with-4 glasss, 25 ℃) and reaches 220-420.Reinforced, reaction adopts airtight band to compress into row.The modified resin that obtains is a yellow tawny transparent liquid, and solid part is 55 ± 2%.
The present invention's modified fluoride-containing resin manufacture in experiment adopts following two kinds of prescription effects also better.
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8.0-20.0% 8.0-20.0%
Poly-just or inclined to one side two, trifluoro-ethylene, 10.0-20.0%
Fluorinated ethylene propylene 6.0-15.0%
Voltalef 0.5-2.0% 15.0-37.0%
Tetrafluoroethylene 5.0-15.0% 5.0-15.0%
Fluoride monomers 12.0-25.0% 12.0-25.0%
Solvent 17.0-35.0% 17.0-35.0%
Two. the preparation of coating.Used fluoro-resin, modified fluoride-containing resin, natural alkaloid, peptide and auxiliary agent etc. are made, and raw material variety and proportioning (w%) are:
Fluoro-resin PC level 25-35
Contain fluorine modified resin 13-23
Natural alkaloid 10-20
Peptide compounds 1-5
Solvent 10-25
Ionized water 2-8
Flow agent 1-5
Filler, pigment and auxiliary agent 5-15
Above-mentioned natural alkaloid is an ocean marine alga-get 130-150 ℃ of extraction as sea tangle-water; Peptide compounds is to extract and make from 180 ℃ of hydrolysis of ocean Sponge water; Solvent is a butanols.
In the formulating process of coating, better with following prescription effect:
Fluoro-resin PC level 28-33%
Modified fluoride-containing resin 15-20%
Alkaloid 15-20%
Peptides 1-3%
Butanols 15-20%
Ionized water 4%
Flow agent 3%
Filler, pigment and auxiliary agent 8-12%
The linking agent that when using coating, also need add above total amount 1-6%.
Its method for making for fluoro-resin, contain fluorine modified resin and other raw material forms coating in grinding machine for grinding.Dope viscosity (Pa.s), rotational viscosimeter method are 1.5-1.6.
Antifouling mechanism of the present invention is: the anti-pollution function of ship bottom antifouling paint is that the characteristic by paint film reaches, under the effect of seawater, make the cross-linking density height in the paint film top layer, adhesion property reduces, alkaloid and peptides natural compound are oozed out, reach the purpose that prevents that marine organisms from adhering to, and marine plant and shellfish are not had influence.No matter being experiment or practical probation, this coating of the present invention proving all and prevents marine organisms that particularly the adhering to of shellfish biology, parasitism are highly effective.Not only use at the underwater portion of ship, and in the ocean drilling platform, pipeline, cut down on door and the facility and use, all obtain the good antifouling effect.
The present invention is-kind of bionical nontoxic anti-fouling ship paint, mainly is to prevent or limit other material adhesive capacity with the fluoropolymer characteristic, and the active substance composition of cooperation extracted form natural plant-kind of novel antifouling coating.Comparing with existing antifouling paint, do not have toxic substance, is that the natural product with bionical thing prevents that with organic the combination pollutent from adhering to.Be a kind ofly can weaken and even eliminate fully stained property marine organisms and adhere to coating, simultaneously by by means of less mechanical force (as the weight of dirt settling itself) or boats and ships the shearing force when navigating by water remove and adhere to stained property biology.Prevent that not only marine organisms are strong, effective to the ability of adhering to of boats and ships, avoid simultaneously because of using poisonous antifouling paint to cause gathering of Toxic to pollution of the sea with to the mankind's harm.
Embodiment:
The preparation of example 1 marine antifouling ship-bottom paint
(1) preparation of modified fluoride-containing resin, raw material and consumption (Kg):
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 14
Poly(vinylidene fluoride) 14
Fluorinated ethylene propylene 12
Voltalef 1
Tetrafluoroethylene 10
Vinyl fluoride 18
Propyl carbinol 20
Acetone 11
The preparation method is: vinyl fluoride is dissolved in the 10Kg butanols adds reactor.Then just the heating back becomes aqueous voltalef and 3g benzoyl peroxide to add, and is heated with stirring to 240 ℃, then slowly the raw material outside the tetrafluoroethylene is added, and adds tetrafluoroethylene and residue butanols at last, at 220-240 ℃ of reaction 1h.Be cooled to below 200 ℃ and add butanone, react under 180-230 ℃ and reach 13mgKOH/g to acid number and end, cooling adds ionized water and is diluted to viscosity (being coated with-4 glasss 25 ℃) and ends for 220-320s.The confining zone press operation is all adopted in reinforced and reaction.
(2) preparation of coating: raw materials used and consumption (Kg) is:
Fluoro-resin PC level 30
Modified fluorin resin 18
Alkaloid 15
Peptides 2
Butanols 18
Ionized water 4
Flow agent 3
Acid calcium 10
Described PC level fluoro-resin is for being to sell product, and alkaloid is that marine alga (sea tangle) adds 130 ℃ of extracts of water, and peptides is that cavernous body forms 180 ℃ of hydrolysis.Its preparation technology is in the taper grinding machine for grinding and be uniformly dispersed.Its viscosity (Pa.s) is measured as 1.5-1.6 with rotational viscosimeter.
(3) performance test.Be painted on the standard test piece with 50g coating, making and doing the back film thickness is 150-200 μ m, behind the actual drying, by the relevant performance of relevant ship bottom anti-fouling paint standard testing, and comprises that real extra large detected result is:
| Test event | Testing standard | The result |
| Paint film adhesion (level) | GB1720-86 | 2 |
| Paint film flexibility (mm) | GB1731-93 | 2 |
| Surface drying time (h) | GB1728-79 | ∠5 |
| Do solid work the time (h) | GB1728-79 | ∠24 |
| Film consumption degree (second) | 0.14 | |
| Marine life adheres to | Do not have |
The preparation of example 2 ship bottom antifouling paints
(1) modified fluoride-containing resins.Raw material and consumption (hg) are:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 18
Poly-inclined to one side trifluoro-ethylene 12
Fluorinated ethylene propylene 8
Voltalef 0.8
Tetrafluoroethylene 8.2
Fluoride monomers 20
Butanols 23
Butanone 10
Method for making is with example 1
(2) preparation of coating.Raw material consumption (kg) is:
Fluoro-resin PC level 25
Modified fluorin resin 23
Alkaloid 14
Peptides 4
Butanols 15
Ionized water 7
Flow agent 4
Filler (natural ore powder, lime carbonate) 8
Method for making such as example 1.
The manufacturing of coating of example 3 offshore drill raised platforms around a well and underwater pipeline, equipment.
(1) manufacturing of modified fluorin resin.Raw material and consumption (kg) are:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 10
Poly(vinylidene fluoride) 18
Fluorinated ethylene propylene 10.5
Voltalef 0.5
Tetrafluoroethylene 12
Fluoride monomers 16
Butanols 22
Butanone 11
Method for making such as example 1.Product outward appearance yellow transparent liquid is coated with-4 glasss of (25 ℃) viscosity 230-280s, solid part 54 ± 2%.
(2) coating manufacturing such as example 1.
Antifouling paint is made under example 4 seawater
The preparation of modified fluorin resin.Raw material and consumption (kg) are:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 12
Voltalef 27
Tetrafluoroethylene 7
Trifluorochloroethylene monomer 23
Solvent butanols 21
Butanone 10
Its preparation technology such as example 1 adopt withstand voltage reactor capping.Coating is made as example 1.
Claims (5)
1. bionic poisonless ship pollution prevention coating, it is characterized in that: be made up of fluoro-resin, modified fluoride-containing resin, alkaloid, peptides, solvent, filler, pigment and auxiliary agent, be Huang-tawny transparent liquid, viscosity Pa.s is 1.5-1.6; Contained component and weight percent thereof consist of:
Fluoro-resin 25-35%
Modified fluoride-containing resin 13-23%
Alkaloid 10-20%
Peptides 1-5%
Butanols 10-25%
Ionized water 2-8%
Flow agent 1-5%
Filler, pigment and auxiliary agent 5-15%
Described modified fluoride-containing resin is by 4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide, contain fluoroethylene polymer, contain fluoride monomers, solvent, reaction in the presence of initiator and making, and it is raw materials used to be following weight percent proportioning:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8.0-20.0
Contain fluoroethylene polymer 20.0-53.0
Contain fluoride monomers 12-25
Solvent 17-35
And the initiator of above-mentioned raw materials total amount 2-6%; Described alkaloid is the marine algae water extract, and described peptides is that the Sponge hydrolysis gets.
2. bionic poisonless ship pollution prevention coating according to claim 1, it is characterized in that: contained component and weight percent thereof consist of:
Fluoro-resin PC level 28-33%
Modified fluoride-containing resin 15-20%
Alkaloid 15-20%
Peptides 1-3%
Butanols 15-20%
Ionized water 4%
Flow agent 3%
Filler, pigment and auxiliary agent 8-12%
Described alkaloid is the sea tangle water extract.
3. the method for making of a bionic poisonless ship pollution prevention coating is characterized in that: with following raw material and weight percent proportioning thereof, thorough mixing disperses to form in shredder:
Fluoro-resin 25-35%
Modified fluoride-containing resin 13-23%
Alkaloid 10-20%
Peptides 1-5%
Butanols 10-25%
Ionized water 2-8%
Flow agent 1-5%
Filler, pigment and auxiliary agent 5-15%
Described modified fluoride-containing resin is to form with following raw material and the reaction of weight percent proportioning thereof:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8.0-20.0
Contain fluoroethylene polymer 20.0-53.0
Contain fluoride monomers 12-25
Solvent 17-35
Wherein containing fluoroethylene polymer is fluorinated ethylene propylene, poly-just, inclined to one side two or trifluoro-ethylene, two kinds and two or more combination in voltalef, the tetrafluoroethylene; Containing fluoride monomers is a vinyl fluoride, just or inclined to one side two, trifluoro-ethylene, and trifluorochloroethylene, a kind of and more than one combinations in the tetrafluoroethylene; Described solvent is two kinds of butanols, butanone; The initiator that also need add above total amount 2-6% in addition is organo-peroxide or azo-compound; Its manufacturing process is: add the solution of being made by fluoride monomers and part butanols in the reactor successively, be heated into the trifluorochloroethylene polymkeric substance and the initiator of liquid, stirring also is warming up to 210-240 ℃, add the raw material except that tetrafluoroethylene more successively, the butanols of tetrafluoroethylene and residual content, and under this temperature, keep 0.5-3.0h, be cooled to 180-200 ℃ and add butanone, the stopped reaction during at 13.0-14.0mgKOH/g in 180-230 ℃ of back flow reaction to the reactant acid number, cooling, add ionized water, the one 4 glasss of sticking shelfs (25 ℃) that are coated with of adjusting material are 220-420s, modified resin is a yellow tawny transparent liquid, and solid part is 55 ± 2%; Reinforced and reaction adopts airtight band to compress into row.
4. according to the method for making of the described bionic poisonless ship pollution prevention of claim 3 coating, it is characterized in that coating is made raw materials used and the weight percent proportioning is:
Fluoro-resin PC level 28-33%
Modified fluoride-containing resin 15-20%
Alkaloid 15-20%
Peptides 1-3%
Butanols 15-20%
Ionized water 4%
Flow agent 3%
Filler, pigment and auxiliary agent 8-12%
The raw materials used weight percent proportioning of the manufacturing of required modified fluoride-containing resin is:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8.0-20%
Poly-just or inclined to one side two, trifluoro-ethylene 10.0-20.0%
Fluorinated ethylene propylene 6.0-15.0%
Voltalef 0.5-2.0%
Tetrafluoroethylene 5.0-15.0%
Fluoride monomers 12.0-25.0%
Solvent 17.0-35.0%
5. the method for making of bionic poisonless ship pollution prevention coating according to claim 3 is characterized in that raw materials used and weight percent proportioning is in the described modified fluoride-containing resin:
4-tert-butyl-phenyl tetrafluoro thiophene oxyhydroxide 8.0-20.0%
Voltalef 15.0-37.0%
Tetrafluoroethylene 5.0-15.0%
Trifluorochloroethylene monomer 12.0-25.0%
Solvent 17.0-35.0%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132491 CN1238447C (en) | 2002-06-28 | 2002-06-28 | Bionic poisonless anti-pollution paint for ship and its preducing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132491 CN1238447C (en) | 2002-06-28 | 2002-06-28 | Bionic poisonless anti-pollution paint for ship and its preducing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392208A CN1392208A (en) | 2003-01-22 |
| CN1238447C true CN1238447C (en) | 2006-01-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02132491 Expired - Lifetime CN1238447C (en) | 2002-06-28 | 2002-06-28 | Bionic poisonless anti-pollution paint for ship and its preducing method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7311766B2 (en) * | 2005-03-11 | 2007-12-25 | I-Tech Ab | Method and use of nanoparticles to bind biocides in paints |
| CN102702910A (en) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | Freshwater domain corresponding type anti-fouling paint composition and coating and antifouling method thereof |
| CN103694754B (en) * | 2013-12-12 | 2016-01-13 | 青岛海洋新材料科技有限公司 | A kind of Bionic Marine Antifouling Coatings |
| CN115353789A (en) * | 2022-08-24 | 2022-11-18 | 广西瑞朗生物科技有限公司 | Bionic non-toxic marine antifouling paint and preparation method thereof |
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2002
- 2002-06-28 CN CN 02132491 patent/CN1238447C/en not_active Expired - Lifetime
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Effective date of registration: 20200901 Address after: 112611 new town, Tieling County, Liaoning, Tieling Patentee after: Liaoning Shenyi Special Coatings Co.,Ltd. Address before: 508 room 116031, block A, Dr. Pioneer Park, Dalian hi tech park, Liaoning Patentee before: Wang Junyu |
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Granted publication date: 20060125 |