CN102617795A - Aqueous self-polishing antifouling coating substrate resin and antifouling coating prepared from same - Google Patents
Aqueous self-polishing antifouling coating substrate resin and antifouling coating prepared from same Download PDFInfo
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- CN102617795A CN102617795A CN201210095146XA CN201210095146A CN102617795A CN 102617795 A CN102617795 A CN 102617795A CN 201210095146X A CN201210095146X A CN 201210095146XA CN 201210095146 A CN201210095146 A CN 201210095146A CN 102617795 A CN102617795 A CN 102617795A
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Abstract
The invention provides aqueous self-polishing antifouling coating substrate resin and an antifouling coating prepared from the same. The resin is prepared with a simple preparation method, and does not contain toxic agents such as DDT (Dichlorodiphenyltrichloroethane), organic tin and the like. The self-polishing antifouling coating is aqueous, has the characteristics of low VOC (Volatile Organic Compound) content, sea environmental friendliness, easiness and convenient for construction, easiness for maintaining and the like, and can be applied to a special substrate surface; and moreover, the substrate resin has self-polishing performance, so that the dissolution rate of an organic antifouling agent in seawater is controlled, the antifouling period can be prolonged, and the antifouling requirement is met.
Description
Technical field
The present invention relates to the antifouling paint field, be specifically related to a kind of water-based self polishing copolymer antifouling paint matrix resin and with the antifouling paint of this resins.
Background technology
Since the mankind get into the ocean, just unremitting struggle has been carried out in the harm of naval vessel and maritime facilities, solved in the stained method of settled organism, to use antifouling paint the most extensive, also effective with marine attaching organism.Antifouling paint in the past all is a solvent-based system.Solvent based coating influences health of operators in coating process, have potential safety hazard simultaneously.Improving constantly of Along with people's environmental consciousness, antifouling paint is an inexorable trend to environment-friendly type, Water-borne modification development.
Since the research of nineteen nineties water-based marine antifouling coating, be mainly used in culture fishery abroad.Be base-material mostly with the water-base resin, Red copper oxide adds the compound stain control agent system of organic stain control agent, VOC content lower (less than 200g/l), and the antifouling phase imitated five months to 12 months.Traditional water-based antifouling paint is a base-material with the water-based emulsion mostly, does not possess from polishing performance.Aquasafe w like Norway GJOCO A/S company; The Aqua-Net of Steen-Hansen Maling AS company, Net-Guard; The Flexgard of U.S. Flexabar Aquatech company; The Net-Clear of Australia Wattyl company etc.
China has obtained gratifying achievement to the research of the marine antifouling coating history of existing four more than ten years, and solvent-borne type tin-free self-polishing antifouling paint has obtained successful Application.But the research to the water-based self polishing copolymer antifouling paint is still blank.
Summary of the invention
The purpose of this invention is to provide a kind of water-based self polishing copolymer antifouling paint matrix resin and with the antifouling paint of this resins; This antifouling paint VOC content is few; Do not contain toxic agent such as DDT, organotin, this antifouling paint has from polishing performance, has good anti-fouling effect.
Technical scheme of the present invention is:
A kind of water-based self polishing copolymer antifouling paint matrix resin, its structural formula is made up of the structural unit shown in the following I-IV:
M:n:x:y=1:8～15:3～8:1～5 wherein;
R2 representes to have the organic group of unsaturated link(age), is selected from alkyl, naphthenic base, aryl etc.; R3 representes alkyl, naphthenic base or arylidene; M representes atoms metal, is selected from zinc, copper or magnesium metal.
This resin obtains through following method is synthetic:
Make the unsaturated vinyl monomer (a1) that contains a divalent-metal ion; Under action of evocating; After other metal-free unsaturated vinyl monomer (a2) copolymerizations, this polymkeric substance again through with one or both basic cpd hybrid reactions, make it become water-base resin.
Described basic cpd can be one or both in saturated ammoniacal liquor, thanomin, the diethylolamine.Wherein the structural formula of (a1) is:
R
1-COO-M-COO-R
2 （a1）
R
1, R
2Expression has the organic group of unsaturated link(age), is selected from alkyl, naphthenic base, aryl etc.; M representes atoms metal, is selected from zinc, copper or magnesium metal.
Described other metal-free unsaturated vinyl monomers (a2) are at least a to be selected from the monomer that following general formula representes and to form:
R
4OCO-CH(R
3)=CH
2
R wherein
3Expression Wasserstoffatoms or methyl, R
4Expression alkyl, naphthenic base or arylidene;
The perhaps at least a monomer of being represented by following general formula is formed:
R
7R
6OCO-CH(R
5)=CH
2
Wherein R5 representes Wasserstoffatoms or methyl, and R6 representes alkylidene group, ring alkylidene group or arylidene, and R7 representes hydroxyl, epoxy group(ing), cycloalkyloxy or aryloxy.
Described initiator is mainly peroxide and azo class, and the former is like Lucidol (BPO), dilauroyl peroxide (LPO) etc.; The latter such as Diisopropyl azodicarboxylate (AIBN), AMBN etc.
A kind of water-based self polishing copolymer antifouling paint, it is to be cooperated by above-mentioned matrix resin from polishing performance, additive, auxiliary agent, solubility promoter, water and at least two kinds of stain control agents, is mixed with to obtain.
Its basal component is: (by mass parts)
From polishing resin 25～65
At least two kinds of stain control agents 30～75
Additive 5～15
Solubility promoter 5～15
Water 5～15
Wherein said stain control agent is that organic cpds, copper are mineral compound.Organic cpds is curing two (a thiocarbonyl group n n dimetylaniline), 1; 2-ethylidene-two (dithiocarbamic acid) zinc salt, 1; 2-ethylidene-two (dithiocarbamic acid) MnZn salt, two (2-mercaptopyridine-1-oxide compound) zinc, two (2-mercaptopyridine-1-oxide compound) copper, 2; 4; 5,6-daconil M, N-dichloro fluorine methylthio group-N, N'-dimethyl--N-phenyl sulfuryl diamide, N-dichloro fluorine methylthio group-N-p-methylphenyl-N '; N '-dimethyl sulphide acid diamide, N-(3; The 4-dichlorophenyl)-and N', N'-dimethyl urea, uncle's 2-fourth amino-4-cyclopropylamino-6-methylthio group-s-triazine, 4, a kind of in the U.S. holder of 5-two chloro-N-octyl groups-4-isothiazoline-3-ketone, 2-thiocyanogen methyl-thio-benzothiazole, ziram, pyridine triphenyl-boron, copper pyrithione, ZPT, trichlorophenyl maleimide, 4-bromo-2-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN, the hydrochloric acid pyrimidine.Copper is that mineral compound is a kind of in copper, copper alloy, Red copper oxide, the cuprous thiocyanate.
Wherein said additive comprises softening agent, antisettling agent.Softening agent is a kind of in clorafin, DOP, Witcizer 300, epoxy soybean oil, epoxy oleum lini, the tritolyl phosphate.Antisettling agent is a kind of in organobentonite, polyamide wax, the aerosil.
Wherein said solubility promoter is the hydroxyl solvent that excellent compatibility is arranged with matrix resin, as several kinds in methyl alcohol, ethanol, propyl carbinol, hexalin, propylene glycol monomethyl ether and so on the alcohols.
Advantage of the present invention is that self polishing copolymer antifouling paint is a water-based; Have low VOC content, friendly to ocean environment, construction is simple and convenient, be easy to characteristics such as maintenance; Can be used for the special substrate surface, and, make that the dissolution rate of organic stain control agent in seawater is controlled because matrix resin has from polishing performance; Can prolong antifouling phase effect like this, satisfy antifouling demand.
Embodiment
The preparation of water-based self polishing copolymer antifouling paint matrix resin
Embodiment 1
Described water-based is processed through two-step approach from polishing resin, unsaturated vinyl monomer (a1) CH who contains divalent-metal ion of the first step preparation
3-COO-Zn-COO-(C
2H
5)
2Under the effect of initiator Lucidol, with other metal-free unsaturated vinyl monomers (a2) CH
3OCO-CH (R
3)=CH
2Copolymerization is prepared into a polymkeric substance, and this polymkeric substance and one or both basic cpd hybrid reactions are finally processed water-base resin.Concrete steps are following:
1) contains the preparation of the unsaturated vinyl monomer (a1) of a divalent-metal ion
Take by weighing zinc or the MOX or the oxyhydroxide of copper, the organic acid that contains unsaturated double-bond such as vinylformic acid etc. that mol ratio is 1:2 respectively.Stoichiometric organic mixed solvent and the MOX that has taken by weighing or oxyhydroxide are joined in the four-hole bottle that whipping appts, prolong, tap funnel, TM are housed; Be warming up to 80 ℃; Within 3 hours above-mentioned mixing acid is added drop-wise in the four-hole bottle, is incubated again till the mixed solution clear.Make the unsaturated vinyl monomer (a1) of metal ion.
2) water-based is from the preparation of polishing resin
Stoichiometric organic mixed solvent and part propylene acid esters monomer are joined in the four-hole bottle that whipping appts, prolong, tap funnel, TM are housed, be warming up to 100 ℃, monomer and (methyl) esters of acrylic acid such as methyl acrylate, ethyl propenoate and the initiator etc. of preparation in above-mentioned 1 are mixed by weight 2:4～10:1～2; Be added drop-wise in the mixed solvent, dripped 3～4 hours, be incubated 2 hours; Add initiator again, add the back insulation 1 hour that finishes, be warming up to 130 ℃; Distill out partial solvent, be cooled to 70 ℃ again, be added dropwise to the basic cpd that mol ratio is 1:1～10; Kept this temperature 30 minutes; Adding the solid content that an amount of zero(ppm) water is adjusted to polymkeric substance is 50%, and cooling discharge obtains water-based of the present invention from polishing resin.
The wherein said organic acid that contains unsaturated double-bond has at least a in vinylformic acid, methylacrylic acid, methylene-succinic acid, the toxilic acid etc.
Wherein relate to (a2) monomer and can be several kinds in (methyl) acrylate monomer such as methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, tert-butyl acrylate, Isooctyl acrylate monomer, TEB 3K, NSC 20956, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, the Isooctyl methacrylate.
Unsaturated monomer (a2) also can be that the monomer of hydroxylation is like (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester or (methyl) vinylformic acid 4-hydroxyl butyl ester.
Unsaturated monomer (a2) also can be monomer with poly-hydroxy group like (methyl) vinylformic acid glyceryl ester, have the vinyl monomer of primary amino or secondary amino group, like (methyl) vinylformic acid butyl amino ethyl ester or butyl amino-ethyl (methyl) third rare acid amides or the like.
Embodiment 2
1. prepare metallic monomer a1-1
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 70 mass parts propylene glycol monomethyl ethers and 40 mass parts zinc oxide, be heated to 80 ℃.From tap funnel, drip the mixture 3 hours of 45 mass parts methylacrylic acids, 30 mass parts vinylformic acid and 20 mass parts water.Be incubated again till the mixed solution clear.Make metallic monomer a1-1.
2. the preparation water-based is from polishing resin 1
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 52 mass parts propylene glycol monomethyl ethers, 30 mass parts YLENE and 5 parts of ethyl propenoates, be heated to 100 ℃.From tap funnel, dripped the mixing liquid formed by 25 mass parts TEB 3Ks, 45 mass parts ethyl propenoates, 5 mass parts Bing Xisuandingzhis, 50 mass parts monomer a1-1,10 mass parts YLENE, 2.5 parts of Diisopropyl azodicarboxylates 4 hours.After dropwising, be incubated 2 hours, add the Diisopropyl azodicarboxylate and the 7 mass parts YLENE of 0.5 mass parts; After being incubated 2 hours, temperature is risen to 130 ℃, remove partial solvent; Be cooled to 70 ℃, add saturated ammoniacal liquor of 26 mass parts and 30 mass parts deionized waters, cooling discharge.Make water-based from polishing resin 1.
Embodiment 3
1. prepare metallic monomer a1-2
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 25 mass parts propyl carbinols, 75 mass parts YLENE and 40 mass parts zinc oxide, be heated to 80 ℃.From tap funnel, drip the mixture 3 hours of 45 mass parts methylacrylic acids, 30 mass parts vinylformic acid and 20 mass parts water.Be incubated again till the mixed solution clear.Make metallic monomer a1-2.
2. the preparation water-based is from polishing resin 2
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 52 mass parts propylene glycol monomethyl ethers, 30 mass parts YLENE and 5 mass parts ethyl propenoates, be heated to 100 ℃.From tap funnel, dripped the mixing liquid formed by 25 mass parts TEB 3Ks, 45 mass parts ethyl propenoates, 5 mass parts Bing Xisuandingzhis, 50 mass parts monomer a1-2,10 mass parts YLENE, 2.5 mass parts Diisopropyl azodicarboxylates 4 hours.After dropwising, be incubated 2 hours, add the Diisopropyl azodicarboxylate and the 7 mass parts YLENE of 0.5 mass parts; After being incubated 2 hours; Temperature is risen to 130 ℃, remove partial solvent, be cooled to 70 ℃; Add the saturated ammoniacal liquor of 20 mass parts, 3 mass parts thanomins and 47 mass parts deionized waters, cooling discharge.Get water-based from polishing resin 2.
Embodiment 4
1. prepare metallic monomer a1-3
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 70 mass parts propylene glycol monomethyl ethers and 40 mass parts Natural manganese dioxide, be heated to 80 ℃.From tap funnel, drip the mixture 3 hours of 85 mass parts methylacrylic acids, 75 mass parts vinylformic acid and 20 mass parts water.Be incubated again till the mixed solution clear.Make metallic monomer a1-3.
2. the preparation water-based is from polishing resin 3
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 52 mass parts propylene glycol monomethyl ethers, 30 mass parts YLENE and 5 mass parts ethyl propenoates, be heated to 100 ℃.From tap funnel, dripped the mixing liquid formed by 25 mass parts TEB 3Ks, 45 mass parts ethyl propenoates, 5 mass parts Bing Xisuandingzhis, 50 mass parts monomer a1-3,10 mass parts YLENE, 2.5 mass parts Diisopropyl azodicarboxylates 4 hours.After dropwising, be incubated 2 hours, add Diisopropyl azodicarboxylate and 7 parts of YLENE of 0.5 part; After being incubated 2 hours, temperature is risen to 130 ℃, remove partial solvent; Be cooled to 70 ℃, add saturated ammoniacal liquor of 26 mass parts and 30 mass parts deionized waters, cooling discharge.Make water-based from polishing resin 3.
Embodiment 5
1. prepare metallic monomer a1-4
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 70 mass parts propylene glycol monomethyl ethers and 49 mass parts verditers, be heated to 80 ℃.From tap funnel, drip the mixture 3 hours of 45 mass parts methylacrylic acids, 30 mass parts vinylformic acid and 20 mass parts water.Be incubated again till the mixed solution clear.Make metallic monomer a1-3.
2. prepare water-based polished resin 4
In a four-hole bottle that whipping appts, prolong, tap funnel, TM be housed, under agitation add 52 mass parts propylene glycol monomethyl ethers, 30 mass parts YLENE and 5 mass parts ethyl propenoates, be heated to 100 ℃.From tap funnel, dripped the mixing liquid formed by 25 mass parts TEB 3Ks, 45 mass parts ethyl propenoates, 5 mass parts Bing Xisuandingzhis, 50 mass parts monomer a1-3,10 mass parts YLENE, 2.5 mass parts Diisopropyl azodicarboxylates 4 hours.After dropwising, be incubated 2 hours, add the Diisopropyl azodicarboxylate and the 7 mass parts YLENE of 0.5 mass parts; After being incubated 2 hours; Temperature is risen to 130 ℃, remove partial solvent, be cooled to 70 ℃; Add the saturated ammoniacal liquor of 20 mass parts, 3 mass parts thanomins and 47 mass parts deionized waters, cooling discharge.Make water-based from polishing resin 4.
The preparation of water-based self polishing copolymer antifouling paint
Embodiment 6
With the water-based of 25 mass parts embodiment 1 preparation from 4 of the Red copper oxide that polishes resin 1,45 mass parts, 15 mass parts; 5-two chloro-N-octyl groups-4-isothiazoline-3-ketone; 5 mass parts clorafins, 2 mass parts aerosils, 15 mass parts water and 8 mass parts propylene glycol monomethyl ethers; Mixing and stirring is ground and is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-1 of system.
Embodiment 7
The water-based of 25 mass parts embodiment, 1 preparation is polished the Red copper oxide of resin 1,45 mass parts, the ZPT of 5 mass parts certainly; 4 of 10 mass parts; 5-two chloro-N-octyl groups-4-isothiazoline-3-ketone, 5 mass parts clorafins, 2 mass parts aerosils, 15 mass parts water and 8 mass parts propylene glycol monomethyl ethers, mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-2 of system.
Embodiment 8
The water-based of 35 mass parts embodiment, 2 preparations is polished the Red copper oxide of resin 2,35 mass parts, the copper pyrithione of 10 mass parts certainly; 4 mass parts tritolyl phosphates, 3 mass parts polyamide waxes, 10 mass parts water and 8 mass parts propyl carbinol mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-3 of system.
Embodiment 9
The water-based of 35 mass parts embodiment, 2 preparations is polished the Red copper oxide of resin 2,35 mass parts, the N-(3 of 10 mass parts certainly; The 4-dichlorophenyl)-N'; The N'-dimethyl urea; 4 mass parts tritolyl phosphates, 3 mass parts polyamide waxes, 10 mass parts water and 8 mass parts propyl carbinol mixing and stirring are ground and are dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-4 of system.
Embodiment 10
The water-based of 45 mass parts embodiment, 3 preparations is polished certainly Red copper oxide, the 8 mass parts uncle 2-fourth amino-4-cyclopropylamino-6-methylthio group-s-triazines of resin 3,30 mass parts; 2 mass parts DOPs, 4 mass parts organobentonites, 5 mass parts water and 5 mass parts propylene glycol monomethyl ethers; Mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-5 of system.
Embodiment 11
The water-based of 45 mass parts embodiment, 3 preparations is polished Red copper oxide, the 8 mass parts trichlorophenyl maleimides of resin 3,30 mass parts certainly; 2 mass parts DOPs, 4 mass parts organobentonites, 5 mass parts water and 5 mass parts propylene glycol monomethyl ethers; Mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-6 of system.
Embodiment 12
The water-based of 65 mass parts embodiment, 4 preparations is polished the cuprous thiocyanate of resin 4,25 mass parts, 10 mass parts pyridine triphenyl-borons certainly; The Witcizer 300 of 4 mass parts; 2 mass parts polyamide waxes, 8 mass parts water and 8 mass parts ethanol, mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-7 of system.
Embodiment 13
The water-based of 65 mass parts embodiment, 4 preparations is polished cuprous thiocyanate, 5 mass parts pyridine triphenyl-borons, the 5 mass parts N-dichloro fluorine methylthio group-N of resin 4,25 mass parts certainly; The Witcizer 300 of N'-dimethyl--N-phenyl sulfuryl diamide, 4 mass parts, 2 mass parts polyamide waxes, 8 mass parts water and 8 mass parts ethanol; Mixing and stirring; Grinding is dispersed to fineness less than 50 μ m, the water-based self polishing copolymer antifouling paint AF-8 of system.
Claims (8)
1. water-based self polishing copolymer antifouling paint matrix resin is characterized in that its structural formula comprises structural unit shown in the following I-IV:
Wherein m, n, x, y are selected from the natural number greater than 0; And m:n:x:y=1:8～15:3～8:1～5;
R2 representes to have the organic group of unsaturated link(age), is selected from alkyl, naphthenic base, aryl etc.; R3 representes alkyl, naphthenic base or arylidene; M representes atoms metal, is selected from zinc, copper or magnesium metal.
2. the preparation method of water-based self polishing copolymer antifouling paint matrix resin as claimed in claim 1 is characterized in that, comprises following steps:
The unsaturated vinyl monomer (a1) that will contain a divalent-metal ion; Under action of evocating; After other metal-free unsaturated vinyl monomer (a2) copolymerizations, this polymkeric substance again through with one or both basic cpd hybrid reactions, make it become water-base resin;
Described basic cpd can be one or both in saturated ammoniacal liquor, thanomin, the diethylolamine;
Wherein the structural formula of (a1) is:
R
1-COO-M-COO-R
2 （a1）
R
1, R
2Expression has the organic group of unsaturated link(age), is selected from alkyl, naphthenic base or aryl; M representes atoms metal, is selected from zinc, copper or magnesium metal;
At least a monomer of being represented by following general formula that is selected from of described other metal-free unsaturated vinyl monomers (a2) is formed:
R
4OCO-CH(R
3)=CH
2
R wherein
3Expression Wasserstoffatoms or methyl, R
4Expression alkyl, naphthenic base or arylidene; And at least a monomer of being represented by following general formula is formed:
R
7R
6OCO-CH(R
5)=CH
2
Wherein R5 representes Wasserstoffatoms or methyl, and R6 representes alkylidene group, ring alkylidene group or arylidene, and R7 representes hydroxyl, epoxy group(ing), cycloalkyloxy or aryloxy.
3. water-based self polishing copolymer antifouling paint that contains water-based self polishing copolymer antifouling paint matrix resin; It is characterized in that; Its composition comprises: polish resin 25～6 5 mass parts, at least two kinds of stain control agent 30～75 mass parts, additive 5～15 mass parts, solubility promoter 5～15 mass parts, water 5～15 mass parts certainly, wherein said additive comprises softening agent, antisettling agent.
4. water-based self polishing copolymer antifouling paint according to claim 3 is characterized in that, it is in the mineral compound one or more that said stain control agent is selected from organic cpds and copper.
5. water-based self polishing copolymer antifouling paint according to claim 4; It is characterized in that; Said organic cpds is for being selected from curing two (thiocarbonyl group n n dimetylaniline), 1; 2-ethylidene-two (dithiocarbamic acid) zinc salt, ethylene-two (dithiocarbamic acid) MnZn salt, two (2-mercaptopyridine-1-oxide compound) zinc, two (2-mercaptopyridine-1-oxide compound) copper, 2,4; 5; 6-daconil M, N-dichloro fluorine methylthio group-N, N'-dimethyl--N-phenyl sulfuryl diamide, N-dichloro fluorine methylthio group-N-p-methylphenyl-N ', N '-dimethyl sulphide acid diamide, N-(3; The 4-dichlorophenyl)-N'; N'-dimethyl urea, uncle's 2-fourth amino-4-cyclopropylamino-6-methylthio group-s-triazine, 4, one or more in the U.S. holder of 5-two chloro-N-octyl groups-4-isothiazoline-3-ketone, 2-thiocyanogen methyl-thio-benzothiazole, ziram, pyridine triphenyl-boron, copper pyrithione, ZPT, trichlorophenyl maleimide, 4-bromo-2-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN, the hydrochloric acid pyrimidine, said copper are that mineral compound is to be selected from copper, copper alloy, Red copper oxide, the cuprous thiocyanate one or more.
6. according to the described water-based self polishing copolymer antifouling paint of claim 4-5; It is characterized in that; Said softening agent is a kind of in clorafin, DOP, Witcizer 300, epoxy soybean oil, epoxy oleum lini, the tritolyl phosphate, and said antisettling agent is a kind of in organobentonite, polyamide wax, the aerosil.
7. water-based self polishing copolymer antifouling paint according to claim 6 is characterized in that, described solubility promoter is the hydroxyl solvent that excellent compatibility is arranged with matrix resin.
8. water-based self polishing copolymer antifouling paint according to claim 6 is characterized in that, said solubility promoter is one or more in methyl alcohol, ethanol, propyl carbinol, hexalin, propylene glycol monomethyl ether and so on the alcohols.
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| CN106675294A (en) * | 2016-12-20 | 2017-05-17 | 海洋化工研究院有限公司 | Copper-free and environment-friendly self-polishing ocean antifouling paint |
| CN110511633A (en) * | 2018-05-22 | 2019-11-29 | 海洋化工研究院有限公司 | A kind of aqueous marine antifouling coating of low VOC content |
| CN110577777A (en) * | 2019-09-11 | 2019-12-17 | 徐悦 | Environment-friendly water-based antifouling paint and preparation method and application thereof |
| CN115895321A (en) * | 2021-09-30 | 2023-04-04 | 上海富元塑胶科技有限公司 | Antifouling intrinsic coating and preparation method and application thereof |
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| CN106675294A (en) * | 2016-12-20 | 2017-05-17 | 海洋化工研究院有限公司 | Copper-free and environment-friendly self-polishing ocean antifouling paint |
| CN106675294B (en) * | 2016-12-20 | 2019-04-19 | 海洋化工研究院有限公司 | No copper ring is protected from polishing marine antifouling coating |
| CN110511633A (en) * | 2018-05-22 | 2019-11-29 | 海洋化工研究院有限公司 | A kind of aqueous marine antifouling coating of low VOC content |
| CN110577777A (en) * | 2019-09-11 | 2019-12-17 | 徐悦 | Environment-friendly water-based antifouling paint and preparation method and application thereof |
| CN115895321A (en) * | 2021-09-30 | 2023-04-04 | 上海富元塑胶科技有限公司 | Antifouling intrinsic coating and preparation method and application thereof |
| CN115895321B (en) * | 2021-09-30 | 2024-06-07 | 上海富元塑胶科技有限公司 | Antifouling intrinsic coating and preparation method and application thereof |
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Application publication date: 20120801 |