CN102807797B - 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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- CN102807797B CN102807797B CN201210161805.5A CN201210161805A CN102807797B CN 102807797 B CN102807797 B CN 102807797B CN 201210161805 A CN201210161805 A CN 201210161805A CN 102807797 B CN102807797 B CN 102807797B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 238000013270 controlled release Methods 0.000 title claims abstract description 37
- 239000002519 antifouling agent Substances 0.000 title abstract description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 39
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 11
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 11
- 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
- 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
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 88
- 241000196251 Ulva arasakii Species 0.000 claims description 75
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 35
- 229920001661 Chitosan Polymers 0.000 claims description 33
- 239000003973 paint Substances 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
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 238000009775 high-speed stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 10
- 239000005662 Paraffin oil Substances 0.000 claims description 8
- 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
- 238000000605 extraction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000010992 reflux Methods 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
- -1 6 ~ 10 parts Chemical compound 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 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
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract description 2
- 241000196259 Ulva pertusa Species 0.000 abstract 1
- 239000000440 bentonite Substances 0.000 abstract 1
- 229910000278 bentonite Inorganic materials 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000002245 particle Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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
- 230000007547 defect Effects 0.000 description 2
- 239000013535 sea water Substances 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
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009422 growth inhibiting effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 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 stain control agent, be specifically related to wide spectrum controlled release stain control agent for a kind of ocean high-efficiency pollution-proof coating and ocean high-efficiency pollution-proof coating, this ocean high-efficiency pollution-proof coating is to be applied to prevent that marine fouling organism from adhering to affect, use on boats and ships and other ocean structures, and ocean high-efficiency pollution-proof coating is a kind of stain control agent of preparing marine antifouling coating with wide spectrum controlled release stain control agent.
Background technology
Boats and ships sail in a mighty ocean the important problem that runs into be exactly marine organisms 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 sea farming netting gear, the mesh that can result in blockage, reduction exchange of seawater efficiency, can cause cultivating fish and shellfish dysplasia even dead; Be attached on 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.Application antifouling paint is to solve stained problem not only economy but also efficient important channel.Have again every year a very large expense be used in compensation because antifouling paint lost efficacy, causing slow down upper, for application is again antirust, antifouling paint also will spend a large amount of expenses.Therefore developing efficient antifouling paint, is an important problem.
Antifouling paint is general main to be consisted of compositions such as base-material, stain control agent, subsidiary material, color stuffing and solvents.Rely on being progressively discharged into of stain control agent in seawater, suppress and stop biology adhering to and growing on the ocean structures such as boats and ships, thereby reach antifouling object.Main stain control agent used was the stain control agent of stanniferous, mercury and the poison material such as plumbous in the past, utilized its toxicity to drive away marine fouling organism.The tributyl tin compound TBT adding and DDT class poison material content reach 1ppm and can cause shellfish teratogenesis, and can enter human body by food chain transmission, unhealthful.Therefore, International Maritime Organizaton passed a resolution in calendar year 2001: on January 1st, 2008, on all boats and ships in the whole world, forbid organotin antifouling paint.The < < 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 is used Red copper oxide for stain control agent in a large number, because Red copper oxide is than great and wetting ability is strong, in antifouling paint storage process Red copper oxide easily condense, deposited phenomenon, to antifouling property, bring many disadvantageous effects.At present there is biological species to suppress that scope is less, stain control agent rate of release is unstable etc. to make the problems such as work-ing life of antifouling paint is not permanent in stain control agent in addition.
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 antifouling paint, for preventing that marine organisms from adhering on the surface of boats and ships, maritime facilities etc., this coating is to using silicate antifoulant (20 ~ 60 weight part) to be equipped with the poison material such as organotin, Red copper oxide, copper sulfate (6 ~ 40 weight part) as composite anti-fouling agent, adds the components such as film-forming resin (20 ~ 50 weight part), dispersion agent, anti-heavy agent and appropriate solvent to form.The antifouling paint of this invention is unprocessed with Red copper oxide, can not improve that Red copper oxide easily condenses in 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 current antifouling paint exists and suppress that scope is little, stain control agent rate of release is unstable, antifouling paint short problem in work-ing life, and a kind of ocean high-efficiency pollution-proof coating is provided.
Another object of the present invention is that solution Red copper oxide stain control agent easily condenses in antifouling paint storage process, deposited phenomenon, brings the problem of many disadvantageous effects, wide spectrum controlled release stain control agent for the high-efficiency pollution-proof coating of a kind of ocean to antifouling property.
In order to solve the problems of the technologies described above, the present invention is achieved through the following technical solutions:
A kind of ocean high-efficiency pollution-proof coating, count by weight described ocean high-efficiency pollution-proof coating composed of the following components: 20 ~ 25 parts of wide spectrum controlled release stain control agents, 17 ~ 23 parts of acrylic resins, 13 ~ 17 parts of rosin, 2 ~ 4 parts of ferric oxide, 6 ~ 10 parts, zinc oxide, 2 ~ 5 parts of talcum powder, 1 ~ 3 part of wilkinite, 20 ~ 24 parts of dimethylbenzene.
Thereby wide spectrum controlled release stain control agent is a kind of stain control agent rate of release of can controlling extends the antifouling paint stain control agent in work-ing life, and acrylic resin is as base-material, and dimethylbenzene is as solvent, and ferric oxide is rust-preventive agent, and talcum powder, wilkinite, dimethylbenzene are filler.
As preferably, described wide spectrum controlled release stain control agent is prepared from by microcapsule preparation process after mixing by Red copper oxide and hole sea lettuce extract, specifically comprises the following steps:
(1) Red copper oxide and hole sea lettuce extract are mixed, 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 paraffin oil, obtain mixing oil phase;
Red copper oxide and hole sea lettuce extract be jointly as stain control agent, vacuum oil and paraffin oil as wall material in order to generate microcapsule.
(2) according to the mass ratio of chitosan and acetic acid, be that 4～6:1 is dissolved in chitosan in 2 ~ 5% acetum, filtered through gauze; According to mix stain control agent and the mass ratio of chitosan be 1:3～6, to adding in filtrate, mix stain control agent; Then according to mixing oil phase and acetum volume ratio, be that 1 ~ 3:1 joins and mixes in oil phase, stir and obtain stain control agent base-material;
Chitosan as wall material microcapsule wall material is not soluble in water, under the effect of acetic acid, can accelerate the dissolving of chitosan, and filtered through gauze is fallen impurity, then with mix oil phase co-production latex solution.
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step 2 of 1:2～8, be then warming up to 40 ~ 45 ℃, reaction 1 ~ 1.5h, obtains reaction solution;
Glutaraldehyde, as solidifying agent, is cured the mixed solution in stain control agent base-material.Thereby chitosan is coated cuprous oxide particle, forms microcapsule particle, the add-on of glutaraldehyde has certain influence to the particle diameter of microcapsule particle, add that too much can to cause microcapsule particle to be gone through excessive.
(4) the pH value of reaction solution step 3 being obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h, filters, and obtains thick product;
Regulate pH can accelerate chitosan separating out in solution, accelerate the formation of microcapsule, the size of pH exerts an influence to the size of microcapsule particle simultaneously,
(5) thick product step 4 being obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and vacuum-drying at 50 ~ 60 ℃ obtains wide spectrum controlled release stain control agent for antifouling paint.
As preferably, hole sea lettuce extract is prepared from by following steps: get fresh hole sea lettuce and dry in 30 ~ 50 ℃ of air dry ovens, then be crushed to 200 ~ 300 orders, ethanol refluxing extraction 5 ~ 10h at 50 ~ 90 ℃ of temperature by volume fraction 40 ~ 95%, the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2 ~ 3h at 70 ~ 80 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, obtain hole sea lettuce extract.
As preferably, described ocean high-efficiency pollution-proof coating is prepared from by following steps: acrylic resin and rosin are dissolved in dimethylbenzene, then add successively wide spectrum controlled release stain control agent, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, high-speed stirring again after grinding, obtains ocean high-efficiency pollution-proof coating.
A wide spectrum controlled release stain control agent for the high-efficiency pollution-proof coating of ocean, described wide spectrum controlled release stain control agent is prepared from by microcapsule preparation process after mixing by Red copper oxide and hole sea lettuce extract, specifically comprises the following steps:
(1) Red copper oxide and hole sea lettuce extract are mixed, 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 paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 4～6:1 is dissolved in chitosan in 2 ~ 5% acetum, filtered through gauze; According to mix stain control agent and the mass ratio of chitosan be 1:3～6, to adding in filtrate, mix stain control agent; Then according to mixing oil phase and acetum volume ratio, be that 1 ~ 3:1 joins and mixes in oil phase, stir and obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step 2 of 1:2～8, be then warming up to 40 ~ 45 ℃, reaction 1 ~ 1.5h, obtains reaction solution;
(4) the pH value of reaction solution step 3 being obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h, filters, and obtains thick product;
(5) thick product step 4 being obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and vacuum-drying at 50 ~ 60 ℃ obtains wide spectrum controlled release stain control agent for the high-efficiency pollution-proof coating of ocean.
Red copper oxide is conventional copper class stain control agent, but has the defect of easily condensing, precipitating in antifouling paint.Hole sea lettuce extract has stronger growth-inhibiting effect to diatom and mussel etc., and inhibition is better.Microcapsulary is that micro substance is wrapped in to the technology in polymeric film, is the microdisplay package technology of a kind of store solids, liquids and gases.By microcapsulary, can effectively control the release of encapsulated material.Microcapsule preparation process of the present invention is that the mixture of Red copper oxide and hole sea lettuce extract is prepared into microcapsule with Chitosan-coated, by microcapsule, control the rate of release of Red copper oxide and hole sea lettuce extract, thereby extend the useful life of stain control agent, and then the work-ing life of improving antifouling paint, also reduced on the other hand the addition of Red copper oxide.Meanwhile, the Red copper oxide existing with microcapsule and hole sea lettuce extract have also solved the defect that Red copper oxide easily condenses, precipitates in antifouling paint, have improved the stability in storage of coating.
As preferably, hole sea lettuce extract is prepared from by following steps: get fresh hole sea lettuce and dry in 30 ~ 50 ℃ of air dry ovens, then be crushed to 200 ~ 300 orders, ethanol refluxing extraction 5 ~ 10h at 50 ~ 90 ℃ of temperature by volume fraction 40 ~ 95%, the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2 ~ 3h at 70 ~ 80 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, obtain hole sea lettuce extract.Hole sea lettuce extract, as good algae and shellfish amicine, can simply extract by present method from the sea lettuce of hole, for marine antifouling coating used.
Owing to adopting technique scheme, the invention has the beneficial effects as follows: ocean of the present invention high-efficiency pollution-proof coating has the effect that Red copper oxide consumption is few, suppress the large and long service life of marine life kind scope, ocean of the present invention high-efficiency pollution-proof coating has solved with wide spectrum controlled release stain control agent that Red copper oxide stain control agent easily condenses in antifouling paint storage process, the problem of deposited phenomenon, thereby improved antifouling efficiency, extended the work-ing life of antifouling paint.
Embodiment
With specific embodiment, the present invention is described further below.
Embodiment 1:
Get fresh hole sea lettuce dries in 30 ℃ of air dry ovens, then be crushed to 250 orders, by volume fraction 95%, quality, be ethanol refluxing extraction 6h at 50 ℃ of temperature of 2 times of hole sea lettuces, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2h at 80 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 35 ℃ of air dry ovens, obtain hole sea lettuce extract.
The Red copper oxide that is 80% by mass percent and 20% hole sea lettuce extract are prepared from by following microcapsule preparation process after mixing:
(1) Red copper oxide and hole sea lettuce extract are mixed, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:4 with paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 6:1 is dissolved in chitosan in 2% acetum, filtered through gauze, then according to mix stain control agent and the mass ratio of chitosan be 1:5, to adding in filtrate, mix stain control agent, then according to mixing oil phase and acetum volume ratio, be that 1:1 joins and mixes in oil phase, stir and obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step (2) of 1:8, be then warming up to 40 ℃, reaction 1.3h, obtains reaction solution;
(4) the pH value of reaction solution step (3) being obtained is adjusted to 9, and is warming up to 60 ℃, reaction 3.5h, and vacuum filtration, obtains thick product;
(5) thick product step (4) being obtained washs respectively 3 times with sherwood oil, Virahol and water successively, and vacuum-drying at 50 ℃ obtains wide spectrum controlled release stain control agent for antifouling paint.
According to the proportioning in table 1, acrylic resin and rosin are dissolved in dimethylbenzene, then add successively wide spectrum controlled release stain control agent, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, and be ground to mean particle size≤80 μ m high-speed stirring again, obtain ocean high-efficiency pollution-proof coating.
Embodiment 2:
Get fresh hole sea lettuce dries in 45 ℃ of air dry ovens, then be crushed to 300 orders, by volume fraction 40%, quality, be ethanol refluxing extraction 10h at 70 ℃ of temperature of 3 times of hole sea lettuces, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2.5h at 70 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 50 ℃ of air dry ovens, obtain hole sea lettuce extract.
The Red copper oxide that is 60% by mass percent and 40% hole sea lettuce extract are prepared from by following microcapsule preparation process after mixing:
(1) Red copper oxide and hole sea lettuce extract are mixed, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:3 with paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 5:1 is dissolved in chitosan in 5% acetum, filtered through gauze, then according to mix stain control agent and the mass ratio of chitosan be 1:3, to adding in filtrate, mix stain control agent, then according to mixing oil phase and acetum volume ratio, be that 1:2 joins and mixes in oil phase, stir and obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step (2) of 1:5, be then warming up to 45 ℃, reaction 1h, obtains reaction solution;
(4) the pH value of reaction solution step (3) being obtained is adjusted to 8.5, and is warming up to 65 ℃, reaction 3h, and vacuum filtration, obtains thick product;
(5) thick product step (4) being obtained washs respectively 2 times with sherwood oil, Virahol and water successively, and vacuum-drying at 60 ℃ obtains wide spectrum controlled release stain control agent for antifouling paint.
According to the proportioning in table 1, acrylic resin and rosin are dissolved in dimethylbenzene, then add successively wide spectrum controlled release stain control agent, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, and be ground to mean particle size≤80 μ m high-speed stirring again, obtain ocean high-efficiency pollution-proof coating.
Embodiment 3:
Get fresh hole sea lettuce dries in 50 ℃ of air dry ovens, then be crushed to 200 orders, by volume fraction 60%, quality, be ethanol refluxing extraction 5h at 90 ℃ of temperature of 2.5 times of hole sea lettuces, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 3h at 75 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 30 ℃ of air dry ovens, obtain hole sea lettuce extract.
The Red copper oxide that is 70% by mass percent and 30% hole sea lettuce extract are prepared from by following microcapsule preparation process after mixing:
(1) Red copper oxide and hole sea lettuce extract are mixed, obtain mixing stain control agent, vacuum oil is mixed according to the volume ratio of 1:4.5 with paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 4:1 is dissolved in chitosan in 3% acetum, filtered through gauze, then according to mix stain control agent and the mass ratio of chitosan be 1:6, to adding in filtrate, mix stain control agent, then according to mixing oil phase and acetum volume ratio, be that 1:3 joins and mixes in oil phase, stir, obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step (2) of 1:2, be then warming up to 43 ℃, reaction 1.5h, obtains reaction solution;
(4) the pH value of reaction solution step (3) being obtained is adjusted to 8, and is warming up to 62 ℃, reaction 4h, and vacuum filtration, obtains thick product;
(5) thick product step (4) being obtained washs respectively 2 times with sherwood oil, Virahol and water successively, and vacuum-drying at 55 ℃ obtains wide spectrum controlled release stain control agent for antifouling paint.
According to the proportioning in table 1, acrylic resin and rosin are dissolved in dimethylbenzene, then add successively wide spectrum controlled release stain control agent, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, and be ground to mean particle size≤80 μ m high-speed stirring again, obtain ocean high-efficiency pollution-proof coating.
Comparative example:
According to the proportioning in table 1, acrylic resin and rosin are dissolved in dimethylbenzene, then add successively Red copper oxide, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, and be ground to mean particle size≤80 μ m high-speed stirring again, obtain marine antifouling coating.
To adopting the antifouling paint of wide spectrum controlled release stain control agent of the present invention, according to GB/T6822-2007, under acceleration environment, store after 30 days, after testing, there is not precipitation in antifouling paint, and stability is better, and the coating of comparative example is under same testing conditions, there is obvious throw out in coating lower floor, result demonstration, and wide spectrum controlled release stain control agent of the present invention has the poly-effect of obvious anti-freezing.
To adopting the coating GB/T6822-2007 < < ship bottom anti-fouling paint general technical specifications > > of wide spectrum controlled release stain control agent of the present invention to detect, 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, resistance to immersion is good, resistance to blistering is good, storage period more than 1 year, antifouling life are greater than 1.5 years, the dynamic antifouling property in 3 cycles is good.
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), by antifouling paint brushing long for 250mm, wide be that on the soft steel test piece of 150mm, the thick 2mm of being, coating thickness is 80 ~ 150 μ m.Test piece is hung over to (2 years) in the offshore test platform of Zhoushan Fei Whaleqi industry company limited and obtained goodish test-results, and each detects once after the 6th, 12,18,24 months, find that marine organisms are variant at blank model, the adhesive rate that scribbles on ocean high-efficiency pollution-proof coating model and contrast marine antifouling coating, concrete bound percentage is in Table 2.
The efficient marine antifouling coating proportioning of table 1
| Each component concentration (g) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Wide spectrum controlled release stain control agent | 2000 | 2500 | 2200 | 2300 |
| Acrylic resin | 2300 | 1700 | 1900 | 1700 |
| Rosin | 1300 | 1700 | 1500 | 1400 |
| Ferric oxide | 200 | 300 | 400 | 350 |
| Zinc oxide | 1000 | 600 | 800 | 700 |
| Talcum powder | 200 | 500 | 400 | 300 |
| Wilkinite | 100 | 200 | 250 | 300 |
| Dimethylbenzene | 2400 | 2000 | 2300 | 2200 |
Table 2 marine organisms adhesive rate
| Time/adhesive rate | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example | 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 (5)
1. an ocean high-efficiency pollution-proof coating, it is characterized in that, count by weight described ocean high-efficiency pollution-proof coating composed of the following components: 20 ~ 25 parts of wide spectrum controlled release stain control agents, 17 ~ 23 parts of acrylic resins, 13 ~ 17 parts of rosin, 2 ~ 4 parts of ferric oxide, 6 ~ 10 parts, zinc oxide, 2 ~ 5 parts of talcum powder, 1 ~ 3 part of wilkinite, 20 ~ 24 parts of dimethylbenzene;
Described wide spectrum controlled release stain control agent is prepared from by microcapsule preparation process after mixing by Red copper oxide and hole sea lettuce extract, specifically comprises the following steps:
(1) Red copper oxide and hole sea lettuce extract are mixed, 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 paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 4～6:1 is dissolved in chitosan in 2 ~ 5% acetum, filtered through gauze; According to mix stain control agent and the mass ratio of chitosan be 1:3～6, to adding in filtrate, mix stain control agent; Then according to mixing oil phase and acetum volume ratio, be that 1 ~ 3:1 joins and mixes in oil phase, stir and obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step 2 of 1:2～8, be then warming up to 40 ~ 45 ℃, reaction 1 ~ 1.5h, obtains reaction solution;
(4) the pH value of reaction solution step 3 being obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h, filters, and obtains thick product;
(5) thick product step 4 being obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and vacuum-drying at 50 ~ 60 ℃ obtains wide spectrum controlled release stain control agent for antifouling paint.
2. a kind of ocean according to claim 1 high-efficiency pollution-proof coating, it is characterized in that, hole sea lettuce extract is prepared from by following steps: get fresh hole sea lettuce and dry in 30 ~ 50 ℃ of air dry ovens, then be crushed to 200 ~ 300 orders, ethanol refluxing extraction 5 ~ 10h at 50 ~ 90 ℃ of temperature by volume fraction 40 ~ 95%, the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2 ~ 3h at 70 ~ 80 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, obtain hole sea lettuce extract.
3. a kind of ocean according to claim 1 high-efficiency pollution-proof coating, it is characterized in that, described ocean high-efficiency pollution-proof coating is prepared from by following steps: by acrylic resin and rosin, be dissolved in dimethylbenzene, then add successively wide spectrum controlled release stain control agent, ferric oxide, zinc oxide, talcum powder and wilkinite, then high-speed stirring, high-speed stirring again after grinding, obtains ocean high-efficiency pollution-proof coating.
4. a wide spectrum controlled release stain control agent for a kind of ocean as claimed in claim 1 high-efficiency pollution-proof coating, it is characterized in that, described wide spectrum controlled release stain control agent is prepared from by microcapsule preparation process after mixing by Red copper oxide and hole sea lettuce extract, specifically comprises the following steps:
(1) Red copper oxide and hole sea lettuce extract are mixed, 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 paraffin oil, obtain mixing oil phase;
(2) according to the mass ratio of chitosan and acetic acid, be that 4～6:1 is dissolved in chitosan in 2 ~ 5% acetum, filtered through gauze; According to mix stain control agent and the mass ratio of chitosan be 1:3～6, to adding in filtrate, mix stain control agent; Then according to mixing oil phase and acetum volume ratio, be that 1 ~ 3:1 joins and mixes in oil phase, stir and obtain stain control agent base-material;
(3) according to the mass ratio of glutaraldehyde and chitosan, be to add glutaraldehyde in the stain control agent base-material that obtains to step 2 of 1:2～8, be then warming up to 40 ~ 45 ℃, reaction 1 ~ 1.5h, obtains reaction solution;
(4) the pH value of reaction solution step 3 being obtained is adjusted to 8～9, and is warming up to 60 ~ 65 ℃, and reaction 3 ~ 4h, filters, and obtains thick product;
(5) thick product step 4 being obtained washs respectively 2 ~ 3 times with sherwood oil, Virahol and water successively, and vacuum-drying at 50 ~ 60 ℃ obtains wide spectrum controlled release stain control agent for the high-efficiency pollution-proof coating of ocean.
5. wide spectrum controlled release stain control agent for the high-efficiency pollution-proof coating of ocean according to claim 4, it is characterized in that, hole sea lettuce extract is prepared from by following steps: get fresh hole sea lettuce and dry in 30 ~ 50 ℃ of air dry ovens, then be crushed to 200 ~ 300 orders, ethanol refluxing extraction 5 ~ 10h at 50 ~ 90 ℃ of temperature by volume fraction 40 ~ 95%, the mass ratio of hole sea lettuce and ethanolic soln is 1:2 ~ 3, then suction filtration obtains hole sea lettuce extracting solution, hole sea lettuce extracting solution is distilled to 2 ~ 3h at 70 ~ 80 ℃ of temperature, obtain hole sea lettuce paste extract, finally hole sea lettuce paste extract is dried in 30 ~ 50 ℃ of air dry ovens, obtain hole sea lettuce extract.
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| WO2017041196A1 (en) * | 2015-09-11 | 2017-03-16 | Universidad De Concepcion | Antifouling bio-paint comprising extracts of macroalgae that attract epibiont bacteria and active extracts of bacteria with antifouling property |
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| CN103992447B (en) * | 2014-06-05 | 2017-03-22 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
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| CN110726804B (en) * | 2019-07-11 | 2021-12-31 | 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 |
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