CN102337063B - Preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil, paint and construction method - Google Patents
Preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil, paint and construction method Download PDFInfo
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Abstract
The invention discloses a preparation method of low-surface-energy ship antifouling paint capable of releasing silicone oil. The preparation method comprises the following steps: 1) preparing a raw material in advance; and 2) preparing the paint. The invention also discloses paint for implementing the preparation method of the low-surface-energy ship antifouling paint capable of releasing the silicone oil and a construction method for applying the paint. The method provided by the invention has simple preparation process and has high production efficiency, and is easy to realize; the surface energy of the paint provided by the invention is low, the silicon oil releasing speed is slow, and the antifouling property can be maintained for a long time under the condition of the same coating thickness, thereby reducing the maintenance cost of a ship antifouling coating; the VOC (volatile organic compound) content of the antifouling paint is low, thereby reducing atmosphere pollution; and the coating releases low-toxicity silicone oil, thereby lowering the pollution on marine environment. The construction method provided by the invention is simple and has low cost; and by using the construction method, the antifouling function of the paint is effectively exerted.
Description
Technical field
The invention belongs to Marine Antifouling Coatings, be specifically related to a kind of low-surface-energy ship antifouling paint preparation method, coating and constructional method of energy releasing silicone oil.
Background technology
Boats and ships are important channels of international staple commodities transportation, and in ocean environment, boats and ships can be subject to sea-water corrosion, also are subject to adhering to of marine microorganism simultaneously and the biological pollution that causes.According to statistics, many kinds of marine fouling organisms of 2000-3000 are arranged in the marine site all over the world, wherein about 600 kinds of attached plants and 1300 kinds of epizoites, the larva of these microorganisms and spore be floating in the ocean, move about, when it is grown to a certain degree adhering to alow, settle down and further breeding, after boats and ships adhere to marine life, can cause surface friction drag to increase, reduce ship's speed, increase fuel consumption, increase the frequency of maintenance that lies up.
For preventing that marine organisms from adhering to, effective means is at shell surface-coated antifouling paint.In the past few decades, the antifouling paint that contains organotin was once used in a large number.But disengage thing marine organisms have been caused teratogenesis and long-term Marine Environmental Pollution.Therefore, from 1 day January in 2008, Marine Environmental Protection Committee (MEPC) completely forbade use.At present, the substitute is the less hypotoxic stain control agents such as Red copper oxide of toxicity.But the result shows according to current research, and the halobiontic kind reduction of some International Ports and the minimizing of biomass and the use of copper class stain control agent have very large relation.Therefore, the exploitation hypotoxicity antifouling paint that disengages thing, low surface energy becomes main solution.
At present, the antifouling paint that has a low surface energy constantly is developed.Chinese patent CN1498252A has described a kind of antifouling paint compositions, comprising PFPE, silicone resin, solidifying agent etc.This coating composition has low surface energy, only relies on low surface energy to reach and reduces biological adhering to, and in the marine low speed operation, when length of port stay is longer, its anti-fouling effect is difficult to guarantee.
Chinese patent CN1492010A has described a kind of multipolymer by fluoro-acrylate monomer, vinylformic acid three organic radical silyl ester monomers, acrylic monomer polymerization, and utilize this multipolymer as film forming matter, cooperate Red copper oxide and ferric oxide etc. to be mixed with antifouling paint.By regulating the proportioning of monomer, multipolymer has 1～200 micron/month etch rates.This coating has low surface energy, the feature of polishing certainly, have good application prospect, but this coating contains the Red copper oxide stain control agent, still ocean environment is had potential danger, destructiveness, and ejecta is difficult to be biodegradable, and the residence time is long.
Summary of the invention
For above-mentioned deficiency, one of the object of the invention is, provides a kind of technique simple and easy, the low-surface-energy ship antifouling paint preparation method of the energy releasing silicone oil that is easy to produce;
Two of the object of the invention is, a kind of coating of implementing the low-surface-energy ship antifouling paint preparation method of above-mentioned energy releasing silicone oil is provided, this coating utilizes the didirtresistance of its low surface energy, slowly the biological tack of releasing silicone oil reduction reaches dual anti-fouling effect, and this double effects gives coating good antifouling property.
Three of the object of the invention is, a kind of constructional method of implementing above-mentioned coating is provided.
For achieving the above object, technical scheme provided by the present invention is:
A kind of low-surface-energy ship antifouling paint preparation method of energy releasing silicone oil is characterized in that it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are as follows:
Fluorine silicon acrylic resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Described solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Catalyzer is organotin catalysts.
(2) preparation coating: fluorine silicon acrylic resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
The preparation method of the fluorine silicon acrylic resin in the described step (1) specifically comprises the steps:
(1.1) preparation the first mixing solutions: the weight percentage of the first mixing solutions is 5～30%, adds N-BUTYL ACETATE in dimethylbenzene, and evenly mixing makes the first mixing solutions; The weight percentage of dimethylbenzene in the first mixing solutions is 30～70%;
(1.2) preparation the second mixing solutions: prepare the raw material of the second mixing solutions, each component and the weight percentage thereof of this raw material are as follows:
Methyl methacrylate 20～50%;
Butyl acrylate 10～20%;
Hydroxyethyl methylacrylate 3～10%;
Initiator 0.5～5%;
The mixing solutions 3～20% of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate,
The mixing solutions of methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate, initiator, fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate of corresponding proportional quantity evenly mixed make the second mixing solutions; The weight percentage of fluorine-containing (methyl) acrylate in the mixing solutions of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate is 20～80%.
(1.3) drip mixing: the first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to the second mixing solutions, until dropwise;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon acrylic resin.
The median size of the powder in the described step (1) is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.Described dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Described anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Described step (2), it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon acrylic resin, silicone oil, anti-sagging agent are mixed, and add in the agitator with thermometer, 35～45 ℃ of lower mix and blends 25～35 minutes, make the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon acrylic resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and the grinding distribution time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
Powder 30～20%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
A kind of coating of implementing the low-surface-energy ship antifouling paint preparation method preparation of above-mentioned energy releasing silicone oil is characterized in that its each component and weight percentage thereof are as follows:
Fluorine silicon acrylic resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Described catalyzer is organotin catalysts;
The median size of described powder is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.Described dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Described anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Described flaky material is that sericite or the talcum powder of 1～10 μ m made by particle size diameter.
A kind of constructional method of implementing above-mentioned coating is characterized in that it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
Described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick-slurry type modified epoxy slurry lacquer, and thickness is 45～80 μ m.
Described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
Beneficial effect of the present invention is: the preparation technology of method provided by the invention is simple and easy, be easy to realize that production efficiency is high; The surface energy of coating provided by the invention is low, and the silicone oil release rate is slow, under the condition of same coat-thickness, can keep more muchly antifouling property, has reduced the maintenance cost of marine antifouling coating; And the VOC content of antifouling paint is low, has reduced air environmental pollution, and what coating discharged is hypotoxic silicone oil, has reduced the pollution to ocean environment.Constructional method provided by the invention is simple, and cost is low, can make coating effectively give play to its anti-pollution function.
Below in conjunction with drawings and Examples, the invention will be further described.
Description of drawings
Fig. 1 is preparation flow figure of the present invention.
Embodiment
Embodiment 1: referring to Fig. 1,
A kind of low-surface-energy ship antifouling paint preparation method of energy releasing silicone oil, it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are as follows:
Fluorine silicon acrylic resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Described solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Catalyzer is organotin catalysts;
Dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S.
Anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Wherein the preparation method of fluorine silicon acrylic resin specifically comprises the steps:
(1.1) preparation the first mixing solutions: the weight percentage of the first mixing solutions is 5～30%, adds N-BUTYL ACETATE in dimethylbenzene, and evenly mixing makes the first mixing solutions; The weight percentage of dimethylbenzene in the first mixing solutions is 30～70%;
(1.2) preparation the second mixing solutions: prepare the raw material of the second mixing solutions, each component and the weight percentage thereof of this raw material are as follows:
Methyl methacrylate 20～50%;
Butyl acrylate 10～20%;
Hydroxyethyl methylacrylate 3～10%;
Initiator 0.5～5%;
The mixing solutions 3～20% of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate,
The mixing solutions of methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate, initiator, fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate of corresponding proportional quantity evenly mixed make the second mixing solutions; The weight percentage of fluorine-containing (methyl) acrylate in the mixing solutions of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate is 20～80%.
(1.3) drip mixing: the first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to the second mixing solutions, until dropwise;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon acrylic resin.
The median size of described powder is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.
(2) preparation coating: fluorine silicon acrylic resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
The low-surface-energy ship antifouling paint preparation method of described energy releasing silicone oil, described step (2), it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon acrylic resin, silicone oil, anti-sagging agent are mixed, and add in the agitator with thermometer, 35～45 ℃ of lower mix and blends 25～35 minutes, make the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon acrylic resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and the grinding distribution time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
Powder 30～20%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
A kind of coating of implementing the low-surface-energy ship antifouling paint preparation method preparation of above-mentioned energy releasing silicone oil, its each component and weight percentage thereof are as follows:
Fluorine silicon acrylic resin 15～50%;
Powder 30～20%;
Silicone oil 5～30%;
Solvent 10～25%;
Catalyzer 0.1～5%;
Dispersion agent 0.2～2%;
Anti-sagging agent 0.2～2%;
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Described catalyzer is organotin catalysts.
The median size of the powder in the described coating is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least.
Dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S.
Anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
Described flaky material is that sericite or the talcum powder of 1～10 μ m made by particle size diameter.
A kind of constructional method of implementing above-mentioned coating, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
Described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick-slurry type modified epoxy slurry lacquer, and thickness is 45～80 μ m;
Described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
Embodiment 2, and low-surface-energy ship antifouling paint preparation method, coating and the constructional method of energy releasing silicone oil are as follows:
A component: take by weighing fluorine silicon acrylic resin 235g, dimethylbenzene 20g, tetrahydrofuran (THF) 30g, hydroxy silicon oil 220g, BYK-430 are 4.8g, add in the agitator with thermometer, 40 ℃ of lower mixed stirrings 0.5 hours.
B component: take by weighing nano silica powder 75g, join and consist of BYK-140 reagent 5g, in the miscellany of dimethylbenzene 60g, tetrahydrofuran (THF) 45g, N-BUTYL ACETATE 40g, dibutyl tin laurate 2.2g.In shredder, with 1000 rev/mins of rotating speeds, grinding distribution 3 hours.
During use, A component and B component are mixed, stirring at room 120 minutes can be used.
The constructional method of coating, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the epoxy zinc rich primer that plays rust inhibition to the surface of steel, epoxy zinc rich primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 50 μ m;
3) preparation epoxy micaceous iron intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 200 μ m;
4) coating of the present invention evenly is coated on the middle layer, forming thickness is the top coat layer of 350 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Embodiment 3: the distinctive points of itself and embodiment 2 is as follows:
The content of each component and preparation method are as follows in the coating:
A component: fluorine silicon acrylic resin 280g, dimethylbenzene 60g, tetrahydrofuran (THF) 30g, N-BUTYL ACETATE 50g, dimethyl silicone oil 350g, dibutyl tin laurate 3 grams are mixed.In the agitator of adding with thermometer, 40 ℃ of lower mixed stirrings 0.5 hour.
B component: at room temperature, take by weighing 100g nano-titanium dioxide powder, 5g BYK-323, with mixed solvent and the 3.5g BYK-163 of 60g dimethylbenzene, 45g tetrahydrofuran (THF), 40g N-BUTYL ACETATE composition, in shredder, with 1200 rev/mins of rotating speeds, grinding distribution 4 hours.
During use, A component and B component are mixed, room temperature strong stirring 2 hours can use.
The constructional method of coating, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and thick-slurry type modified epoxy slurry lacquer evenly is coated on the surface of steel, and forming thickness is the prime coat of 50 μ m;
3) the preparation acrylic polyurethane coating evenly is coated in it on prime coat, and forming thickness is the middle layer of 200 μ m;
4) coating of the present invention evenly is coated on the middle layer, forming thickness is the top coat layer of 300 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Embodiment 4: the distinctive points of itself and embodiment 2 is as follows:
The content of each component and preparation method are as follows in the coating:
A component: take by weighing fluorine silicon acrylic resin 1020g, dimethylbenzene 110g, tetrahydrofuran (THF) 80g, hydroxy silicon oil 800g, BYK-323 are 20g, add in the agitator with thermometer, 40 ℃ of lower mixed stirrings 0.5 hours.
B component: take by weighing nano silica powder 300g, join and consist of BYK-140S reagent 22g, in the miscellany of dimethylbenzene 210g, tetrahydrofuran (THF) 180g, N-BUTYL ACETATE 140g, dibutyl tin laurate 8g.In shredder, with 1000 rev/mins of rotating speeds, grinding distribution 3 hours.
During use, A component and B component are mixed, stirring at room 2 hours can be used.
The constructional method of coating, it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed; The surface of steel plate degree of cleaning reach the Sa2 of GB/T 8923-1988 regulation
1/
2Level.
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, zinc-rich coating evenly is coated on the surface of steel, and forming thickness is the prime coat of 80 μ m;
3) preparation epoxy micaceous iron intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 150 μ m;
4) coating of the present invention evenly is coated on the middle layer, forming thickness is the top coat layer of 400 μ m.
Drying conditions is 25 ℃, 50% relative humidity, and be 7 days time of drying, makes the marine antifouling coating.
Table 1 is to adopt the resulting finish paint coating process of the above embodiment of the present invention and physico-chemical parameter, and design parameter is as follows:
Table 1: embodiment finish paint performance perameter
Can find out that by the performance index in the table 1 because the surface energy of coating is low, utilizes the didirtresistance of the low surface energy of coating, slow releasing silicone oil to reduce biological tack and reach dual anti-fouling effect, this double effects gives coating good antifouling property.This coating system matrix resin is the fluorine silicon acrylic resin, has low surface energy; It is silicone oil that coating is disengaged thing, and it has low toxicity, the slow characteristics of release rate.This coating has longer antifouling phase, better didirtresistance, low VOC content and the hypotoxic characteristics of releaser.Under the condition of same coat-thickness, can keep more muchly antifouling property, reduced the maintenance cost of marine antifouling coating.And the VOC content of antifouling paint is low, has reduced air environmental pollution, and what coating discharged is hypotoxic silicone oil, has reduced the pollution to ocean environment.
As described in the above embodiment of the present invention, adopt method same or similar with it and component and other anti-fouling ship paint and the constructional method that obtain, all in protection domain of the present invention.
Claims (9)
1. the low-surface-energy ship antifouling paint preparation method of an energy releasing silicone oil is characterized in that it may further comprise the steps:
(1) preparing material: each component and the weight percentage thereof of coating are as follows:
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Described solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Catalyzer is organotin catalysts;
The preparation method of described fluorine silicon acrylic resin specifically comprises the steps:
(1.1) preparation the first mixing solutions: the weight percentage of the first mixing solutions is 5～30%, adds N-BUTYL ACETATE in dimethylbenzene, and evenly mixing makes the first mixing solutions; The weight percentage of dimethylbenzene in the first mixing solutions is 30～70%;
(1.2) preparation the second mixing solutions: prepare the raw material of the second mixing solutions, each component and the weight percentage thereof of this raw material are as follows:
The mixing solutions 15% of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate,
The mixing solutions of methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate, initiator, fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate of corresponding proportional quantity evenly mixed make the second mixing solutions; The weight percentage of fluorine-containing (methyl) acrylate in the mixing solutions of fluorine-containing (methyl) acrylate and siliceous (methyl) acrylate is 20～80%;
(1.3) drip mixing: the first mixing solutions is heated, when being warmed up to 60～100 ℃, slowly be added dropwise to the second mixing solutions, until dropwise;
(1.4) insulation: after dropwising, constant temperature kept 2～20 hours, made the fluorine silicon acrylic resin;
(2) preparation coating: fluorine silicon acrylic resin, powder, silicone oil, solvent, catalyzer, dispersion agent, the anti-sagging agent of corresponding proportional quantity are carried out dispersing and mixing, make coating.
2. the low-surface-energy ship antifouling paint preparation method of energy releasing silicone oil according to claim 1 is characterized in that,
The median size of the powder in the described step (1) is 20～1000nm;
The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least;
Described dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S;
Described anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
3. the low-surface-energy ship antifouling paint preparation method of energy releasing silicone oil according to claim 1 is characterized in that, described step (2), and it specifically comprises the steps:
(2.1) preparation A component: by corresponding proportional quantity fluorine silicon acrylic resin, silicone oil, anti-sagging agent are mixed, and in the agitator of adding with thermometer, mix and blend is 25～35 minutes under 35～45 ° of C, makes the A component;
More than the quality percentage composition of each component in coating be:
Fluorine silicon acrylic resin 15～50%;
Silicone oil 5～30%;
Anti-sagging agent 0.2～2%,
(2.2) preparation B component: press corresponding proportional quantity with powder, dispersion agent, solvent, catalyst mix, and be transferred in the shredder, start shredder, the speed setting of this shredder is 900～1100 rev/mins, and the grinding distribution time is 110～250 minutes;
More than the quality percentage composition of each component in coating be:
(2.3) A component and B component are mixed, and at room temperature stirred 110～250 minutes, make coating.
4. coating of implementing the described low-surface-energy ship antifouling paint preparation method preparation that can releasing silicone oil of claim 1 is characterized in that its each component and weight percentage thereof are as follows:
Described powder is for including at least a kind of in silicon-dioxide, aluminum oxide, the titanium dioxide;
Solvent is mixed by in benzene,toluene,xylene, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, vinyl acetic monomer, N-BUTYL ACETATE, 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), the tetrahydrofuran (THF) two or more;
Described catalyzer is organotin catalysts.
5. coating according to claim 4 is characterized in that, the median size of described powder is 20～1000nm; The molecular-weight average of silicone oil is 1000～10000g/mol, and it includes a kind of in the polysiloxane that amino polysiloxane, polysiloxane, polydimethylsiloxane, PSI, one or both ends that one or both ends are hydroxyl are alkoxyl group at least; Described dispersion agent is that model is one or both mixing in the dispersion agent of BYK-110, BYK-140, BYK-163, BYK-104S; Described anti-sagging agent is that model is one or both mixing in the anti-sagging agent of Dapro BEZ-75, BYK-323, BYK-430.
6. coating according to claim 4 is characterized in that, described flaky material is that sericite or the talcum powder of 1～10 μ m made by particle size diameter.
7. constructional method of implementing the described coating of claim 4 is characterized in that it may further comprise the steps:
1) surface of the steel of required coating is cleaned with roughness processed;
2) preparation has good sticking power and the steel anti-corrosion primer that plays rust inhibition to the surface of steel, and this steel anti-corrosion primer evenly is coated on the surface of steel, and forming thickness is the prime coat of 45～80 μ m;
3) the preparation intermediate coat evenly is coated in it on prime coat, and forming thickness is the middle layer of 140～210 μ m;
4) coating evenly is coated on the middle layer, forming thickness is the top coat layer of 230～320 μ m.
8. coating according to claim 7 is characterized in that, described steel anti-corrosion primer is a kind of in epoxy zinc rich primer, zinc-rich coating, the thick-slurry type modified epoxy slurry lacquer, and thickness is 45～80 μ m.
9. coating according to claim 7 is characterized in that, described intermediate coat is epoxy micaceous iron intermediate coat or acrylic polyurethane coating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634374A (en) * | 2016-10-11 | 2017-05-10 | 安徽卡塔门窗有限公司 | Aluminum alloy bathroom door and production method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10385221B2 (en) | 2014-04-03 | 2019-08-20 | Ppg Coatings Europe B.V. | Erodible antifouling coating composition |
| CN104893569A (en) * | 2015-06-10 | 2015-09-09 | 上海大学 | Silica sol enhanced organic silicon antifouling paint and preparation method thereof |
| CN105400419A (en) * | 2015-12-22 | 2016-03-16 | 天津米一科技有限公司 | Epoxy modified silane marine anti-corrosion and anti-fouling paint |
| CN106280820A (en) * | 2016-07-27 | 2017-01-04 | 上海巨峰化工有限公司 | A kind of fluorine silicon acrylate paint |
| CN110358015B (en) * | 2019-06-26 | 2022-01-07 | 嘉宝莉化工集团股份有限公司 | Self-lubricating hydrophobic silicone-acrylic emulsion and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492010A (en) * | 2002-01-03 | 2004-04-28 | ���з��ɻ�ѧ�ɷ�����˾ | Copolymers containing fluorine and silyl groups and their use in marine antifouling compositions |
| CN1861714A (en) * | 2006-06-02 | 2006-11-15 | 北京首创纳米科技有限公司 | Nano composite top facing paint with hydrophobic foul resisting sticking-proof and preparation process thereof |
| CN101250378A (en) * | 2008-03-14 | 2008-08-27 | 厦门大学 | Silicone-acrylate low surface energy ocean anti-fouling paint and preparation method thereof |
-
2011
- 2011-08-15 CN CN 201110233105 patent/CN102337063B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492010A (en) * | 2002-01-03 | 2004-04-28 | ���з��ɻ�ѧ�ɷ�����˾ | Copolymers containing fluorine and silyl groups and their use in marine antifouling compositions |
| CN1861714A (en) * | 2006-06-02 | 2006-11-15 | 北京首创纳米科技有限公司 | Nano composite top facing paint with hydrophobic foul resisting sticking-proof and preparation process thereof |
| CN101250378A (en) * | 2008-03-14 | 2008-08-27 | 厦门大学 | Silicone-acrylate low surface energy ocean anti-fouling paint and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634374A (en) * | 2016-10-11 | 2017-05-10 | 安徽卡塔门窗有限公司 | Aluminum alloy bathroom door and production method thereof |
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