CN103740163B - The antifouling preparation of bionic poisonless environmental friendliness - Google Patents
The antifouling preparation of bionic poisonless environmental friendliness Download PDFInfo
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- CN103740163B CN103740163B CN201310737051.8A CN201310737051A CN103740163B CN 103740163 B CN103740163 B CN 103740163B CN 201310737051 A CN201310737051 A CN 201310737051A CN 103740163 B CN103740163 B CN 103740163B
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Abstract
The invention discloses the antifouling preparation of a kind of bionic poisonless environmental friendliness, the described antifouling preparation of bionic poisonless environmental friendliness is mixed by least two kinds of mixed mixtures in compd A and compd B, C, D; The quality proportioning of compd A and mixture is A: mixture=1: 2 ~ 70; Described compd A is Weibull; Compd B is zinc curing carbamate; Compound C is diiodomethyl antihistamine sulfo group; Compound D is 2.4.6-Trichlorophenol maleinamide.Antifouling Formulation of the present invention is simple, easy to prepare, not containing organotin, nontoxic, pollution-free.
Description
Technical field
The present invention relates to a kind of antifouling preparation, particularly the antifouling preparation of a kind of bionic poisonless environmental friendliness, mainly with the antifouling paint used with preparation Offshore Units, boats and ships.
Background technology
The antifouling paint of maritime facilities and boats and ships use in the past, because containing a large amount of heavy metal organo-tin compounds, huge pollution is caused to the marine eco-environment, particularly organo-tin compound has been decided to be by world maritime environmental protection organization and has prohibitted the use product, because organo-tin compound result in a large amount of halobiontic death and the abnormal variation of property, cause the large-area minimizing of marine organisms, marine organisms population quantity is finally caused to decline so that extinction, since 20 beginnings of the century developed antifouling paint, substantially marine organisms attachment issue is solved, but, mostly be tool toxic product.20 century 70 later stages, along with various heavy metal compound is disabled, as mercury, arsenic etc. play the stain control agent of main anti-fouling effect, after removing comprehensively and forbidding, organo-tin compound " TBT " just becomes antifouling preparation representative at that time, and among the antifouling paint being widely used in boats and ships and maritime facilities.Find that containing organo-tin compound be main antifouling preparation the eighties in 20th century, remain fish and body of shellfish inner accumulated, cause the multiple pathology of marine organisms and inheritable variation, so various countries and world maritime environmental protection organization, start legislation, and require production and the use of the antifouling paint completely forbidden containing organo-tin compound.Current market still exists the antifouling paint product containing this compound, but it is fewer and feweri, the marine antifouling coating 80% ~ 95% used now all uses Red copper oxide as stain control agent, but because Red copper oxide wetting ability is relatively good, heavyly in ocean can gather, be discharged in water body, cause a large amount of marine alga dead, thus the damage and pollution eubiosis, Red copper oxide makes the desertification of pasture, seabed, so within very fast for some time, also will be all disabled.Therefore whole world various countries start to drop into huge fund to the antifouling preparation of the environment-friendly type researching and developing Novel pollution-free one after another, to meet the antifouling needs of world ocean facility and boats and ships.Marine organisms are in the attachment of maritime facilities and marine surface and growth, be called as marine biofouling, sea marine organism pollution brings great harm to boats and ships and maritime facilities, it increases the deadweight of hull and the friction resistance of ship's navigation on the one hand, ship's speed is slowed down, fuel consumption increases, but also hull and maritime facilities corrosion can be made to accelerate, shorten the normal service life of boats and ships and maritime facilities, make Multibeam distortion, various pipeline and the blocking of cultivation netting gear, add the harm power of offshore oil drilling platform, military installations and Military activity is made to receive great loss, according to incompletely statistics, worldwide because marine biofouling, the financial loss caused is very huge, direct economic loss is every year about nearly 500-800 hundred million dollars, boats and ships friction resistance more than 80% under sail comes from hull surface, and drag size depends on halobiontic stained situation, when marine biofouling rate is 5%, the running resistance of boats and ships, the 3-5 of navigation during boats and ships clean surface will be increased to doubly, fuel consumption increases by 30%, so prevent marine biofouling from having become one of major subjects of world's tackling of key scientific and technical problems research in this regard.
Summary of the invention
The object of this invention is to provide a kind of preparation simple, easy to prepare, not containing organotin, the antifouling preparation of nontoxic, free of contamination bionic poisonless environmental friendliness, for the antifouling paint preparing nontoxic, free of contamination Offshore Units, boats and ships use, overcome the deficiencies in the prior art.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, is mixed by least two kinds of mixed mixtures in compd A and compd B, C, D; The quality proportioning of compd A and mixture is A: mixture=1: 2 ~ 70;
Described compd A is Weibull;
Compd B is zinc curing carbamate;
Compound C is diiodomethyl antihistamine sulfo group;
Compound D is 2.4.6-Trichlorophenol maleinamide.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, wherein said compd A is 1: 2 ~ 50 with the mixture quality ratio of compd B, Compound C, and wherein the quality proportioning of compd B and Compound C is 1: 1 ~ 3.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, wherein said compd A is 1: 4 ~ 70 with the mixture quality ratio of compd B, Compound D, and wherein the quality proportioning of compd B and Compound D is 1: 3 ~ 6.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, wherein said compd A is 1: 2 ~ 40 with the mixture quality ratio of Compound C, Compound D, and wherein the quality proportioning of Compound C and Compound D is 1: 4 ~ 6.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, wherein said compd A is 1: 2 ~ 3 with the mixture quality ratio of compd B, Compound C, Compound D, and wherein the quality proportioning of compd B and Compound C, Compound D is 1: 4 ~ 6: 4 ~ 6.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, owing to containing compd A Weibull, as the first effective ingredient, it is the extract of sea, land symbiotic plant, can have an effect with multiple alkaloid and heavy metal ion and generate throw out.The chemical structure of Tannin compounds has the constitutional features of polyphenol, so it also has attribute and the effect of the sterilization of polyphenol antioxygen, Tannin compounds it and protein have very strong interaction, therefore under the environment having protein to exist, Tannin compounds can discharge from its immobilized state, and, all marine attaching organisms, active attachment phenomenon in any case, all relevant with protein synthesis, therefore, with the Tannin compounds that protein interaction is strong, the promotor as sterilization can prevent marine organisms from adhering to.
Zinc curing carbamate cpd, has preservative mechanism usefulness and the anti-virus agent effect of wide spectrum.
Diiodomethyl antihistamine sulfo-compounds, has very strong antifouling and anti-algae performance.
2.4.6-Trichlorophenol maleinamide compound is a kind of aquatic organism repellent.
In above-mentioned three kinds of compounds, the mixing of at least two kinds is as second effective ingredient of this antifouling preparation.
Antifouling Formulation of the present invention is simple, easy to prepare, not containing organotin, nontoxic, pollution-free.
Accompanying drawing explanation
Fig. 1 isolates the compound with antifouling effect from seaweed, analyzes its structure and activity, the schema of separation and purification;
Fig. 2 is the test schematic diagram of the bionic poisonless evil environmental friendliness antifouling paint utilizing antifouling Formulation of the present invention;
Fig. 3 is bionic poisonless evil environmental friendliness antifouling coating structural representation;
Fig. 4 is the development structure block diagram of the calculating design software based on the bionic poisonless environmental friendliness antifouling paint in Orthogonal Optimization Test design basis.
Wherein Fig. 3 indicates and utilizes fluorided-modified silicone resin as base-material, by on the siloxane main chain of line style with fluorine carbon side chain, fluorine carbon side chain is arranged by certain orientation relationship in film, makes film have higher elasticity, be unfavorable for that ocean can't harm the attachment of thing.
Embodiment
Tool present embodiment of the present invention can referring to Fig. 1,2,3,4.
The antifouling preparation of bionic poisonless environmental friendliness of the present invention, is mixed by least two kinds of mixed mixtures in compd A and compd B, C, D; The quality proportioning of compd A and mixture is A: mixture is 1: 2 or 4 or 10 or 20 or 30 or 40 or 50 or 60 or 70, namely between 1: 2 ~ 70.
Compd A is Weibull; Compd B is zinc curing carbamate; Compound C is diiodomethyl antihistamine sulfo group; Compound D is 2.4.6-Trichlorophenol maleinamide.
concrete mode one: the antifouling preparation of bionic poisonless environmental friendliness of the present invention, mixed by the mixture of compd A and compd B, Compound C, its quality proportioning is 1: 2 or 10 or 20 or 30 or 40 or 50, namely between 1: 2 ~ 50.Wherein the quality proportioning of compd B and Compound C is 1: 1 or 1.5 or 2 or 2.5 or 3, namely between 1: 1 ~ 3.
concrete mode two: the antifouling preparation of bionic poisonless environmental friendliness of the present invention, mixed by the mixture of compd A and compd B, Compound D, its quality proportioning is 1: 4 or 10 or 20 or 30 or 40 or 50 or 60 or 70, namely between 1: 4 ~ 70.Wherein the quality proportioning of compd B and Compound D is 1: 3 or 4 or 5 or 6, namely between 1: 3 ~ 6.
concrete mode three: the antifouling preparation of bionic poisonless environmental friendliness of the present invention, mixed by the mixture of compd A and Compound C, Compound D, its quality proportioning is 1: 2 or 10 or 15 or 20 or 25 or 30 or 35 or 40, namely between 1: 2 ~ 40.Wherein the quality proportioning of Compound C and Compound D is 1: 4 or 4.5 or 5 or 5.5 or 6, namely between 1: 4 ~ 6.
concrete mode four: the antifouling preparation of bionic poisonless environmental friendliness of the present invention, mixed by the mixture of compd A and compd B, Compound C, Compound D, its mass ratio is 1: 2 or 2.5 or 3, namely between 1: 2 ~ 3.Wherein the quality proportioning of compd B and Compound C, Compound D is 1: 4 or 4.5 or 5 or 5.5 or 6: 4 or 4.5 or 5 or 5.5 or 6.Namely between 1: 4 ~ 6: 4 ~ 6.
The structural formula of above-mentioned each compound is as follows:
Compd A---Weibull
Compd B---zinc dithio-carbamate
Compound C---diiodomethyl antihistamine sulfo group
Compound D---2.4.6-Trichlorophenol maleinamide
Utilize antifouling Formulation antifouling paint example of the present invention:
example 1:
Mix with Gum Rosin, chlorinated rubber resin, zinc oxide, iron oxide red, organic silica gel fat, talcum powder, dimethylbenzene, isobutyl ketone, butanols with the antifouling preparation that above-mentioned concrete mode one is prepared, prepare antifouling paint, after each composition accounts for mixing, the ratio of total mass is: antifouling preparation 20%, Gum Rosin 10%, chlorinated rubber resin 25%, zinc oxide 15%, iron oxide red 5%, organic silica gel fat 3%, talcum powder 3%, dimethylbenzene 10%, isobutyl ketone 5%, butanols 4%.
example 2:
Mix with zinc oxide, aromatic hydrocarbon ethylene modified resin, colcother, talcum powder, dimethylbenzene, isobutyl ketone with the antifouling preparation that above-mentioned concrete mode three is prepared, preparation antifouling paint, after each composition accounts for mixing, the ratio of total mass is: antifouling preparation 25%, zinc oxide 10%, aromatic hydrocarbon ethylene modified resin 30%, colcother 5%, talcum powder 5%, dimethylbenzene 10%, isobutyl ketone 15%.
example 3:
Mix with zinc oxide, epoxy modified resin, red iron oxide, talcum powder, wilkinite, dimethylbenzene, isobutyl ketone, butanols with the antifouling preparation that above-mentioned concrete mode two is prepared, preparation antifouling paint, after each composition accounts for mixing, the ratio of total mass is: antifouling preparation 25%, zinc oxide 10%, epoxy modified resin 30%, red iron oxide 5%, talcum powder 5%, wilkinite 3%, dimethylbenzene 10%, isobutyl ketone 10%, butanols 2%.
example 4:
Mix with the antifouling preparation that above-mentioned concrete mode four is prepared with ferrotitanium powder, fluorocarbon resin, zinc oxide, wilkinite, red iron oxide, anti-settling agent " 202P ", dimethylbenzene, isobutyl aldehyde radical ketone, prepare antifouling paint.After each composition accounts for mixing, the ratio of total mass is: antifouling preparation 30%, zinc oxide 5%, ferrotitanium powder 5%, fluorocarbon resin 31%, red iron oxide 5%, anti-settling agent 202P3%, wilkinite 2%, dimethylbenzene 10%, isobutyl ketone 9%.
According to above-mentioned example 1,2,3,4 mixing ratio, by the bionic poisonless antifouling paint that various composition hybrid modulation becomes, carry out the real extra large experiment test of link plate and the detection of real ship ocean, three kinds of antifouling paints are coated in respectively and carry out various technical parameter on brassboard and on real ship and compare, find out best group mode and scale-up factor with this, obtain the bionical antifouling paint of fitst water anti-fouling effect.
On the steel plate through sandblasting, first coat ship-used rust-proof coating, with hairbrush and spray gun on film after the drying, the test plate (panel) (150mm × 300mm) of 1-4 various antifouling paint combinations is implemented to brushing or the spraying of respective kind, again 1-4 kinds of test plate (panel)s are carried out brushing 2 times separately, make the build of bionic poisonless environmental friendliness antifouling paint be approximately 100 m.Then be put into by the test board carrying out coating in old iron mountain and sea gulf, the Chinese Bohai Sea, the depth of water is the marine immersion of reality 24 months of 2-3 meters.The test plate (panel) that bionic poisonless environmental friendliness antifouling paint build is about 100 m is made again by the same for the test plate (panel) of 1-4 kinds of antifouling paints, putting it to the marine site depth of water in Yellow Sea of China Changshan Island is 1.5 meters-2.5 meters immersions 24 months, and measure aquatic biological attachment area every month, and the % calculating the per-cent of the anti-fouling effect of each component by the calculation formula of antifouling efficacy theory leads, its calculation result is drawn by formula:
Anti-fouling effect (%)=(1
) × 100%
it is as shown in the table:
Can illustrate from the result shown in upper table, utilize the 1st effective constituent compd A and the 2nd effective constituent compd B in the present invention, C, the bionic poisonless environmental friendliness antifouling paint that in D, after at least two kinds of mixing, the antifouling preparation of mixing is modulated into, the brassboard of example 1-4 kinds of applying coatings done, detect, be immersed in the anti-fouling effect ratio of variant marine site after 18 months, still about 95% ~ 100% is remained on, soak most of antifouling area after 24 months and also maintain 90% ~ 95%, the anti-fouling effect that this stability is high, greatly improve the performance accurately and reliably of the antifouling preparation of bionic poisonless environmental friendliness of this time invention, the antifouling paint effect of modulating as effective constituent single compound used than ever and Red copper oxide usually used is more remarkable, meanwhile, with the antifouling preparation of bionic poisonless environmental friendliness of this invention, the antifouling paint made 1-4 components, be used in application on real ship to detect, particularly be used on the dredger in coastal waters, at 6 months, 12 months, 18 months, in the inspection of the capable operation of real Hainan Airlines in 24 months, anti-fouling effect is excellent, carrying out in the detection of reality sea, respectively to being used in No. 167, Bohai Sea fishing, No. 178 ships and No. 76, east area of the Liao River, coextensive with eastern and southern Liaoning Province Huanghai Sea fishing, No. 59 dredgers, its antifouling paint effect is very excellent, in 18 months, 4 fishing boat bond areas are all less than 0.3% ~ 0.5%, in 24 months, except fishing No. 56 ship bond areas in the east area of the Liao River, coextensive with eastern and southern Liaoning Province are except 0.8%, other ship is all less than 0.5%, its antifouling efficacy is checked to stablize by real ship.Anti-fouling effect majority all reaches more than 95%, and example detection is verified, this time the bionic poisonless environmentally friendly ship antifouling preparation technique advanced feature of invention is reliable.
The antifouling preparation of bionic poisonless environmentally friendly ship of the present invention, make bionic poisonless environmental friendliness antifouling paint by this antifouling preparation, and be coated in the structure surface of the various facility in underwater position and ocean of boats and ships, it can to soak for a long time and to prevent marine organisms as barnacle in the seawater, Ascidian, purple shellfish, sea freshwater mussel, polyzoan, oyster, green laver, the attachment that sea lettuce etc. are biological, and not Marine Pollution eco-activity in the environment, high anti-fouling effect can be given play to again, ocean environment is made to obtain protection effectively fully, the this time eco-friendly antifouling preparation of bionic poisonless of invention, antifouling efficiency is excellent, with this antifouling preparation, the bionic poisonless environmental friendliness antifouling paint be modulated into, in the inspection in real sea, anti-fouling effect is stablized, time length is long, can not work the mischief to the marine eco-environment again.The antifouling paint that the antifouling preparation of bionic poisonless environmental friendliness this time invented is modulated into, considerably beyond the anti-fouling effect of the antifouling paint in use in the past, and with this invention the antifouling preparation of bionic poisonless environmental friendliness, first and second kinds of antifouling effective constituents of compound that the antifouling paint be modulated into uses, to people and animals, fish and marine plant, all there is no toxic.So the antifouling preparation of bionic poisonless environmental friendliness invented with this; the bionic poisonless environmentally friendly ship antifouling paint be modulated into can be used safely; and can in the exploitation of the marine eco-environment and maritime facilities; give play to larger effect, made that the marine eco-environment is more friendly, marine organisms obtain more effective protection.
Claims (5)
1. the antifouling preparation of bionic poisonless environmental friendliness, is characterized in that:
The described antifouling preparation of bionic poisonless environmental friendliness is mixed by least two kinds of mixed mixtures in compd A and compd B, C, D; The quality proportioning of compd A and mixture is A: mixture=1: 2 ~ 70;
Described compd A is Weibull;
Compd B structural formula is as follows:
；
Compound C structural formula is as follows:
；
Compound D structural formula is as follows:
。
2. the antifouling preparation of bionic poisonless environmental friendliness according to claim 1, is characterized in that: described compd A is 1: 2 ~ 50 with the mixture quality ratio of compd B, Compound C, and wherein the quality proportioning of compd B and Compound C is 1: 1 ~ 3.
3. the antifouling preparation of bionic poisonless environmental friendliness according to claim 1, is characterized in that: described compd A is 1: 4 ~ 70 with the mixture quality ratio of compd B, Compound D, and wherein the quality proportioning of compd B and Compound D is 1: 3 ~ 6.
4. the antifouling preparation of bionic poisonless environmental friendliness according to claim 1, is characterized in that: described compd A is 1: 2 ~ 40 with the mixture quality ratio of Compound C, Compound D, and wherein the quality proportioning of Compound C and Compound D is 1: 4 ~ 6.
5. the antifouling preparation of bionic poisonless environmental friendliness according to claim 1, it is characterized in that: described compd A is 1: 2 ~ 3 with the mixture quality ratio of compd B, Compound C, Compound D, wherein the quality proportioning of compd B and Compound C, Compound D is 1: 4 ~ 6: 4 ~ 6.
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| 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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| CN1279132C (en) * | 2004-02-11 | 2006-10-11 | 国家海洋局天津海水淡化与综合利用研究所 | Environmental protection composite antifouling paint |
| ATE447931T1 (en) * | 2005-01-28 | 2009-11-15 | Procter & Gamble | DIIODOMETHYL-P-TOLYLSULFONE AS A PARTICLE DISPERSION IN A LIQUID SOLVENT |
| US20070258996A1 (en) * | 2005-12-23 | 2007-11-08 | The Sterilex Corporation | Antimicrobial compositions |
| EP2369928B1 (en) * | 2008-11-27 | 2016-06-22 | Janssen Pharmaceutica NV | Biocidal compositions comprising thiol group modulating enzyme inhibitors and pyrion compounds |
| CN102106347A (en) * | 2009-12-29 | 2011-06-29 | 江苏省农业科学院 | Cinnamaldehyde, eugenol, thymol and tannin compound bactericide |
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Effective date of registration: 20200813 Address after: 112611 new town, Tieling County, Liaoning, Tieling Patentee after: Liaoning Shenyi Special Coatings Co., Ltd Address before: Bajiazi village Wangtai furfural Co., Ltd., Shengli Economic Development Zone, Kangping County, Shenyang City, Liaoning Province Patentee before: Wang Junyu |