CN101845262A - Low surface energy liquid control release type marine anti-fouling paint - Google Patents
Low surface energy liquid control release type marine anti-fouling paint Download PDFInfo
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Abstract
The invention discloses a low surface energy liquid control release type marine anti-fouling paint, comprising the following components in parts by weight: 30.0-55.0 parts of film-forming resin, 7.0-18.0 parts of lamella cross-linking silicone oil microcapsule, 1.0-10.0 parts of plasticizer, 1.0-3.0 parts of defoaming agent, 15.0-35.0 parts of added pigment and 5.3-22.7 parts of solvent. The lamella cross-linking silicone oil microcapsule is obtained by polymerizing an oil-in-water system in situ; the core material of the lamella cross-linking silicone oil microcapsule is one or several of methyl silicone oil, hydroxy silicone oil, amino silicon oil and alkoxy silicone oil; and the wall material of the lamella cross-linking silicone oil microcapsule can be one of polyacrylamide, polyacrylic acid, polymaleic anhydride and the like which can be swelled in the water. The anti-fouling paint has the advantages of remarkable anti-fouling effects, no pollution to a marine environment, low cost and applicability for industrial application production. The film-forming resin is acrylic resin, the structural general formula of which is shown in the specification of the invention.
Description
Technical field
The present invention relates to anti-marine biofouling paint field, particularly a kind of low surface energy liquid control release type marine anti-fouling paint.
Background technology
The facility of any long-term exposure in seawater as hull bottom, aquaculture net cage etc., is very easy to be sticked to its surface and growth and breeding by various marine fouling organisms, causes the very big infringement of outward appearance and function, and brings enormous economic loss.These marine fouling organisms comprise animals such as barnacle, hydra, Ascidian, algae and mushrooms such as bacterium, fungi such as diatom, green alga.Marine organisms in case alow surface attachment will produce serious harm, mainly contain following several respects: 1. increase the surfaceness and the weight of hull, increase resistance, make the naval vessel speed of a ship or plane slow down, lose maneuvering ability, cause fuel consumption to increase, obnoxious flavour discharges to be increased; 2. increase depressed place frequency of maintenance on the boats and ships, lose time and resource, and can produce a large amount of toxic pollutants simultaneously; 3. quicken the corrosion of base material (steel, aluminium etc.) below the settled organism.
Tradition is used to prevent that the adherent antifouling paint of marine fouling organism from having tributyl tin from polishing type antifouling paint, Red copper oxide class antifouling paint etc., but can pollute and disabled [Claude Alzieu.Impact of tributyltin on marine invertebrates[J] .Ecotoxicology for environment owing to contain heavy metals such as tin, copper in above-mentioned several traditional antifouling paints, 2000, (9): 71-76; F.Garaventa, F.Pellizzato, M.Faimali et al, Imposexin Hexaplex trunculus at some sites on the North Mediterranean Coast as a base-line forfuture evaluation of the effectiveness of the total ban on organotin based antifouling paints[J] .Hydrobiologia, 2006 (555): 281-287; Li Zhengyan, Zhou Mingjiang, Li Jun etc., fentin chloride is to the influence [J] of Isochrysis galbana physiological function, ocean science collected papers, 1996, (37): 115-120; Wang Yongfang, the pollution of organo-tin compound and toxicity thereof [J], Chinese food health impurity, 2003,15 (3): 244-247], and Red copper oxide class antifouling paint, anti-fouling effect is not very desirable, use needs a large amount of uses just can reach certain effect, and a large amount of use Red copper oxide adds heavily contaminated on the one hand, can increase use cost again on the other hand.Particularly present, along with growing to even greater heights of environmental protection cry, various countries make laws one after another and limit the use of organotin, and International Maritime Organizaton (IMO) proposes, in antifouling paint, use organotin to complete prohibition in 2008, and the use of Red copper oxide class antifouling paint will be restricted further also.Therefore, develop to ocean environment free of contamination novel nontoxic, antifouling paint has been trend of the times to replace traditional poisonous antifouling paint efficiently.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of anti-fouling effect remarkable, and consumption is few, cost is low, environmental protection, low surface energy liquid control release type marine anti-fouling paint efficiently.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of low surface energy liquid control release type marine anti-fouling paint, and this coating is made up of each component of following mass fraction:
Film-forming resin: 30.0～55.0 parts
7.0～18.0 parts of shell-crosslinked silicone oil microcapsule
Softening agent: 1.0～10.0 parts
Defoamer: 1.0～3.0 parts
Color stuffing: 15.0～35.0 parts
Solvent: 10.0～40.0 parts,
Wherein, film-forming resin is for having the acrylic resin of formula (I) general structure:
Formula (I)
Wherein, R
1Be H or CH
3, R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3, m is 0～150 integer, n is 2～100 integer.
Above-mentioned film-forming resin is the acrylic resin that the direct from the market molecular formula of buying meets above-mentioned general formula (I), is acrylic resin commonly used in the paint field, need not to specify.
Above-mentioned shell-crosslinked silicone oil microcapsule are the low-energy liquid microcapsule, adopt following method preparation: select for use situ aggregation method to carry out in oil-in-water system, the concrete preparation process of microcapsule is routine techniques preparation in the industry, and roughly step is as follows:
(1) with sorbitan fatty acid ester (Span) and two kinds of surfactant compounds of polysorbate (Tween) as emulsifying agent, each component emulsifying agent with the preparation silicone oil emulsion, water, silicone oil (core) etc. are at 70 ℃ of following high-speed stirring emulsification pretreatments, and the consumption that passes through water-oil ratio example and emulsifying agent is regulated the silicone oil emulsion particle grain size, obtaining silicone oil content is 10%～20%, sorbitan fatty acid ester content is 2%～6%, polysorbate content is 2%～6%, all the other are oil-in-water (O/W) the type silicone oil emulsion of water, and above-mentioned each component concentration is a mass percent;
(2) with the silicone oil emulsion of step (1) gained and the monomeric aqueous solution of water-soluble polymer, wherein the quality proportioning between monomer and the water is 5%～10% in the monomeric aqueous solution of water-soluble polymer, monomer is a polyacrylamide, polyacrylic acid, a kind of in the monomer of polymkeric substance such as polymaleic anhydride, and then in said mixture, add linking agent, addition be water in the monomeric aqueous solution of above-mentioned water-soluble polymer quality 0.1%～1%, utilizing the method for in-situ polymerization is 40 ℃～80 ℃ in temperature of reaction, time is the shell (wall material) that generates a cross-linked polymer under 4～8 hours conditions at silicone oil emulsion particulate surface in situ, this shell coats the silicone oil emulsion particle wherein, thickness by monomeric concentration adjustment shell, the degree of crosslinking of the concentration adjustment shell by linking agent, gained suspension dimethylbenzene, dehydrated alcohol and distilled water wash, filter, obtain the silicone oil microcapsule; Quality proportioning between the monomeric aqueous solution of above-mentioned silicone oil emulsion and water-soluble polymer is 1: 1～5.
Above-mentioned steps 1～2 is all carried out under normal pressure.
In the above-mentioned shell-crosslinked silicone oil microcapsule original position polymerization, the core of shell-crosslinked silicone oil microcapsule is that the silicone oil in the shell-crosslinked silicone oil microcapsule is one or more in methyl-silicone oil, hydroxy silicon oil, amido silicon oil, the alkoxyl group silicone oil.
The wall material of above-mentioned shell-crosslinked silicone oil microcapsule be shell be can be in water wherein a kind of such as swollen polyacrylamide, polyacrylic acid, polymaleic anhydride; Linking agent is meant the linking agent of above-mentioned polyacrylamide, polyacrylic acid, polymaleic anhydride, is preferably diene class linking agents such as methylene-bisacrylamide, as N,N methylene bis acrylamide.
By the shell-crosslinked silicone oil microcapsule that above two steps obtain, the degree of crosslinking of its granular size, wall thickness, shell is all controlled, can regulate the rate of release of silicone oil in seawater by the content in coating by above three factors and microcapsule.
Above-mentioned softening agent is that phthalic ester is [as dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP)], fatty group dibasic acid [as: Octyl adipate (DOA), dioctyl sebacate (DOS)], phosphoric acid ester [as: Tritolyl Phosphate (TCP), phosphate toluene diphenyl ester (CDP)], epoxy compounds (as: epoxidised soybean oil, the epoxyoleic acid butyl ester), Reoplex (as: hexanodioic acid propylene glycol polyester), benzene polyacid ester (as: 1,2, the 4-triisooctyl trimellitate), chloro-plasticizer (as: clorafin, the pentachloro-methyl stearate), alkyl sulfonic ester, a kind of in the polyol ester etc.
Above-mentioned defoamer adopts modified dimethyl polysiloxane class (as epoxy group(ing) modified dimethyl polysiloxane, polyether-modified polydimethylsiloxane BYK300 etc.) or polyethers (as PPE type polyether antifoam agent) or higher alcohols (as DP592 etc.) defoamer.
Above-mentioned color stuffing is selected one or more in process white, titanium dioxide, light calcium carbonate, iron oxide red, zinc oxide, sepiolite, aluminium triphosphate, the carbon black for use.
Above-mentioned solvent is selected at least a in methylethylketone, acetone, pimelinketone, Virahol, propyl carbinol, methyl acetate, ethyl acetate, butylacetate, the dimethylbenzene for use.
Microcapsule content is controlled between 7.0～18.0%, is lower than the decline that this content can cause this coating antifouling property, is higher than this content and then causes unnecessary waste of material, and cost increases, and is unfavorable for applying of this technology.The interpolation of color stuffing gives antifouling paint enough mechanical propertys, prevents that coating from producing phenomenons such as ftractureing, come off, and being added with of various auxiliary agents is beneficial to antifouling paint and forms uniform and stable dispersion system.
Environment-friendly marine antifouling coating provided by the invention compared with prior art, has the following advantages:
1, the present invention is stain control agent with the low-energy liquid, and it is carried out micro encapsulation handle the microcapsule (shell-crosslinked silicone oil microcapsule) that obtained wrapping up low-energy liquid, itself and film-forming resin, softening agent, defoamer, color stuffing and solvent are constituted low-energy liquid slow release type antifouling paint jointly, utilize low-energy liquid to suppress biodeterioration from the slow release of microcapsule, thereby reach the purpose of anti-biological pollution, and do not contain elements such as any tin, copper to ocean environment existence harm, therefore, has advantage nontoxic, that timeliness is long; And because this coating can reach good anti-marine biofouling effect under lower concentration, use the antifouling paint that contains a large amount of Red copper oxide to compare with tradition, therefore use cost greatly reduces, and can overcome existing anti-soil technology weak effect, toxicity is big, cost is high shortcoming preferably;
2, the effect of the anti-marine biofouling of this antifouling paint is remarkable, can effectively prevent adhering to of marine lifes such as barnacle, algae, shellfish in 12 months;
3, this antifouling paint can be by the preparation and the convenient control of the addition in coating thereof of microcapsule in the rate of release of middle low-energy liquid;
4, the preparation technology of this antifouling paint is simple, and easy handling uses conventional equipment fully, is suitable for large-scale application.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Film-forming resin in the embodiment of the invention is a paint field acrylic resin commonly used, and the general structure that its structural formula meets preamble formula (I) all meets service requirements; Color stuffing in the embodiment of the invention, defoamer, softening agent, solvent all adopt the commercially available product that above-mentioned preamble requires that meets, the shell-crosslinked silicone oil microcapsule of the embodiment of the invention adopt preamble step 1～2 described preparations, for routine techniques in the industry, do not repeat them here.
Embodiment 1
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polymethylmethacryla/e /e acrylonitrile acid amides diblock copolymer): 35.0 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are methyl-silicone oil): 16.0 parts
Color stuffing (being mixed into): 24.2 parts by titanium dioxide, light calcium carbonate and iron oxide red mass ratio with 35: 11: 54
Defoamer (modified dimethyl polysiloxane class): 2.2 parts
Softening agent (clorafin): 2.0 parts
Solvent (solvent by dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvents) herein: 20.6 parts
By said ratio all substances are mixed the formation mixture.
Utilize sand milling that said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed (loss that the volatilization of each component etc. causes in the above-mentioned preparation process is ignored, following examples with) promptly obtains environment-friendly marine antifouling coating provided by the invention.
This antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value just reaches about 4% after six months.
Embodiment 2
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polyethyl methacrylate/acrylamide diblock copolymer): 42.8 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are hydroxy silicon oil): 10.0 parts
Color stuffing (being mixed into): 21.9 parts by titanium dioxide, process white and iron oxide red mass ratio with 12: 52: 36
Defoamer (modified dimethyl polysiloxane class): 1.0 parts
Softening agent (clorafin): 2.5 parts
Solvent (dimethylbenzene): 21.8 parts.
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.5 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 6% after six months.
Embodiment 3
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polypropylmethacryla,es/acrylamide diblock copolymer): 35.9 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are amido silicon oil): 7.5 parts
Color stuffing (process white, sepiolite, titanium dioxide and iron oxide red were with 39: 8: 13: 40 mass ratio mixes): 35.0 parts
Defoamer (modified dimethyl polysiloxane class): 2.0 parts
Softening agent (clorafin): 2.0 parts
Solvent (dimethylbenzene): 17.6 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 2.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.Model soaks the stained of rear surface appearance 4% in three months in seawater, after this soiling value maintains about 11%.
Embodiment 4
The mass fraction of each component of this antifouling paint is:
Film-forming resin (poly-n-butyl methacrylate/acrylamide diblock copolymer): 40.8 parts
Shell-crosslinked silicone oil microcapsule (shell is that polymaleic anhydride, silicone oil are alkoxyl group silicone oil): 13.2 parts
Color stuffing (titanium dioxide, light calcium carbonate and iron oxide red mix with 35: 11: 54 mass ratio): 17.2 parts
Defoamer (modified dimethyl polysiloxane class): 1.2 parts
Softening agent (clorafin): 2.3 parts
Solvent (dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvent): 25.3 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 4% after six months.
Embodiment 5
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polymethyl acrylate/acrylamide diblock copolymer): 44.8 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylamide, silicone oil are methyl-silicone oil): 9.7 parts
Color stuffing (titanium dioxide, process white and iron oxide red mix with 12: 52: 36 mass ratio): 23.0 parts
Defoamer (modified dimethyl polysiloxane class): 1.2 parts
Softening agent (clorafin): 2.6 parts
Solvent (dimethylbenzene): 18.7 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.5 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 5% after six months.
Embodiment 6
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polyethyl acrylate/acrylamide diblock copolymer): 41.0 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are hydroxy silicon oil): 8.4 parts
Color stuffing (process white, zinc oxide, titanium dioxide and iron oxide red were with 39: 8: 13: 40 mass ratio mixes): 35.0 parts
Defoamer (modified dimethyl polysiloxane class): 2.0 parts
Softening agent (clorafin): 2.0 parts
Solvent (dimethylbenzene): 11.6 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 2.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 9% after six months.
Embodiment 7
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polyacrylic acid propyl ester/acrylamide diblock copolymer): 30.5 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are alkoxyl group silicone oil): 16.5 parts
Color stuffing (titanium dioxide, light calcium carbonate and iron oxide red mix with 35: 11: 54 mass ratio): 24.2 parts
Defoamer (modified dimethyl polysiloxane class): 1.5 parts
Softening agent (clorafin): 2.0 parts
Solvent (dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvent): 25.3 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 8% after six months.
Embodiment 8
The mass fraction of each component of this antifouling paint is:
Film-forming resin (butyl polyacrylate/acrylamide diblock copolymer): 43.8 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are hydroxy silicon oil): 17.0 parts
Color stuffing (titanium dioxide, light calcium carbonate and iron oxide red mix with 35: 11: 54 mass ratio): 18.4 parts
Defoamer (modified dimethyl polysiloxane class): 1.0 parts
Softening agent (clorafin): 2.5 parts
Solvent (dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvent): 17.3 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, occurs 8% contaminated area in the time of six months, and after this soiling value rises to about 10%.
Embodiment 9
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polyethyl methacrylate/acrylamide diblock copolymer): 49.8 parts
Shell-crosslinked silicone oil microcapsule (shell is that polymaleic anhydride, silicone oil are methyl-silicone oil): 7.0 parts
Color stuffing (titanium dioxide, light calcium carbonate and iron oxide red mix with 35: 11: 54 mass ratio): 20.9 parts
Defoamer (higher alcohols defoamer DP592): 1.0 parts
Softening agent (clorafin): 3.5 parts
Solvent (dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvent): 18.0 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
This this antifouling paint brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.3% stained area promptly appearred in three months in the real extra large link plate of model, and soiling value is increased to 9% in the time of six months, after this maintains about 13% substantially.
Embodiment 10
The mass fraction of each component of this antifouling paint is:
Film-forming resin (polypropylmethacryla,es/acrylamide diblock copolymer): 32.4 parts
Shell-crosslinked silicone oil microcapsule (shell is that polyacrylic acid, silicone oil are amido silicon oil): 17.0 parts
Color stuffing (titanium dioxide, light calcium carbonate and iron oxide red mix with 35: 11: 54 mass ratio): 30.0 parts
Defoamer (modified dimethyl polysiloxane class: polyether-modified polydimethylsiloxane BYK300): 2.1 parts
Softening agent (clorafin): 2.0 parts
Solvent (dimethylbenzene and propyl carbinol with 7: 3 volume ratio blended mixed solvent): 16.5 parts
By said ratio all substances are mixed the formation mixture.
Said mixture was fully stirred 3.0 hours, make it to be uniformly dispersed, promptly obtain environment-friendly marine antifouling coating provided by the invention.
The antifouling paint sample of inventive embodiments preparation brushed on the steel substrate that applies epoxy anticorrosion primer make model, the room temperature thorough drying.Place natural sea-water to carry out the extra large board experiment of reality then, the soiling value of model surface different time sections is as shown in table 1.The no any marine life in model surface adheres in the first three months, and model surface contamination value is about 6% after six months.
Table 1 model surface different time sections fouling organism bond area
The antifouling paint of above-mentioned 10 embodiment is made model, and it is as follows that model is hung over its result of rate of release who measures silicone oil in the simulated seawater:
The rate of release of table 2 silicone oil from antifouling coating
Claims (9)
1. low surface energy liquid control release type marine anti-fouling paint, it is characterized in that: this coating is made up of each component of following mass fraction:
Film-forming resin: 30.0～55.0 parts
Shell-crosslinked silicone oil microcapsule: 7.0～18.0 parts
Softening agent: 1.0～10.0 parts
Defoamer: 1.0～3.0 parts
Color stuffing: 15.0～35.0 parts
Solvent: 10.0～40.0 parts,
Film-forming resin wherein is for having the acrylic resin as shown in the formula (I) general structure:
In the described formula (I), R
1Be H or CH
3, R
2Be CH
3, CH
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3In any one, m is 0～150 integer, n is 2～100 integer.
2. low surface energy liquid control release type marine anti-fouling paint according to claim 1 is characterized in that: described shell-crosslinked silicone oil microcapsule, and its concrete preparation process is as follows:
(1) with sorbitan fatty acid ester and two kinds of surfactant compounds of polysorbate as emulsifying agent, with each component of preparation silicone oil emulsion is that emulsifying agent, water, silicone oil are at 70 ℃ of following high-speed stirring emulsification pretreatments, and the consumption that passes through water-oil ratio example and emulsifying agent is regulated the silicone oil emulsion particle grain size, obtain silicone oil content and be 10%～20%, sorbitan fatty acid ester content is 2%～6%, polysorbate content is 2%～6%, all the other are the oil-in-water-type silicone oil emulsion of water, above-mentioned each component concentration is a mass percent;
(2) with the silicone oil emulsion of step (1) gained and the monomeric aqueous solution of water-soluble polymer, wherein monomeric mass percent is 5%～10% in the monomeric aqueous solution of water-soluble polymer, monomer is a polyacrylamide, polyacrylic acid, a kind of in the monomer of polymaleic anhydride correspondence, and then in said mixture, add linking agent, addition be water in the monomeric aqueous solution of above-mentioned water-soluble polymer quality 0.1%～1%, utilizing the method for in-situ polymerization is 40 ℃～80 ℃ in temperature of reaction, time is the shell that generates a cross-linked polymer under 4～8 hours conditions at silicone oil emulsion particulate surface in situ, this shell coats the silicone oil emulsion particle wherein, thickness by monomeric concentration adjustment shell, the degree of crosslinking of the concentration adjustment shell by linking agent, gained suspension dimethylbenzene, dehydrated alcohol and distilled water wash, filter, obtain shell-crosslinked silicone oil microcapsule; Quality proportioning between the monomeric aqueous solution of above-mentioned silicone oil emulsion and water-soluble polymer is 1: 1～5.
3. low surface energy liquid control release type marine anti-fouling paint according to claim 2 is characterized in that: the core of described shell-crosslinked silicone oil microcapsule is that silicone oil is one or more in methyl-silicone oil, hydroxy silicon oil, amido silicon oil, the alkoxyl group silicone oil.
4. low surface energy liquid control release type marine anti-fouling paint according to claim 2 is characterized in that: the wall material of described shell-crosslinked silicone oil microcapsule is that shell is a kind of in polyacrylamide, polyacrylic acid, the polymaleic anhydride.
5. low surface energy liquid control release type marine anti-fouling paint according to claim 2 is characterized in that: the linking agent described in the step (2) is a methylene-bisacrylamide diene class linking agent.
6. low surface energy liquid control release type marine anti-fouling paint according to claim 1, it is characterized in that: described softening agent is clorafin, pentachloro-methyl stearate, dioctyl phthalate (DOP), dibutyl phthalate, Octyl adipate, dioctyl sebacate, Tritolyl Phosphate, phosphate toluene diphenyl ester, epoxidised soybean oil, epoxyoleic acid butyl ester, hexanodioic acid propylene glycol polyester, 1,2, a kind of in 4-triisooctyl trimellitate, alkyl sulfonic ester or the polyol ester.
7. low surface energy liquid control release type marine anti-fouling paint according to claim 1 is characterized in that: described defoamer is modified dimethyl polysiloxane class or polyethers or higher alcohols defoamer.
8. low surface energy liquid control release type marine anti-fouling paint according to claim 1 is characterized in that: described color stuffing is a kind of or its several combination arbitrarily in process white, titanium dioxide, sepiolite, light calcium carbonate, iron oxide red, zinc oxide, aluminium triphosphate or the carbon black.
9. low surface energy liquid control release type marine anti-fouling paint according to claim 1 is characterized in that: described solvent is a kind of or its several combination arbitrarily in methylethylketone, acetone, pimelinketone, Virahol, propyl carbinol, methyl acetate, ethyl acetate, butylacetate or the dimethylbenzene.
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| CN2010101646287A CN101845262B (en) | 2010-05-07 | 2010-05-07 | Low surface energy liquid control release type marine anti-fouling paint |
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| CN2010101646287A CN101845262B (en) | 2010-05-07 | 2010-05-07 | Low surface energy liquid control release type marine anti-fouling paint |
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Cited By (11)
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| CN102070863A (en) * | 2010-12-15 | 2011-05-25 | 中国科学技术大学 | Antifouling material and application thereof |
| CN102127185A (en) * | 2010-12-15 | 2011-07-20 | 浙江海洋学院 | Acrylic resin with epoxy cycle on side chain and preparation and use thereof |
| CN102181126A (en) * | 2011-01-27 | 2011-09-14 | 武汉材料保护研究所 | Low surface energy polymer microcapsules and preparation method thereof |
| CN102212306A (en) * | 2011-05-31 | 2011-10-12 | 浙江大学 | Organosilicon type marine antifouling paint binder and preparation method and application thereof |
| CN102220080A (en) * | 2011-05-31 | 2011-10-19 | 浙江大学 | Quaternary ammonium salt modified organosilicon polyurethane ocean antifouling paint and preparation method and application thereof |
| CN104845467A (en) * | 2015-04-29 | 2015-08-19 | 天津纳微华瑞科技有限公司 | Environment-friendly antifouling damping complex-function coating and preparation method thereof |
| CN105062248A (en) * | 2015-08-03 | 2015-11-18 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
| CN105199517A (en) * | 2015-11-04 | 2015-12-30 | 济南思拓新源医药科技有限公司 | Coating and preparation method thereof |
| CN109021747A (en) * | 2018-07-02 | 2018-12-18 | 巢湖市天宇渔具有限公司 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
| CN109609029A (en) * | 2018-12-05 | 2019-04-12 | 杭州师范大学 | It is a kind of with the low surface energy antifouling coating for seas and preparation method thereof for delaying low molecular weight lubricant release action |
| CN110509579A (en) * | 2019-09-12 | 2019-11-29 | 浙江道明光电科技有限公司 | A kind of compound board manufacturing method of PMMA alloy-PC |
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| CN101024741A (en) * | 2007-02-09 | 2007-08-29 | 重庆大学 | Anti-corrosion anti-dirt method or biological anti-dirt and conductive anti-dirt combination |
| CN101659816A (en) * | 2009-09-24 | 2010-03-03 | 中国人民解放军后勤工程学院 | Paraffin microcapsule phase change heat storage and insulation coating and preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101024741A (en) * | 2007-02-09 | 2007-08-29 | 重庆大学 | Anti-corrosion anti-dirt method or biological anti-dirt and conductive anti-dirt combination |
| CN101659816A (en) * | 2009-09-24 | 2010-03-03 | 中国人民解放军后勤工程学院 | Paraffin microcapsule phase change heat storage and insulation coating and preparing method |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127185A (en) * | 2010-12-15 | 2011-07-20 | 浙江海洋学院 | Acrylic resin with epoxy cycle on side chain and preparation and use thereof |
| CN102070863B (en) * | 2010-12-15 | 2013-05-29 | 中国科学技术大学 | Antifouling material and application thereof |
| CN102070863A (en) * | 2010-12-15 | 2011-05-25 | 中国科学技术大学 | Antifouling material and application thereof |
| CN102127185B (en) * | 2010-12-15 | 2013-01-09 | 浙江海洋学院 | Acrylic resin with epoxy cycle on side chain and preparation and use thereof |
| CN102181126B (en) * | 2011-01-27 | 2013-01-30 | 武汉材料保护研究所 | Low surface energy polymer microcapsules and preparation method thereof |
| CN102181126A (en) * | 2011-01-27 | 2011-09-14 | 武汉材料保护研究所 | Low surface energy polymer microcapsules and preparation method thereof |
| CN102220080A (en) * | 2011-05-31 | 2011-10-19 | 浙江大学 | Quaternary ammonium salt modified organosilicon polyurethane ocean antifouling paint and preparation method and application thereof |
| CN102212306B (en) * | 2011-05-31 | 2013-05-08 | 浙江大学 | Organosilicon type marine antifouling paint binder and preparation method and application thereof |
| CN102212306A (en) * | 2011-05-31 | 2011-10-12 | 浙江大学 | Organosilicon type marine antifouling paint binder and preparation method and application thereof |
| CN104845467A (en) * | 2015-04-29 | 2015-08-19 | 天津纳微华瑞科技有限公司 | Environment-friendly antifouling damping complex-function coating and preparation method thereof |
| CN105062248A (en) * | 2015-08-03 | 2015-11-18 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
| CN105199517A (en) * | 2015-11-04 | 2015-12-30 | 济南思拓新源医药科技有限公司 | Coating and preparation method thereof |
| CN109021747A (en) * | 2018-07-02 | 2018-12-18 | 巢湖市天宇渔具有限公司 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
| CN109609029A (en) * | 2018-12-05 | 2019-04-12 | 杭州师范大学 | It is a kind of with the low surface energy antifouling coating for seas and preparation method thereof for delaying low molecular weight lubricant release action |
| CN110509579A (en) * | 2019-09-12 | 2019-11-29 | 浙江道明光电科技有限公司 | A kind of compound board manufacturing method of PMMA alloy-PC |
| CN110509579B (en) * | 2019-09-12 | 2021-12-31 | 浙江道明光电科技有限公司 | Method for manufacturing PMMA alloy-PC composite board |
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