CN102807797A - Efficient marine antifouling coating and broad-spectrum controlled-release antifouling agent for same - Google Patents
Efficient marine antifouling coating and broad-spectrum controlled-release antifouling agent for same Download PDFInfo
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- CN102807797A CN102807797A CN2012101618055A CN201210161805A CN102807797A CN 102807797 A CN102807797 A CN 102807797A CN 2012101618055 A CN2012101618055 A CN 2012101618055A CN 201210161805 A CN201210161805 A CN 201210161805A CN 102807797 A CN102807797 A CN 102807797A
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 83
- 238000013270 controlled release Methods 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title abstract description 19
- 238000000576 coating method Methods 0.000 title abstract description 19
- 239000002519 antifouling agent Substances 0.000 title abstract description 9
- 239000000284 extract Substances 0.000 claims abstract description 55
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003094 microcapsule Substances 0.000 claims abstract description 19
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 11
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 89
- 241000196251 Ulva arasakii Species 0.000 claims description 75
- 239000003973 paint Substances 0.000 claims description 63
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 34
- 229920001661 Chitosan Polymers 0.000 claims description 33
- 238000001228 spectrum Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- 238000009775 high-speed stirring Methods 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 4
- 229940112669 cuprous oxide Drugs 0.000 abstract description 4
- 241000894007 species Species 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 229920000178 Acrylic resin Polymers 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 241000196259 Ulva pertusa Species 0.000 abstract 1
- 239000000440 bentonite Substances 0.000 abstract 1
- 229910000278 bentonite Inorganic materials 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 10
- 230000003245 working effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 241000196252 Ulva Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 235000015170 shellfish Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 206010058314 Dysplasia Diseases 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
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- 238000009313 farming Methods 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009422 growth inhibiting effect Effects 0.000 description 1
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- 239000004922 lacquer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000002966 varnish Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to an efficient marine antifouling coating and a broad-spectrum controlled-release antifouling agent for the same. The efficient marine antifouling coating comprises the following components in parts by weight: 20 to 25 parts of broad-spectrum controlled-release antifouling agent, 1 to 5 parts of auxiliary antifouling agent, 17 to 23 parts of acrylic resin, 13 to 17 parts of rosin, 2 to 4 parts of iron oxide, 6 to 10 parts of zinc oxide, 2 to 5 parts of talc powder, 1 to 3 parts of bentonite and 20 to 24 parts of xylene. Cuprous oxide and an Ulva pertusa Kjellm extract are mixed to prepare the broad-spectrum controlled-release antifouling agent by a microencapsulation preparation process, and the release rate of the broad-spectrum controlled-release antifouling agent existing in a microcapsule form can be effectively controlled. The efficient marine antifouling coating provided by the invention has the effects of small amount of cuprous oxide, wide range of inhibition of marine species and long service time, and the broad-spectrum controlled-release antifouling agent solves the problems that the cuprous oxide antifouling agent is easily coagulated and precipitated in the storage process of the antifouling coating.
Description
Technical field
The present invention relates to a kind of antifouling paint and antifouling paint and use stain control agent; Be specifically related to the efficient antifouling paint of efficient antifouling paint in a kind of ocean and ocean with wide spectrum controlled release stain control agent; The efficient antifouling paint in this ocean is to be applied to use to prevent that marine fouling organism from adhering to influence on boats and ships and other ocean structures, and the efficient antifouling paint in ocean is a kind of stain control agent of preparation marine antifouling coating with wide spectrum controlled release stain control agent.
Background technology
Boats and ships sail in a mighty ocean the important difficult problem that runs into be exactly sea life to hull bottom adhere to and stained, marine fouling organism is attached to hull bottom, can increase running resistance, reduces ship's speed, consume fuel more; Be attached to the sea farming netting gear, the mesh that can result in blockage, reduction exchange of seawater efficient can cause culturing fish and shellfish dysplasia even death; Be attached on the oceanographic instrumentation, can cause instrument signal distortion, degradation; Be attached to torpedo, gain in weight and running resistance, cause the unbalance inefficacy of torpedo, thereby cause heavy losses.The application antifouling paint is to solve stained problem not only economy but also important channel efficiently.It is to be used in compensation because antifouling paint lost efficacy and to cause in the deceleration that a very big expense is arranged again every year, and, antifouling paint antirust for application again also will spend a large amount of expenses.Therefore developing antifouling paint efficiently, is an important problem.
Antifouling paint is general main to be made up of compositions such as base-material, stain control agent, subsidiary material, color stuffing and solvents.Rely on progressively being discharged into of stain control agent to suppress in the seawater and stops biology adhering to and grow on ocean structures such as boats and ships, thereby reach antifouling purpose.Used in the past main stain control agent is the stain control agent of poison material such as stanniferous, mercury and lead, utilizes its toxicity to drive away marine fouling organism.Tributyl tin compound TBT that is added and DDT class poison material content reach 1ppm and can cause the shellfish teratogenesis, and can get into human body through the food chain transmission, and is unhealthful.Therefore, International Maritime Organizaton passed a resolution in calendar year 2001: on January 1st, 2008, and forbidding organotin antifouling paint on all boats and ships of the whole world." China Ocean Agenda 21 " that China National Bureau of Oceanography formulates also clearly proposes to develop pollution-free ocean anticorrosion and antifouling technology.At present antifouling paint uses Red copper oxide to be stain control agent in a large number because Red copper oxide is stronger with wetting ability than great, in the antifouling paint storage process Red copper oxide be prone to condense, deposited phenomenon, bring many disadvantageous effects to antifouling property.Problems such as the work-ing life that at present stain control agent exists that biological species suppresses that scope is less in addition, stain control agent rate of release instability etc. makes antifouling paint is impermanent.
One " a kind of silicate compound anti-fouling paint " by name; Notification number is CN 1101841C; The day for announcing is that the Chinese invention patent of 2003.02.19 discloses a kind of ocean and uses antifouling paint; Be used to prevent that sea life from adhering on the surface of boats and ships, maritime facilities etc.; This coating is to be equipped with poison material (6 ~ 40 weight part) such as organotin, Red copper oxide, copper sulfate with silicate antifoulant (20 ~ 60 weight part) as compound stain control agent, adds components such as film-forming resin (20 ~ 50 weight part), dispersion agent, anti-heavy agent and an amount of solvent and forms.The antifouling paint of this invention is unprocessed with Red copper oxide, can not improve that Red copper oxide is prone to condense in the antifouling paint storage process, the problem of deposited phenomenon.
Summary of the invention
An object of the present invention is to solve marine life kind that present antifouling paint exists and suppress that scope is little, the stain control agent rate of release unstable, antifouling paint short problem in work-ing life, provide a kind of ocean efficient antifouling paint.
Another object of the present invention is to solve that the Red copper oxide stain control agent is prone to condense in the antifouling paint storage process, deposited phenomenon, brings the problem of many disadvantageous effects to antifouling property, and the efficient antifouling paint in a kind of ocean is with wide spectrum controlled release stain control agent.
In order to solve the problems of the technologies described above, the present invention realizes through following technical scheme:
The efficient antifouling paint in a kind of ocean, it is composed of the following components to count the efficient antifouling paint in said ocean by weight: 20 ~ 25 parts of wide spectrum controlled release stain control agents, 17 ~ 23 parts of vinyl resins; 13 ~ 17 parts of rosin; 2 ~ 4 parts of red stone, 6 ~ 10 parts in zinc oxide, 2 ~ 5 parts of talcum powder; 1 ~ 3 part of wilkinite, 20 ~ 24 parts of YLENE.
Thereby wide spectrum controlled release stain control agent is a kind of stain control agent rate of release of can controlling prolongs the antifouling paint stain control agent in work-ing life, and vinyl resin is as base-material, and YLENE is as solvent, and red stone is a rust-preventive agent, and talcum powder, wilkinite, YLENE are filler.
As preferably, said wide spectrum controlled release stain control agent is prepared from through microcapsule preparation technology after mix Red copper oxide and hole sea lettuce extract, specifically may further comprise the steps:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, the mass percent of Red copper oxide is 60 ~ 80%, and the mass percent of hole sea lettuce extract is 20 ~ 40%; Vacuum oil is mixed according to the volume ratio of 1:3～4.5 with Yellow Protopet 2A, obtain mixing oil phase;
Red copper oxide and hole sea lettuce extract be jointly as stain control agent, vacuum oil and Yellow Protopet 2A as the wall material in order to generate microcapsule.
(2) be that 4～6:1 is dissolved in chitosan in 2 ~ 5% the acetum filtered through gauze according to the mass ratio of chitosan and acetic acid; Is that 1:3～6 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan; Be that 1 ~ 3:1 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
Chitosan as wall material microcapsule wall material is not soluble in water, under the effect of acetic acid, can quicken the dissolving of chitosan, and filtered through gauze is fallen impurity, then with mix oil phase co-production latex solution.
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:2～8 add LUTARALDEHYDE in the stain control agent base-material that step 2 obtains, and is warming up to 40 ~ 45 ℃ then, and reaction 1 ~ 1.5h obtains reaction solution;
LUTARALDEHYDE is cured the mixed solution in the stain control agent base-material as solidifying agent.Thereby chitosan is coated cuprous oxide particle, form microcapsule particle, the add-on of LUTARALDEHYDE has certain influence to the particle diameter of microcapsule particle, and it is excessive that adding too much can cause microcapsule particle to be gone through.
The pH value of the reaction solution that (4) step 3 is obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h filters, and obtains thick product;
Regulate pH and can accelerate chitosan separating out in solution, quicken the formation of microcapsule, the size of pH exerts an influence to the size of microcapsule particle simultaneously,
(5) the thick product that step 4 is obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and 50 ~ 60 ℃ of following vacuum-dryings get antifouling paint with wide spectrum controlled release stain control agent.
As preferably; Hole sea lettuce extract is prepared from following steps: get fresh hole sea lettuce and in 30 ~ 50 ℃ of air dry ovens, dry, be crushed to 200 ~ 300 orders then, extract 5 ~ 10h with the ethanol of volume(tric)fraction 40 ~ 95% 50 ~ 90 ℃ of temperature refluxed; The mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3; Then suction filtration obtains hole sea lettuce extracting solution, and hole sea lettuce extracting solution is distilled 2 ~ 3h under 70 ~ 80 ℃ of temperature, obtains hole sea lettuce paste extract; At last hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, promptly get hole sea lettuce extract.
As preferably; The efficient antifouling paint in said ocean is prepared from following steps: vinyl resin and rosin are dissolved in the YLENE; Add wide spectrum controlled release stain control agent, red stone, zinc oxide, talcum powder and wilkinite then successively; High-speed stirring then, high-speed stirring once more after the grinding obtains the efficient antifouling paint in ocean.
The efficient antifouling paint in a kind of ocean is with wide spectrum controlled release stain control agent, and said wide spectrum controlled release stain control agent is prepared from through microcapsule preparation technology after mix Red copper oxide and hole sea lettuce extract, specifically may further comprise the steps:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, the mass percent of Red copper oxide is 60 ~ 80%, and the mass percent of hole sea lettuce extract is 20 ~ 40%; Vacuum oil is mixed according to the volume ratio of 1:3～4.5 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 4～6:1 is dissolved in chitosan in 2 ~ 5% the acetum filtered through gauze according to the mass ratio of chitosan and acetic acid; Is that 1:3～6 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan; Be that 1 ~ 3:1 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:2～8 add LUTARALDEHYDE in the stain control agent base-material that step 2 obtains, and is warming up to 40 ~ 45 ℃ then, and reaction 1 ~ 1.5h obtains reaction solution;
The pH value of the reaction solution that (4) step 3 is obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h filters, and obtains thick product;
(5) the thick product that step 4 is obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and 50 ~ 60 ℃ of following vacuum-dryings get the efficient antifouling paint in ocean with wide spectrum controlled release stain control agent.
Red copper oxide is the copper class stain control agent of using always, but in antifouling paint, exist to be prone to condense, sedimentary defective.Hole sea lettuce extract has stronger growth-inhibiting effect to diatom and mussel etc., and it is better to suppress effect.Microcapsulary is that micro substance is wrapped in the technology in the polymeric film, is the microdisplay package technology of a kind of store solids, liquids and gases.Can effectively control the release of encapsulated material through microcapsulary.Microcapsule preparation technology of the present invention coats the mixture of Red copper oxide and hole sea lettuce extract to be prepared into microcapsule with chitosan; Come the cuprous rate of release with hole sea lettuce extract of controlled oxidation through microcapsule; Thereby prolong the useful life of stain control agent; And then the work-ing life of improving antifouling paint, also reduced the addition of Red copper oxide on the other hand.Simultaneously, Red copper oxide that exists with microcapsule and hole sea lettuce extract have solved also that Red copper oxide is prone to condense, sedimentary defective in antifouling paint, improved the stability in storage of coating.
As preferably; Hole sea lettuce extract is prepared from following steps: get fresh hole sea lettuce and in 30 ~ 50 ℃ of air dry ovens, dry, be crushed to 200 ~ 300 orders then, extract 5 ~ 10h with the ethanol of volume(tric)fraction 40 ~ 95% 50 ~ 90 ℃ of temperature refluxed; The mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3; Then suction filtration obtains hole sea lettuce extracting solution, and hole sea lettuce extracting solution is distilled 2 ~ 3h under 70 ~ 80 ℃ of temperature, obtains hole sea lettuce paste extract; At last hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, promptly get hole sea lettuce extract.Hole sea lettuce extract can simply extract in the sea lettuce of hole through present method as good algae and shellfish amicine, for marine antifouling coating used.
Owing to adopt technique scheme; The invention has the beneficial effects as follows: the efficient antifouling paint in ocean of the present invention has the effect that the Red copper oxide consumption is few, suppress the big and long service life of marine life kind scope; The efficient antifouling paint in ocean of the present invention has solved with wide spectrum controlled release stain control agent that the Red copper oxide stain control agent is prone to condense, the problem of deposited phenomenon in the antifouling paint storage process; Thereby improved antifouling efficient, prolonged the work-ing life of antifouling paint.
Embodiment
With specific embodiment the present invention is done further explanation below.
Embodiment 1:
Getting fresh hole sea lettuce dries in 30 ℃ of air dry ovens; Be crushed to 250 orders then, use volume(tric)fraction 95%, quality to extract 6h as the ethanol of 2 times of hole sea lettuces 50 ℃ of temperature refluxed, then suction filtration obtains hole sea lettuce extracting solution; Hole sea lettuce extracting solution is distilled 2h under 80 ℃ of temperature; Obtain hole sea lettuce paste extract, at last hole sea lettuce paste extract is dried in 35 ℃ of air dry ovens, promptly get hole sea lettuce extract.
With mass percent is that 80% Red copper oxide and 20% hole sea lettuce extract are prepared from through following microcapsule preparation technology after mix:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:4 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 6:1 is dissolved in chitosan in 2% the acetum according to the mass ratio of chitosan and acetic acid; Filtered through gauze; Be that 1:5 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan then; Be that 1:1 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:8 adds LUTARALDEHYDE in the stain control agent base-material that step (2) obtains, and is warming up to 40 ℃ then, and reaction 1.3h obtains reaction solution;
The pH value of the reaction solution that (4) step (3) is obtained is adjusted to 9, and is warming up to 60 ℃, reaction 3.5h, and vacuum filtration obtains thick product;
(5) the thick product that step (4) is obtained washs respectively 3 times with sherwood oil, Virahol and water successively, and 50 ℃ of following vacuum-dryings get antifouling paint with wide spectrum controlled release stain control agent.
According to the proportioning in the table 1; Vinyl resin and rosin are dissolved in the YLENE, add wide spectrum controlled release stain control agent, red stone, zinc oxide, talcum powder and wilkinite, high-speed stirring then then successively; And be ground to mean particle size≤80 μ m high-speed stirring once more, obtain the efficient antifouling paint in ocean.
Embodiment 2:
Getting fresh hole sea lettuce dries in 45 ℃ of air dry ovens; Be crushed to 300 orders then, use volume(tric)fraction 40%, quality to extract 10h as the ethanol of 3 times of hole sea lettuces 70 ℃ of temperature refluxed, then suction filtration obtains hole sea lettuce extracting solution; Hole sea lettuce extracting solution is distilled 2.5h under 70 ℃ of temperature; Obtain hole sea lettuce paste extract, at last hole sea lettuce paste extract is dried in 50 ℃ of air dry ovens, promptly get hole sea lettuce extract.
With mass percent is that 60% Red copper oxide and 40% hole sea lettuce extract are prepared from through following microcapsule preparation technology after mix:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:3 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 5:1 is dissolved in chitosan in 5% the acetum according to the mass ratio of chitosan and acetic acid; Filtered through gauze; Be that 1:3 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan then; Be that 1:2 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:5 adds LUTARALDEHYDE in the stain control agent base-material that step (2) obtains, and is warming up to 45 ℃ then, and reaction 1h obtains reaction solution;
The pH value of the reaction solution that (4) step (3) is obtained is adjusted to 8.5, and is warming up to 65 ℃, reaction 3h, and vacuum filtration obtains thick product;
(5) the thick product that step (4) is obtained washs respectively 2 times with sherwood oil, Virahol and water successively, and 60 ℃ of following vacuum-dryings get antifouling paint with wide spectrum controlled release stain control agent.
According to the proportioning in the table 1; Vinyl resin and rosin are dissolved in the YLENE, add wide spectrum controlled release stain control agent, red stone, zinc oxide, talcum powder and wilkinite, high-speed stirring then then successively; And be ground to mean particle size≤80 μ m high-speed stirring once more, obtain the efficient antifouling paint in ocean.
Embodiment 3:
Getting fresh hole sea lettuce dries in 50 ℃ of air dry ovens; Be crushed to 200 orders then, use volume(tric)fraction 60%, quality to extract 5h as the ethanol of 2.5 times of hole sea lettuces 90 ℃ of temperature refluxed, then suction filtration obtains hole sea lettuce extracting solution; Hole sea lettuce extracting solution is distilled 3h under 75 ℃ of temperature; Obtain hole sea lettuce paste extract, at last hole sea lettuce paste extract is dried in 30 ℃ of air dry ovens, promptly get hole sea lettuce extract.
With mass percent is that 70% Red copper oxide and 30% hole sea lettuce extract are prepared from through following microcapsule preparation technology after mix:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:4.5 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 4:1 is dissolved in chitosan in 3% the acetum according to the mass ratio of chitosan and acetic acid; Filtered through gauze; Be that 1:6 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan then; Be that 1:3 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stir, obtain the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:2 adds LUTARALDEHYDE in the stain control agent base-material that step (2) obtains, and is warming up to 43 ℃ then, and reaction 1.5h obtains reaction solution;
The pH value of the reaction solution that (4) step (3) is obtained is adjusted to 8, and is warming up to 62 ℃, reaction 4h, and vacuum filtration obtains thick product;
(5) the thick product that step (4) is obtained washs respectively 2 times with sherwood oil, Virahol and water successively, and 55 ℃ of following vacuum-dryings get antifouling paint with wide spectrum controlled release stain control agent.
According to the proportioning in the table 1; Vinyl resin and rosin are dissolved in the YLENE, add wide spectrum controlled release stain control agent, red stone, zinc oxide, talcum powder and wilkinite, high-speed stirring then then successively; And be ground to mean particle size≤80 μ m high-speed stirring once more, obtain the efficient antifouling paint in ocean.
Comparative Examples:
According to the proportioning in the table 1; Vinyl resin and rosin are dissolved in the YLENE, add Red copper oxide, red stone, zinc oxide, talcum powder and wilkinite, high-speed stirring then then successively; And be ground to mean particle size≤80 μ m high-speed stirring once more, obtain marine antifouling coating.
To adopting the antifouling paint of wide spectrum controlled release stain control agent of the present invention,, under acceleration environment, store after 30 days according to GB/T6822-2007; Through detecting, deposition does not appear in antifouling paint, and stability better; And the coating of Comparative Examples is under the similar detection condition; Tangible throw out appears in coating lower floor, and the result shows that wide spectrum controlled release stain control agent of the present invention has the effect that tangible anti-freezing gathers.
Coating GB/T6822-2007 " ship bottom anti-fouling paint general technical specifications " to adopting wide spectrum controlled release stain control agent of the present invention detects, and the result shows that the viscosity of each coating all reaches 70 ~ 80mm
2/ s, fineness≤80 μ m, coating time of drying at 15 ~ 20h, anti-immersion property is good, resistance to blistering is good, storage period more than 1 year, antifouling life are good greater than 1.5 years, the dynamic antifouling property in 3 cycles.
For detecting the antifouling property of efficient marine antifouling coating; With reference to national standard " antifouling varnish model shallow sea soak test method " (GB5370-85); With the antifouling paint brushing long for 250mm, wide be 150mm, thick be that coating thickness is 80 ~ 150 μ m on the soft steel test piece of 2mm.Test piece is hung on the OTP that the Zhoushan city flies whale lacquer industry Co., Ltd (2 years) obtained goodish result of the test; And each detects once after the 6th, 12,18,24 month; Find that marine organisms are variant at blank model, the adhesive rate that scribbles on efficient antifouling paint model in ocean and the contrast marine antifouling coating, concrete bound percentage sees Table 2.
The efficient marine antifouling coating proportioning of table 1
| Each component concentration (g) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples |
| Wide spectrum controlled release stain control agent | 2000 | 2500 | 2200 | 2300 |
| Vinyl resin | 2300 | 1700 | 1900 | 1700 |
| Rosin | 1300 | 1700 | 1500 | 1400 |
| Red stone | 200 | 300 | 400 | 350 |
| Zinc oxide | 1000 | 600 | 800 | 700 |
| Talcum powder | 200 | 500 | 400 | 300 |
| Wilkinite | 100 | 200 | 250 | 300 |
| YLENE | 2400 | 2000 | 2300 | 2200 |
Table 2 sea life adhesive rate
| Time/adhesive rate | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples | Blank |
| 6 months | 0% | 0% | 0% | 1% | 10% |
| 12 months | 0% | 0% | 0% | 2% | 30% |
| 18 months | 2% | 2.1% | 1.9% | 6% | 70% |
| 24 months | 3% | 3.5% | 3.3% | 13% | 100% |
Claims (6)
1. the efficient antifouling paint in ocean is characterized in that, it is composed of the following components to count the efficient antifouling paint in said ocean by weight: 20 ~ 25 parts of wide spectrum controlled release stain control agents; 17 ~ 23 parts of vinyl resins, 13 ~ 17 parts of rosin, 2 ~ 4 parts of red stone; 6 ~ 10 parts in zinc oxide; 2 ~ 5 parts of talcum powder, 1 ~ 3 part of wilkinite, 20 ~ 24 parts of YLENE.
2. the efficient antifouling paint in a kind of ocean according to claim 1 is characterized in that, said wide spectrum controlled release stain control agent is prepared from through microcapsule preparation technology after mix Red copper oxide and hole sea lettuce extract, specifically may further comprise the steps:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, the mass percent of Red copper oxide is 60 ~ 80%, and the mass percent of hole sea lettuce extract is 20 ~ 40%; Vacuum oil is mixed according to the volume ratio of 1:3～4.5 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 4～6:1 is dissolved in chitosan in 2 ~ 5% the acetum filtered through gauze according to the mass ratio of chitosan and acetic acid; Is that 1:3～6 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan; Be that 1 ~ 3:1 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:2～8 add LUTARALDEHYDE in the stain control agent base-material that step 2 obtains, and is warming up to 40 ~ 45 ℃ then, and reaction 1 ~ 1.5h obtains reaction solution;
The pH value of the reaction solution that (4) step 3 is obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h filters, and obtains thick product;
(5) the thick product that step 4 is obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and 50 ~ 60 ℃ of following vacuum-dryings get antifouling paint with wide spectrum controlled release stain control agent.
3. the efficient antifouling paint in a kind of ocean according to claim 1 and 2 is characterized in that, hole sea lettuce extract is prepared from following steps: get fresh hole sea lettuce and in 30 ~ 50 ℃ of air dry ovens, dry; Be crushed to 200 ~ 300 orders then; Ethanol with volume(tric)fraction 40 ~ 95% extracts 5 ~ 10h 50 ~ 90 ℃ of temperature refluxed, and the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, and then suction filtration obtains hole sea lettuce extracting solution; Hole sea lettuce extracting solution is distilled 2 ~ 3h under 70 ~ 80 ℃ of temperature; Obtain hole sea lettuce paste extract, at last hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, promptly get hole sea lettuce extract.
4. the efficient antifouling paint in a kind of ocean according to claim 1 and 2; It is characterized in that; The efficient antifouling paint in said ocean is prepared from following steps: with vinyl resin and rosin, separate in YLENE, add wide spectrum controlled release stain control agent, red stone, zinc oxide, talcum powder and wilkinite, high-speed stirring then then successively; High-speed stirring once more after the grinding obtains the efficient antifouling paint in ocean.
5. the efficient antifouling paint in a kind of ocean as claimed in claim 1 is with wide spectrum controlled release stain control agent; It is characterized in that; Said wide spectrum controlled release stain control agent is prepared from through microcapsule preparation technology after mix Red copper oxide and hole sea lettuce extract, specifically may further comprise the steps:
(1) Red copper oxide and hole sea lettuce extract are mixed evenly, obtain mixing stain control agent, the mass percent of Red copper oxide is 60 ~ 80%, and the mass percent of hole sea lettuce extract is 20 ~ 40%; Vacuum oil is mixed according to the volume ratio of 1:3～4.5 with Yellow Protopet 2A, obtain mixing oil phase;
(2) be that 4～6:1 is dissolved in chitosan in 2 ~ 5% the acetum filtered through gauze according to the mass ratio of chitosan and acetic acid; Is that 1:3～6 adding in filtrating mixes stain control agent according to mixing stain control agent with the mass ratio of chitosan; Be that 1 ~ 3:1 joins and mixes in the oil phase according to mixing oil phase and acetum volume ratio then, stirring obtains the stain control agent base-material;
(3) mass ratio according to LUTARALDEHYDE and chitosan is that 1:2～8 add LUTARALDEHYDE in the stain control agent base-material that step 2 obtains, and is warming up to 40 ~ 45 ℃ then, and reaction 1 ~ 1.5h obtains reaction solution;
The pH value of the reaction solution that (4) step 3 is obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h filters, and obtains thick product;
(5) the thick product that step 4 is obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and 50 ~ 60 ℃ of following vacuum-dryings get the efficient antifouling paint in ocean with wide spectrum controlled release stain control agent.
6. the efficient antifouling paint in ocean according to claim 5 is characterized in that with wide spectrum controlled release stain control agent hole sea lettuce extract is prepared from following steps: get fresh hole sea lettuce and in 30 ~ 50 ℃ of air dry ovens, dry; Be crushed to 200 ~ 300 orders then; Ethanol with volume(tric)fraction 40 ~ 95% extracts 5 ~ 10h 50 ~ 90 ℃ of temperature refluxed, and the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, and then suction filtration obtains hole sea lettuce extracting solution; Hole sea lettuce extracting solution is distilled 2 ~ 3h under 70 ~ 80 ℃ of temperature; Obtain hole sea lettuce paste extract, at last hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, promptly get hole sea lettuce extract.
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| CN103992447A (en) * | 2014-06-05 | 2014-08-20 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
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| CN105038449A (en) * | 2015-06-30 | 2015-11-11 | 芜湖县双宝建材有限公司 | Wear-resistant high-adhesive force environmental-friendly corrosion-resistant antifouling paint |
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| CN103992447A (en) * | 2014-06-05 | 2014-08-20 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
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| CN105755807A (en) * | 2016-04-14 | 2016-07-13 | 巢湖市荷花渔网有限公司 | Natural antifouling agent for fishing nets |
| CN109439108A (en) * | 2018-09-12 | 2019-03-08 | 安徽康瑞高科新材料技术工程有限公司 | A kind of marine antifouling coating and preparation method thereof |
| CN110726804A (en) * | 2019-07-11 | 2020-01-24 | 浙江省海洋开发研究院 | Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating |
| CN110982359A (en) * | 2019-11-13 | 2020-04-10 | 湖北航天化学技术研究所 | Marine antifouling paint |
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Application publication date: 20121205 Assignee: Zhejiang Gaodun New Material Technology Co.,Ltd. Assignor: ZHEJIANG MARINE DEVELOPMENT Research Institute Contract record no.: X2023980044604 Denomination of invention: A high-efficiency marine antifouling coating and a broad-spectrum controlled release antifouling agent for marine high-efficiency antifouling coatings Granted publication date: 20141015 License type: Common License Record date: 20231025 |
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