CN1039255A - Prevent the paint of marine biofouling - Google Patents
Prevent the paint of marine biofouling Download PDFInfo
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- CN1039255A CN1039255A CN89103696A CN89103696A CN1039255A CN 1039255 A CN1039255 A CN 1039255A CN 89103696 A CN89103696 A CN 89103696A CN 89103696 A CN89103696 A CN 89103696A CN 1039255 A CN1039255 A CN 1039255A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Abstract
A kind of binder for film formation that is used for preventing the paint of marine biofouling, it is the insoluble but hydrolyzable polymkeric substance of seawater, general expression is Z (O-X) n, in the formula Z for can the dissolving of its hydrolyzed state at seawater or the dispersive general expression be the Z (OH) residue of the hydroxy-functional polymkeric substance of n, n is the integer greater than 1, each X respectively does for oneself, and feasible-O-X group is hydrolyzed in seawater-and the part of OH group.The paint of anti-marine biofouling comprises this binder for film formation and other pigment, and this pigment is that ocean biocide or pigment add independent ocean biocide, can be by tackiness agent and other batch mixes are obtained.
Description
The present invention relates to be applied to may with such as the biological surface that contacts of stained property in the water such as marine alga, sea grass and barnacle preventing the paint of marine biofouling, these surfaces are such as, the cooling water outlet in boats and ships, canoe or power station.More particularly, relate to the improvement of the tackiness agent that is used for this class paint.
In recent years, the most successful anti-fouling paint is that polishing antifouling decreases paint voluntarily.The tackiness agent that this paint uses is the linear polymer that contains side group, when polymkeric substance one reacts with seawater, this side group just discharges, last polymkeric substance can be dispersed or dissolved in fully in the seawater and be cleaned from painted surface, expose the new surface of tackiness agent, similar reaction can be carried out to seawater in this new surface.This paint had description in such as English Patent 1457590.The anti-fouling active release of the may command of attenuate gradually biocide of paint films and the pigment that in paint, exists or as leavings group.The well-known benefit of this paint of polishing voluntarily is, this paint films be tending towards keeping at least its initial slickness and may because the effect of the water of relative movement and even become more smooth, and be included in that biocide in the paint trends towards isostatic or constant speed discharges from the surface.
Only to be the coml meaning used tackiness agent from polishing paint is the multipolymer of three organotin esters of alkene unsaturated carboxylic acid.Three organotins provide the effect of the biocide of some paint, and three organotin esters can easily be hydrolyzed, and depend on this hydrolysis from polishing action.Biocidal activity can strengthen by other anti-fouling materials, and these materials are dispersed or dissolved in the paint films.It is advantageous decreasing paint from polishing antifouling, and it does not rely on the release of three organotin groups, because price reasons, and again because the effectiveness of the biocidal effect of three organotins may be unwanted.Considered particularly the environmental influence of three organotin biocides of discharging from yacht.
Many suggestions have been arranged, in the fat that is easy to hydrolysis with a kind of carboxylic acid polyalcohol with formation,, industrially in polishing paint, can replace three organotin parts but also wait in expectation with a kind of group of alternative three organotins.Open No. 84/02915 suggestion of WO of international monopoly such one big class group.No. 23200 suggestion of european patent application a kind of water of one or more hydrolyzable sulfonic acid or sulfate group that comprises easily lose polymkeric substance, this group can produce the acid groups be linked to polymkeric substance accordingly by hydrolysis in aqueous environment.
We have found that the tackiness agent that has decrease hydrolysis rate suitable in the paint from polishing antifouling.
The paint of anti-marine biofouling of the present invention has comprised that pigment is the detailed biological biocide in sea, or pigment adds other ocean biocide, and binder for film formation; It is characterized by described tackiness agent is that general expression is Z(-O-X) the soluble but hydrolyzable polymkeric substance of the seawater of n, can its hydrolyzed state dissolving in seawater or disperse.Z is hydroxy-functional polymkeric substance Z(-OH in the formula) residue of n, n is the integer greater than 1, each part of one-O-X group hydrolysis formation-OH group in seawater naturally of each X.
" with the dissolving of its hydrolyzed state or disperse " be meant when all group-O-X basically all be transformed into-during the OH group, polymkeric substance is as colloidal suspension.When some are soluble or dispersive, be not whole polymkeric substance-O-X groups be hydrolyzed into-OH group and some still with-when the O-X group existed, polymkeric substance generally just became solubilized or dispersible in seawater.When having enough free hydroxyl groups by hydrolysis, polymkeric substance just comes out from the hull of its original coating or the surface dissolution or the dispersion of boat body.
The example of-O-X group has:
General expression is:
Sulfonate ester group, R is an organic group in the formula, for example, is at most the alkyl or aryl of 8 carbon atoms, is attached on the sulphur atom by carbon-sulfur bond;
General expression is
Sulfate group, R in the formula
1Be organic group, for example, the alkyl of 8 carbon atoms is attached on the Sauerstoffatom by carbon-oxygen bond at the most;
General expression is
Sulfite groups, R in the formula
1The same;
General expression is
The-sulfinic acid ester group, R is the same in the formula;
General expression is
Bound phosphate groups, each R in the formula
2Be organic group independently; For example, be at most the alkyl of 8 carbon atoms, be attached on the Sauerstoffatom by carbon one oxygen key;
General expression is
Phosphonate groups, R in the formula
2The same, R
3Be organic group, for example, be at most the alkyl or aryl of 8 carbon atoms, be attached on the phosphorus atom by C;
General expression is
The phosphinate group, each R in the formula
3The same;
General expression is-OSiR
4Disiloxanyl-group, each R in the formula
4Be organic group independently, for example, be at most the alkyl or aryl of 8 carbon atoms, be attached on the Siliciumatom by carbon-silicon key;
And general expression is
Active carboxylic acid's ester group, at least one R in the formula
5Group is the electrophilic polar group, other R
5Group is a hydrogen or such as the organic group that is at most 8 carbon atoms.The example of suitable electrophilic polar group is halogen atom or cyano group, thiocyano, sulfone, aldehyde radical or ketone group.For example ,-the O-X group can be-OOCCCl
3,-OOCCF
3,-OOCCHCl
2,-OOCCH
2Cl or-OOCCH
2CN.Usually, 10 to 10,000 or more a plurality of-O-X base molecular weight is arranged is 2,000 to 500,000 or higher to water-soluble polymers.
The hydroxy-functional polymkeric substance generally is to have the polymkeric substance that is attached at the hydroxyl on the carbon atom in the polymkeric substance separately, is just to be linked to carbon and/or hydrogen atom in addition.The hydroxy-functional polymkeric substance is linear polymer preferably, has the hydroxyl value of 0.1meg/g at least, is more preferably 0.5meg/g at least, and this polymkeric substance is addition polymer preferably.The hydroxy-functional polymkeric substance is a polyvinyl alcohol preferably, and this polyvinyl alcohol has molecular weight 2000 to 500,000 preferably, is 5,000 to 50,000 better.Polyvinyl alcohol generally is that the saponification by Vinyl Acetate Copolymer forms, and is to have the acetic acid group of the Vinyl Acetate Copolymer of at least 50 moles of % to change into hydroxyl preferably, such as 60 to 98 moles of %.Alternately the hydroxy-functional polymkeric substance is a kind of polymkeric substance of the hydrolyzable acrylate monomer such as Hydroxyethyl acrylate or hydroxyethyl methylacrylate.
On the other hand, the hydroxy-functional polymkeric substance can be hydroxy-functional polyester or polyethers.The hydroxy-functional polyester can pass through di-carboxylic acid or its acid anhydrides, for example, terephthalic acid, m-phthalic acid, hexanodioic acid or sebacic acid and/or Tetra hydro Phthalic anhydride, with excessive such as ethylene glycol, propylene glycol, 1, the di-alcohols reaction of 4-butyleneglycol or new propylene glycol and/or ether alcohol and producing.For increasing water-soluble, polyester contains preferably from deriving such as the ether glycols of Diethylene Glycol, triethylene glycol or dipropylene glycol etc. the unit that comes, perhaps can be to contain from polyoxyethylene glycol or poly-(tetramethyl-ether) ethylene glycol to derive and the segmented copolymer of the polyethers section of coming.Polyester also can contain a small amount of acidic group, and these acidic groups are being not enough to give water-soluble with the polyester hydroxyl reaction during with formation-O-X group, but can promote to contain the water-soluble of the polyester of free hydroxyl group.
Suitable hydroxy-functional polyethers is passable, such as, be that the polyethers of amido and epoxide reaction form two (beta-hydroxy) amine groups and form by the top.
At sulfonate ester group RSO
3-in, the R group is the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl or hexyl preferably, but it also can be an aryl, such as, phenyl or right-tolyl.The R group is unsaturated alkyl preferably, can be replaced at random such as inert substituents such as alkoxyl group or halogen atoms best.
In sulfuric ester, sulfite, phosphoric acid ester and phosphonate groups, radicals R
1Or R
2Be to select those can make-O-R preferably
1Or-O-R
2Be attached to the polymkeric substance ratio-O-X group instability still less that gets on, in order to avoid acid sulfate, sulfite, phosphoric acid ester or phosphonate group build on the polymer residue.This acidic-group will produce than the water dissolution of hydroxyl polymkeric substance faster, and therefore draw the almost quick dissolving of unexpected paint.
In phosphoric acid ester and phosphonate groups, alkyl R
2Form the most stable ester bond, in sulfuric ester and sulfite groups, radicals R
1Be branched-chain alkyl preferably, for example, tert-butyl, sec.-propyl or neo-pentyl, for-O-R
1The maximum stable of key.
Radicals R in phosphonic acid ester or the phosphinate group
3Can be alkyl, aryl or aryl groups per alkyl group, replacement or unsubstituted.
Hydrolyzable polymkeric substance can prepare by Raolical polymerizable, adopts randomly and contains with one or more-the O-X group monomer, such as the monomeric comonomer of right-toluenesulphonic acids vinyl acetate.This monomer can react in the ebullient trimethyl carbinol by uncle's fourth potassium oxide and two (tosic acid) glycol ester and get.Another sulphonate monomer is right-toluenesulphonic acids-2-methacrylic acid 2-ethoxyethyl acetate, and it can be by hydroxyethyl methylacrylate and p-toluenesulfonyl chloride in the solvent such as methylene dichloride, preparation in the presence of such as triethylamine alkali and getting.Hydrolyzable addition polymer can be according to No. the 217535th, european patent application, carboxylic acid vinyl ester polymer by for example polymkeric substance such as vinyl acetate or vinyl butyrate and methoxylation trialkyltin such as the methoxylation tributyl tin then get again with such as methylsulfonyl chloride or p-toluenesulfonyl chloride prepared in reaction.The carboxylic acid vinyl ester polymer is Vinyl Acetate Copolymer preferably.Has 30% acetate groups at least.Have 50% to 70% preferably, change into RSO
3-group.On the other hand, can in the presence of alkali, handle and get by using the alkyl or aryl SULPHURYL CHLORIDE such as the hydroxy-functional polymkeric substance of polyvinyl alcohol or poly-(hydroxyethyl vinylformic acid) at pyridine or in organic solvent through sulfonation.
The polymkeric substance that comprises sulphonate, sulfite, phosphoric acid ester, phosphonic acid ester or phosphinate group can be the acid of chloric acid branched-chain alkyl by polyvinyl acetate (PVA) and sulfuric chlorohydrin alkyl ester preferably
Alkyl chlorosulfite; Be chlorine sulfurous acid branched alkyl ester preferably
The chlorine alkyl phosphate
Chlorine phospho acid alkyl ester
Perhaps inferior phosphoryl chloride
Prepared in reaction and get above-mentioned R
1, R
2And R
3Respectively with the same meaning of front.On the other hand, can be with hydroxy functional monomers and sulfuric chlorohydrin alkyl ester, alkyl chlorosulfite, chlorine alkyl phosphate, clodronic acid alkyl ester or phosphoryl chloride reaction such as the methacrylic acid hydroxyethyl ester, the gained monomer can pass through the Raolical polymerizable polymerization.With the reaction of chloride compounds be in the presence of alkali, to carry out, such as triethylamine or pyridine.
The polymkeric substance that comprises active carboxylic acid's ester group can be by being R with hydroxy-functional polymkeric substance and general expression
5 3The acyl chlorides of CCOCl reacts in the presence of tertiary amine and makes.
At three organosilicon part-Si R
4 3In radicals R
4Be such as alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl or hexyls preferably, but also can select for example aryl of phenyl.Radicals R
4Be unsaturated hydroxyl preferably, but can be replaced such as inertia substituents such as alkoxyl group or halogen atoms randomly.-OSi R
4 3The silicon ether group is enough hydrolysis promptly in seawater, but than the estersil base of describing in the United States Patent (USP) the 4593055th more slowly.
Hydrolyzable polymkeric substance can be by comprising-O-Si R
3The Raolical polymerizable of the unsaturated monomer of group reacts with one or more comonomers one randomly, the preparation and get; Perhaps pass through the soluble or dispersible hydroxy-functional polymkeric substance of seawater, for example polyvinyl alcohol or poly-(Hydroxyethyl acrylate, with three organic silylation agent (triorganosilylatiingagent), for example trimethylchlorosilane, tert-butyl dimethylchlorosilane or phenyl dimethyl oxygen silane reaction prepare and get.Reaction can be in the organic solvent such as dimethyl formamide, and in the presence of such as Trimethylamine 99 or pyridine, in 0 to 20 ℃ temperature is carried out.The hydroxy-functional polymkeric substance selectively with hexamethyldisilazane (CH
3)
3SiNSi(CH
3)
3Or two (trimethyl silicon based) urea (CH
3)
3Si-NH-CO-NH-Si(CH
3)
3In organic solvent, react such as dimethylbenzene or methyl iso-butyl ketone (MIBK).On the other hand, such as the hydroxy functional monomers of hydroxyethyl methylacrylate and such as hexamethyldisilazane or two (trimethyl silicon based) urea reaction.To form such as methacrylic acid 2-(trimethylsiloxy group)-the silicon ether monomer of ethyl ester.This monomer can polymerization.Be randomly and one or more inertia comonomers, such as such as methyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate or vinylformic acid methoxyl group ethyl ester, by such as the radical polymerization in the organic solvent of dimethylbenzene or methyl iso-butyl ketone (MIBK).
Comprising general expression is
-the hydrolyzable polymkeric substance of O-X group do not report in the past.Present invention includes the insoluble hydrolyzable polymkeric substance of the seawater that comprises these groups,, also comprised their preparation method particularly as the side group that in addition polymer, is attached on the carbon atom.
In order to form paint, hydrolyzable polymer binder has the marine organisms biocidal, if it is different with pigment.Can use general blend method.Pigment generally in seawater, have be lower than 1,000,000/10(weight) solubleness, be preferably and have 0.5/1000000th to 10(weight in the ocean) the slightly soluble pigment of solubleness, for example, red copper oxid, the inferior ketone of thiocyanic acid, zinc oxide, zinc chromate, two (dithiocarbamic acid) ethene two zinc salts, dithiocarbamic acid dimethyl zinc salt or dithiocarbamic acid diethyl zinc salt.These slightly soluble copper and zn cpds generally are the marine organisms biocides, these slightly soluble pigment produce water soluble metallic compound when reacting with seawater makes granules of pigments can not remain in the surface of paint, and this helps to paint dissolving glibly in the seawater of relative movement.The mixture of operable slightly soluble pigment, for example, two (dithiocarbamic acid) zinc of Red copper oxide, cuprous thiocyanate or vinyl, these the most effective thing pigment of killing livestock, can mix with zinc oxide, it dissolves a little more hurry up in seawater, and is more effective at the aspects such as dissolving glibly that comprise paint.
Paint composite can add ground or selectively comprise pigment nonreactive with seawater and may highly undissolved (solubleness is lower than the 0.5ppm weight part) in seawater, such as, titanium dioxide or ferric oxide.This height insoluble pigment is to use with 40% the ratio of being at most of the gross weight of paint pigment component preferably, most preferably less than 20%(weight).
The ratio of pigment and polymer binder is so preferably, and greater than 20% but the subcritical pigment volume concentration (PVC), best pigment volume concentration (PVC) is 35-50% to the volumetric concentration that can make pigment in the drier oil paint film.
Kill livestock the thing efficient, particularly Red copper oxide of seawater slightly soluble pigment, the inferior ketone of thiocyanic acid and two (dithiocarbamic acid) zinc of vinyl are to be enough to make paint no longer to need other biocides.
Seriously stained to what may run into, paint can comprise additional biocide, for example, is added to and mostly is 50% of pigment total amount.Three organic tin salts and oxide compound, such as triphenyltin fluoride, fluoridize tributyl tin, dibromo-succinic acid tributyl tin, triphenyltin chloride, hydroxide triphenyltin and tributyltin oxide, be effective ocean biocide, and can be used in the paint according to the present invention.The present invention's paint that comprises three organic tin salts (content is at most 25% volume integral of pigment) has three organotins the paint equal anti-fouling and smooth property much higher with three organotin content.In most of the cases need to avoid three organotin ionic to discharge fully.Other conduct prevents that the example of effective biocide of marine biofouling from having: such as two (dithiocarbamic acid) derivative such as vinyl two (dithiocarbamic acid copper) or tetramethylthiuram disulfides, (methylene-bis (thiocarbamide), 4-butyl phenol, Vancide 89, the tetrahydrochysene m-dicyanobenzene, 1-methyl sulfo--3-(tert-butyl amino)-5-(cyclopropyl amino)-the S-triazine, or such as 4,5-two chloro-2-octyl groups-3-isothiazolones (isothicozolone).
Below in conjunction with embodiment the present invention is described.
Embodiment 1
A) preparation of right-toluenesulphonic acids 2-methacrylic acid oxygen ethyl ester
Tosyl chloride 256 grams are dissolved in 400 milliliters of CH
2Among the Cl, again this drips of solution is added to 600 milliliters of CH of 175 gram methacrylic acid 2-hydroxyl ethyl esters and 136 gram triethylamines
2In the solution of Cl.This mixture stirred in nitrogen atmosphere and in ice bath cooling finish reinforced process, produce a kind of settled solution.Continue to stir several hrs, remove white precipitate by filtering, with rare HCl, rare NaHCO
3Solution and washing filtrate.Muddy yellow solution Mg SO will be obtained
4Drying, and remove solvent with the rotary evaporation method.
B) polymer manufacture
Will be as the right-toluenesulphonic acids 2-methacrylic ester oxygen ethylhexyldithiophosphoric acid of 190 grams of above-mentioned preparation with 40%(weight) solution in that to contain with the monomer be the 1%(weight of standard) the butane-2-ketone of Diisopropyl azodicarboxylate as catalyzer in, polymerization is 5 hours under 70 ℃ temperature.
The polymers soln that produces can mix with Red copper oxide with composition and prevents that marine biofouling from painting.
Embodiment 2
With 133.8 the gram methyl methacrylates, 171.3 the gram vinylformic acid just-butyl ester and 230 the gram butane-2-ketone (MEK) be placed on and be heated to 70 ℃ in the flask, use nitrogen purging simultaneously.230 gram 190 among MEK gram tosic acid 2-methacrylic acid 2-ethoxyethyl acetate solution at room temperature equally also several 1 hour with nitrogen purging.2.475 gram Diisopropyl azodicarboxylate initiators are dissolved in the tosic acid methacrylic acyloxy ethyl ester solution, and the initiator of same amount directly is added in the flask.During 115 minutes, tosic acid methacrylic acyloxy ethyl ester is added drop-wise in the solution of the methyl methacrylate/butyl acrylate that is being stirred, in entire reaction course, slowly feed nitrogen.In polymerization process, solution is diluted into 40%(solid part) so that stir.Continue heating 3 hours in the reinforced back of finishing, flask is removed and under nitrogen atmosphere, allowed the content cooling from water-bath.
Filter polymers soln and be cast into film, and it is dried to dura mater at cube shaped applicator.During it immersed seawater, this film demonstrated lasting right-tosylate and is discharged in the seawater, this means that hydrolysis carrying out.
This polymers soln can mix with red copper oxid to form anti-fouling paint.
Embodiment 3
A) preparation of ethyl ester methacrylic acid 2-(trimethylammonium silica)
200 milliliters of toluene that will contain 73 milliliters of hydroxyethyl methylacrylates and 23 milliliters of hexamethyldisilazanes are heated in the backflow, 3 to 4 trimethylammonium oxosilanes are added in the phegma again, can see white precipitate, volatilize ammonia.Backflow is after 1 hour down at 116 ℃, and throw out disappears, and stays settled solution.To from this solution, take out 25 ml sample magnetic resonance detection, and demonstrate hydroxyl and all change into trimethyl silicon based ether group basically.Steam solvent, stay 37.5 gram products.
B) polymer manufacture
Will be as the methacrylic acid 2-(trimethylsiloxy group of above-mentioned preparation) ethyl ester is with the solution of 40% concentration, in the dimethylbenzene and methyl iso-butyl ketone (MIBK) of same volume, in order to monomer weight was that 1% Diisopropyl azodicarboxylate of standard is a catalyzer, 70 ℃ of following polymerizations 5 hours.
The polymers soln that produces can mix with Red copper oxide to form anti-fouling dose.
Embodiment 4
With 40.4 gram methacrylic 2-(trimethylsiloxy groups) ethyl ester, 40.0 gram methyl methacrylates and 51.3 gram butyl acrylates in butane-2-ketone with 1% Diisopropyl azodicarboxylate catalyzer, with the method copolymerization of embodiment 2, produce the polymers soln be suitable for as forming mixture as the tackiness agent of anti-fouling paint with Red copper oxide.
Claims (23)
1, a kind of paint of marine biofouling, the pigment that comprises a kind of ocean biocide or a kind of pigment and independent ocean biocide of preventing with binder for film formation, is characterized in that, tackiness agent be general expression be Z (O-X)
nThe insoluble hydrolyzable polymkeric substance of seawater, in the formula Z be hydroxy-functional polymkeric substance Z (OH)
nResidue, this polymkeric substance can the dissolving of its hydrolyzed state in ocean water or is disperseed, n is the integer greater than 1, each X respectively does for oneself can make-part of O-X group hydrolysis formation-OH group in seawater.
2, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group general expression is
Sulfonate ester group, R is for being the alkyl or aryl of 8 carbon atoms at the most in the formula.
3, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group general expression is
Sulfate group, R in the formula
1For being the alkyl of 8 carbon atoms at the most.
4, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is
The ester group of sulfurous acid, R in the formula
1For being the alkyl of 8 carbon atoms at the most.
5, by claim 3 or 4 described paint, it is characterized in that R
1It is the alkyl of side chain.
6, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is
The-sulfinic acid ester, R is for being the alkyl or aryl of 8 carbon atoms at the most in the formula.
7, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is
Bound phosphate groups, each R in the formula
2Respectively doing for oneself is the alkyl of 8 carbon atoms at the most.
8, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group general expression is
Phosphonate groups, R in the formula
2For being the alkyl of 8 carbon atoms at the most, R
3For being the alkyl or aryl of 8 carbon atoms at the most.
9, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is
The phosphinate group, each R in the formula
3Respectively doing for oneself is the alkyl or aryl of 8 carbon atoms at the most.
10, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is-OSi(R
4)
3The silicon ether group, each R in the formula
4Respectively doing for oneself is the alkyl or aryl of 8 carbon atoms at the most.
11, by the described paint of claim 1, it is characterized in that described polymkeric substance has comprised-the O-X group, this group is that general expression is
Active carboxylic acid's ester group, at least one R in the formula
5Be the electrophilic polar group, other R
5For hydrogen or be the organic group of 8 carbon atoms at the most.
12,, it is characterized in that described electrophilic polar group is halogen atom or cyano group, thiocyanic acid, sulfone, aldehydes or ketones base by the described paint of claim 11.
13,, it is characterized in that described hydroxy-functional polymkeric substance Z(-OH by the described paint of claim 1,2 or 10) n is polyvinyl alcohol.
14,, it is characterized in that described hydroxy-functional polymkeric substance Z(-OH by the described paint of claim 1,2 or 10) n is Hydroxyethyl acrylate or hydroxyethyl methylacrylate polymkeric substance.
15,, it is characterized in that described hydroxy-functional polymkeric substance Z(-OH by the described paint of claim 1,2 or 10) n is hydroxy-functional polyester or polyethers.
16, a kind of general expression is Z(-O-X) the insoluble but hydrolyzable polymkeric substance of the seawater of n, it is characterized in that Z is hydroxy-functional polymkeric substance Z(-OH in the formula) residue of n, this hydroxyl decomposability polymkeric substance can dissolve with the state of its hydrolysis or be dispersed in the seawater, n is the integer greater than 1, the part of each X respectively does for oneself feasible-O-X group hydrolysis formation-OH group in seawater, group-O-X is selected from general expression to be in this polymkeric substance
Sulfonate ester group, R is for being the alkyl or aryl of 8 carbon atoms at the most in the formula;
General expression is
Bound phosphate groups, each R in the formula
2Respectively doing for oneself is the alkyl of 8 carbon atoms at the most;
General expression is
Phosphonate groups, R in the formula
2The same, R
3For being the alkyl or aryl of 8 carbon atoms at the most; General expression is
The-sulfinic acid ester group, R is the same in the formula;
General expression is
The phosphinate group, each R in the formula
3The same separately; Perhaps
General expression is-OSi(R
4)
3The silicon ether group, each R in the formula
4Respectively doing for oneself is the alkyl or aryl of 8 carbon atoms at the most.
17, by the insoluble hydrolyzable polymkeric substance of the described seawater of claim 16, it is characterized in that it comprised the crop that in addition polymer, is attached on the carbon atom be side group-the O-X group.
18, by claim 16 or 17 described polymkeric substance, it is characterized in that group-O-X wherein is a sulfonate ester group.
19, by claim 16 or 17 described polymkeric substance, it is characterized in that group-O-X wherein is the silicon ether group.
20, a kind of production method according to the described polymkeric substance of claim 18 is characterized in that being is RSO with general expression with the hydroxy-functional polymkeric substance under the condition that alkali exists
2The SULPHURYL CHLORIDE reaction of Cl.
21, a kind of production method by the described polymkeric substance of claim 18 is characterized in that hydroxy functional monomers is is RSO with general expression under the condition that alkali exists
2The SULPHURYL CHLORIDE reaction of Cl, and by the Raolical polymerizable polymeric, be randomly and one or more comonomer polymerization.
22, a kind of production method according to the described polymkeric substance of claim 19 is characterized in that hydroxy-functional polymkeric substance and three organic silylation agent reactions.
23, a kind of production method by the described polymkeric substance of claim 19 is characterized in that hydroxy functional monomers is with three organic silylation agent reactions and by the Raolical polymerizable polymerization, is and one or more comonomer polymerization randomly.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB8812172 | 1988-05-23 | ||
| GB888812172A GB8812172D0 (en) | 1988-05-23 | 1988-05-23 | Marine antifouling paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1039255A true CN1039255A (en) | 1990-01-31 |
Family
ID=10637372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89103696A Pending CN1039255A (en) | 1988-05-23 | 1989-05-23 | Prevent the paint of marine biofouling |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPH03505885A (en) |
| KR (1) | KR900701942A (en) |
| CN (1) | CN1039255A (en) |
| AU (1) | AU3689189A (en) |
| BR (1) | BR8907442A (en) |
| DK (1) | DK275790D0 (en) |
| GB (1) | GB8812172D0 (en) |
| PT (1) | PT90618A (en) |
| WO (1) | WO1989011511A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309749C (en) * | 1999-06-26 | 2007-04-11 | 现代电子产业株式会社 | Organic anti-reflective polymer and preparation thereof |
| CN109661442A (en) * | 2016-07-11 | 2019-04-19 | 株式会社可乐丽 | Aquatile repellent coating composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4774080A (en) * | 1985-05-17 | 1988-09-27 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
| GB8521325D0 (en) * | 1985-08-27 | 1985-10-02 | Raychem Ltd | Preparation of side-chain polymers |
| GB8700398D0 (en) * | 1986-01-22 | 1987-02-11 | Ici Plc | Compositions for surface treatment |
-
1988
- 1988-05-23 GB GB888812172A patent/GB8812172D0/en active Pending
-
1989
- 1989-05-19 WO PCT/GB1989/000548 patent/WO1989011511A1/en unknown
- 1989-05-19 JP JP1505630A patent/JPH03505885A/en active Pending
- 1989-05-19 BR BR898907442A patent/BR8907442A/en unknown
- 1989-05-19 AU AU36891/89A patent/AU3689189A/en not_active Abandoned
- 1989-05-19 KR KR1019900700115A patent/KR900701942A/en not_active Application Discontinuation
- 1989-05-22 PT PT90618A patent/PT90618A/en not_active Application Discontinuation
- 1989-05-23 CN CN89103696A patent/CN1039255A/en active Pending
-
1990
- 1990-11-20 DK DK275790A patent/DK275790D0/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309749C (en) * | 1999-06-26 | 2007-04-11 | 现代电子产业株式会社 | Organic anti-reflective polymer and preparation thereof |
| CN109661442A (en) * | 2016-07-11 | 2019-04-19 | 株式会社可乐丽 | Aquatile repellent coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900701942A (en) | 1990-12-05 |
| DK275790A (en) | 1990-11-20 |
| DK275790D0 (en) | 1990-11-20 |
| BR8907442A (en) | 1991-05-07 |
| GB8812172D0 (en) | 1988-06-29 |
| WO1989011511A1 (en) | 1989-11-30 |
| AU3689189A (en) | 1989-12-12 |
| PT90618A (en) | 1989-11-30 |
| JPH03505885A (en) | 1991-12-19 |
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Legal Events
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| C06 | Publication | ||
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |