CN103289007A - Improved preparation method for zinc/copper acrylate resin - Google Patents
Improved preparation method for zinc/copper acrylate resin Download PDFInfo
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Abstract
The invention specifically relates to an improved preparation method for a zinc/copper acrylate resin, which belongs to the technical field of marine anti-fouling paints. The preparation method comprises the following steps: with a mixed system of water and an organic solvent as a disperse medium, reacting a metal salt solution with aqueous alkali to produce zinc/copper hydroxide, fully dispersing the zinc/copper hydroxide in a dispersant and then carrying out filtering and drying so as to obtain high-dispersibility zinc/copper hydroxide; subjecting soft and hard monomers of acrylic acid to free radical polymerization under the action of an initiator at a constant temperature so as to produce an acrylic prepolymer containing a carboxyl group; and reacting the acrylic prepolymer obtained in the previous step with the dispersed zinc/copper hydroxide under the action of an organic acid at a constant temperature so as to prepare the zinc/copper acrylate resin with hydrolysis characteristics. According to the invention, the zinc/copper hydroxide prepared in the invention has good dispersibility and no agglomeration and needs short reaction time during reaction with the acrylic prepolymer, so cost is low, and original equipment does not need to be improved.
Description
Technical field
The invention belongs to the marine antifouling coating technical field, specifically a kind of improved zinc acrylate resin/resin of copper preparation method.
Background technology
Marine fouling organism mainly refers to adhere to animal and plant on hull bottom, buoy and all the artificial facilities and the general name of microorganism, is one of important factor that influences maritime facilities safety and work-ing life.The harm of biodeterioration mainly contains following several respects: increase ship resistance, blocking pipe, acceleration metallic corrosion, fight for adherance and bait with the sea farming shellfish.
The common method that solves biodeterioration is the brushing antifouling paint.Organotin rises the seventies in 20th century from the polishing antifouling technology, the organotin self-polishing coating is that a kind of multipolymer by methacrylic acid tributyl tin ester and methyl methacrylate and Red copper oxide combine, this kind antifouling paint can effectively prevent adhering to of marine fouling organism, its mechanism is that methylmethacrylate copolymer is with the continuous hydrolysis of sea water immersion, tributyl tin (TBT) discharges and brings into play antifouling effect, has broad spectrum, high efficiency, long, the low cost and other advantages of effect of antifouling phase.After the eighties, it is found that TBT that this coating discharges can be deposited on ooze for a long time and is accumulated in the biology, causes serious harm to the marine eco-environment.International Maritime Organizaton in 2003 requires to ban use of organotin as marine antifoulant, and all boats and ships banned use of the organotin antifouling paint in 2008.Therefore, development tin-free self-polishing type antifouling paint is a kind of environmental protection, economy, and can satisfy a kind of low toxicity of current environment requirement, free of contamination antifouling paint.
In recent years, poisonous stain control agent substitute such as organotin is all being set about studying by each state, and makes great efforts the novel tin-free self-polishing antifouling paint of development research, and wherein, vinylformic acid copper/zinc becomes one of research focus.Nineteen ninety, US Patent No. 5080892 was described the method for acrylic acid synthesizing zinc/resin of copper, and this method obtains zinc acrylate resin/resin of copper with zinc hydroxide/copper, organic acid reaction again by synthetic carboxylic acrylic resin.Chinese patent CN1544488A elder generation synthetic alkali formula organic acid zinc/mantoquita in 2004, the acrylate copolymer of resynthesis band carboxyl, both obtain zinc acrylate resin/copper at reaction.Chinese patent CN102167775 elder generation acrylic acid synthesizing zinc/copper small molecule monomer in 2011 generates zinc acrylate resin/resin of copper with the radical polymerization of vinylformic acid soft or hard monomer initiator then.In zinc acrylate resin in the aforesaid method/copper generative process, agglomeration easily takes place in metal base (alkali formula organic acid salt), perhaps is deposited in device bottom, causes zinc acrylate resin/resin of copper stability low, the anti-fouling effect poor repeatability.
Summary of the invention
The purpose of this invention is to provide a kind of improved zinc acrylate resin/resin of copper preparation method.
For achieving the above object, the technical solution used in the present invention is:
A kind of improved zinc acrylate resin/resin of copper preparation method,, metal salt solution and alkaline solution reaction are generated zinc hydroxide/copper, and in dispersion agent, fully disperse as dispersion medium with the mixed system of water, organic solvent, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades;
Under steady temperature, vinylformic acid soft or hard monomer is generated the acrylic polymer that contains carboxyl by initiator generation Raolical polymerizable;
Steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper under the organic acid effect, react and make the zinc acrylate resin/resin of copper with hydrolysis properties;
Detailed process is as follows:
Wherein: R=H or CH
3R
1=CH
3, C
2H
5, C
4H
9Or C
8H
17
R
2=C
6H
5Or C
5H
9(CH
2)
nM=Cu or Zn.
, inorganic zinc/copper salt solution and the inorganic alkali solution reaction of solubility generated zinc hydroxide/copper, and in dispersion agent, fully disperse as dispersion medium with the mixed system of water, organic solvent, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades; Wherein the mol ratio of the inorganic zinc/mantoquita of mineral alkali and solubility is 1.0-1.2:1; In the described dispersion medium between water and the organic solvent volume ratio be 100:0.2-6.
Organic solvent in the described dispersion medium is the mixed solution of alcohol and ketone, and wherein alcohol is the mixed of 1-5:1 with ketone by volume;
Described alcohol is methyl alcohol, ethanol, propyl alcohol or butanols; Ketone is methylethylketone, acetone or butanone; Volume ratio between described zinc hydroxide/copper and dispersion medium is 1:2-5.
Described dispersion agent is a kind of in borax, water glass, Sodium hexametaphosphate 99, trisodium phosphate, Trisodium Citrate, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, fatty acid polyglycol ester, hexadecyl phosphoric acid fat, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, hexenyl bis-stearamides, the polyoxyethylene glycol; Wherein the mass ratio of dispersion agent and zinc hydroxide/copper is 0.1%-1%.
Zinc hydroxide/the copper that generates is carried out dispersed with stirring in dispersion system, jitter time is 1-3h, and dispersion temperature is 40-50 ℃, and stirring velocity is 100-500r/min.
Under steady temperature, vinylformic acid soft or hard monomer is issued the acrylic polymer that living Raolical polymerizable generation contains carboxyl by initiator in the existence of organic solvent; Described polymeric reaction temperature is 70-90 ℃; Polymerization reaction time is 4-8h;
Described vinylformic acid soft or hard monomer is acrylate or methacrylic ester; Wherein, acrylate is vinylformic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Octyl acrylate, Isooctyl acrylate monomer or vinylformic acid n-octyl;
Methacrylic ester is methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, Octyl methacrylate, Isooctyl methacrylate or n octyl methacrylate;
Described organic solvent is that organic solution and dimethylbenzene are formed, and wherein dimethylbenzene mixes by the volume ratio of 4:1 with organic solution; Organic solution is propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone or ethylene glycol monomethyl ether.
Described initiator is a kind of in azo-initiator, the peroxide initiator, and wherein initiator accounts for the 0.1-5% of polymerization system quality; Wherein azo-initiator can be Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN); The peroxide initiator can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
Described under steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper and organic acid under the effect of organic solvent at 70-110 ℃, the zinc acrylate resin/resin of copper with hydrolysis properties is made in reaction under the stirring velocity of 100-500r/min; Wherein, organic acid is phenylformic acid or naphthenic acid; Organic acid is 1.0-1.5:1 with the amount of substance ratio of zinc hydroxide/copper; Described organic solvent is the mixed solvent of dimethylbenzene and propyl carbinol, and volume ratio is 4:1 between dimethylbenzene and the propyl carbinol.
Described zinc acrylate resin/resin of copper as resin with softening agent, pigment, filler, stain control agent, auxiliary agent, help and ooze out agent and organic solvent mixes, namely obtain marine antifouling coating; By weight percentage, 20-30% resin, 1-10% softening agent, 5-10% pigment, 5-10% filler, 5-10% stain control agent, 0.1-0.5% auxiliary agent, 4-10% help ooze out agent, surplus is organic solvent.
Organic solvent is a kind of in propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone, the ethylene glycol monomethyl ether in the described coating, and massfraction is 40-60%; Described stain control agent is capsicine, 1,2-benzisothiazole-3-ketone, 4,5-dichloro--2-n-octyl-4-isothiazoline-3-ketone, pyridine triphenylborane, Zinc Pyrithione or pyrithione ketone; Described pigment is a kind of in ferric oxide, titanium dioxide, zinc oxide, carbon black, iron oxide black, calcium carbonate, Calucium Silicate powder, the talcum powder; Described filler is tetrafluoroethylene, paraffin oil or fluorographite; Described auxiliary agent is flow agent, dispersion agent, defoamer, wetting agent, anti-settling agent; Describedly help that to ooze out agent be rosin.
The present invention has the following advantages:
1. zinc hydroxide/copper employing water and organic solvent are dispersion medium, and after dispersion agent disperseed, its dispersion effect was good, can reach nano level;
2. zinc acrylate resin or acrylate resin synthetic method are than the method that adopts both at home and abroad before, and this method need not to increase equipment cost, and since the high dispersing of zinc hydroxide/copper, the reaction times shortening, thus making the production cost reduction, synthesis technique is optimized;
3. be the antifouling paint that base-material is made by zinc acrylate resin or acrylate resin, good with the sticking power of matrix, the antifouling property height, and can effectively suppress marine fouling organism and adhere to and grow, and pollution-free to the marine eco-environment.
Embodiment
Following examples are to further specify of the present invention, but the invention is not restricted to this.
Improved zinc acrylate resin/resin of copper preparation method:
The reaction of the first step metal salt solution and alkaline solution generates zinc hydroxide/copper, and wherein the mixed system of water, organic solvent is as dispersion medium, after dispersion agent disperses, and filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades;
Second step vinylformic acid soft or hard monomer under steady temperature contains the acrylic polymer of carboxyl by the Raolical polymerizable generation of initiator;
Zinc hydroxide/copper, organic acid reaction under the 3rd step steady temperature after acrylic polymer and the dispersion are made the zinc acrylate resin/resin of copper with hydrolysis properties.
As follows.
Wherein: R=H, CH
3; R
1=CH
3, C
2H
5, C
4H
9, C
8H
17;
R
2=C
6H
5,C
5H
9(CH
2)
n；M=Cu,Zn；
Described second step and three-step reaction temperature are 70-110 ℃; Described stirring velocity is 100-500r/min.Be film forming matter with above-mentioned resin, make self polishing copolymer antifouling paint.
Embodiment 1
1) preparation of zinc hydroxide
In the solution that contains 2.5ml ethanol, 0.5ml acetone, 97ml water, add 32.2g sodium hydroxide, constantly being stirred to sodium hydroxide dissolves fully, with the 0.2g Sodium hexametaphosphate 99 as dispersion agent, under 40 ℃, 500r/min fully stirred 0.5 hour, slowly drip 4.0mol/L zinc nitrate 100ml, show neutral to pH value of solution.Insulation disperseed 1 hour, and vacuum filtration, distilled water 100ml divide 3 washings, drained 80 ℃ of dryings 12 hours.
2) preparation of acrylic polymer
Be equipped with in three mouthfuls of round-bottomed flasks of 500ml of stirring, condenser, constant pressure funnel, add 100g mixed solvent (dimethylbenzene and propyl carbinol mass ratio are 4:1), 80 ℃, 400r/min, drip Acrylic Acid Monomer mixture (23g vinylformic acid, 31g methyl methacrylate, the 41g butyl acrylate) 100g that contains 4g Diisopropyl azodicarboxylate (AIBN), the positive Dodecyl Mercaptan of 1g in the 3h, the dropping process keeps reflux state.Be incubated 1 hour, to wherein adding the mixed solvent 25g that contains 4%AIBN, insulation 2h reacts and finishes, and obtains the acrylic polymer of little yellow clear in half an hour.
3) zinc acrylate resin is synthetic
To be equipped with in three mouthfuls of round-bottomed flasks of 250ml of stirring, condenser, water-and-oil separator, add 100g acrylic polymer, 9.7g zinc hydroxide, 12.2g phenylformic acid, mass ratio is dimethylbenzene and the propyl carbinol 30g of 4:1,80 ℃, 400r/min reacted 6 hours, and the question response mixture is to vitreous state, 105 ℃ of the heating of heating up dewater to distillate to exclusion and end, and obtain the zinc acrylate resin of yellow transparent.
4) preparation of zinc acrylate resin antifouling paint (preparing antifouling paint in a conventional manner),
Take by weighing 120g zinc acrylate resin, clorafin 20g, rosin 15g, dimethylbenzene 60g, auxiliary agent (dispersion agent, defoamer, flow agent, defoamer, anti-settling agent, thickening material) 1.75g successively, 400r/min high speed dispersion 1 hour, add talcum powder 15g, BIT25g, red iron oxide 25g, dimethylbenzene 30g, 2000r/min, high speed dispersion 0.5 hour, skin grinder are ground to fineness and reach below the 25 μ m.
Be the performance of test marine antifouling coating, carry out sticking power with reference to standard GB/T1720 " paint film adhesion assay method " and measure.This experiment will spray the tinplate of one priming paint, middle lacquer and antifouling varnish, soak 48 hours in the artificial seawater, and taking-up is dried, and measure paint film adhesion with drawing the circle method.Paint film adhesion is divided into seven grades of 1-7, and 1 grade of sticking power is best, and 7 grades the poorest.
The antifouling property of the antifouling paint that obtains for test, with reference to standard GB-5370-2007, with the antifouling paint spary on the soft steel of long 250mm, wide 150mm, thick 2mm, brushing epoxy primer 2-4 time, drying at room temperature is after 24 hours, brushing antifouling paint 3 times.Test piece adopts the rectangular batten of trough of belt two ends bolting, carries out the shallow sea immersion test.This is tested in fouling organism and carries out nursery stage-May, chooses coastal seawater culture zone, Yantai and carries out marine link plate, 3 months link plate time, regularly model is checked that employing literal and the mode of taking pictures record the stained situation of model.Remove ooze on the model gently with seawater during observation, remove the zone of template edge 20mm simultaneously to eliminate edge effect.Simultaneously, shorten model as early as possible and take out and observing time, immediately model is immersed in the seawater after the observation, avoid the dead result that influences of settled organism.Calculate fouling organism area occupied in the model according to the result that takes pictures.Experimental result is as shown in table 1
Embodiment 2
Difference from Example 1 is, the preparation of copper hydroxide:
In the solution that contains 2.5ml ethanol, 0.5ml acetone, 97ml water, add 32.2g sodium hydroxide, constantly being stirred to sodium hydroxide dissolves fully, with the 0.2g Sodium hexametaphosphate 99 as dispersion agent, under the 40C, 500r/min fully stirred 0.5 hour, slowly drip 4.0mol/L copper hydroxide 100ml, show neutral to pH value of solution.Insulation disperseed 1 hour, and vacuum filtration, distilled water 100ml divide 3 washings, drained 80 ℃ of dryings 12 hours.
The operational instances of other steps namely obtains vinylformic acid copper antifouling paint with example 1, the results are shown in Table 1.
Embodiment 3
Difference from Example 1 is, the preparation of copper hydroxide:
In the solution that contains 2.0ml ethanol, 1.0ml methylethylketone, 97ml water, add 32.0g sodium hydroxide, constantly being stirred to sodium hydroxide dissolves fully, with the 0.2g polyacrylamide as dispersion agent, under 40 ℃, 500r/min fully stirred 0.5 hour, slowly drip 4.0mol/L zinc chloride 100ml, show neutral to pH value of solution.Insulation disperseed 1 hour, and vacuum filtration, distilled water are washed till detection less than chlorion, drained 80 ℃ of dryings 12 hours.
The operational instances of other steps namely obtains the zinc acrylate resin antifouling paint with example 1, and link plate the results are shown in Table 1.
The improved zinc acrylate resin of table 1/resin of copper antifouling paint performance comparison
Annotate: 1. blank model is except epoxy priming paint, is not coated with marine anti-fouling paint
2. self-control zinc acrylate resin does not contain stain control agent
3. chlorinated rubber resin refers to the chlorinated rubber resin to be film forming matter, adds the antifouling paint of BIT preparation.
Claims (10)
1. improved zinc acrylate resin/resin of copper preparation method, it is characterized in that: with the mixed system of water, organic solvent as dispersion medium, metal salt solution and alkaline solution reaction are generated zinc hydroxide/copper, and in dispersion agent, fully disperse, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades;
Under steady temperature, vinylformic acid soft or hard monomer is generated the acrylic polymer that contains carboxyl by initiator generation Raolical polymerizable;
Steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper under the organic acid effect, react and make the zinc acrylate resin/resin of copper with hydrolysis properties;
Detailed process is as follows:
Wherein: R=H or CH
3R
1=CH
3, C
2H
5, C
4H
9Or C
8H
17
R
2=C
6H
5Or C
5H
9(CH
2)
nM=Cu or Zn.
2. improved zinc acrylate resin according to claim 1/resin of copper preparation method, it is characterized in that: with the mixed system of water, organic solvent as dispersion medium, inorganic zinc/copper salt solution and the inorganic alkali solution reaction of solubility are generated zinc hydroxide/copper, and in dispersion agent, fully disperse, disperse the after-filtration drying, the zinc hydroxide/copper of the diffusing property that secures satisfactory grades; Wherein the mol ratio of the inorganic zinc/mantoquita of mineral alkali and solubility is 1.0-1.2:1; In the described dispersion medium between water and the organic solvent volume ratio be 100:0.2-6.
3. by claim 1 or 2 described improved zinc acrylate resin/resin of copper preparation methods, it is characterized in that: the organic solvent in the described dispersion medium is the mixed solution of alcohol with ketone, and wherein alcohol is the mixed of 1-5:1 with ketone by volume; Described alcohol is methyl alcohol, ethanol, propyl alcohol or butanols; Ketone is methylethylketone, acetone or butanone; Volume ratio between described zinc hydroxide/copper and dispersion medium is 1:2-5.
4. by claim 1 or 2 described improved zinc acrylate resin/resin of copper preparation methods, it is characterized in that: described dispersion agent is a kind of in borax, water glass, Sodium hexametaphosphate 99, trisodium phosphate, Trisodium Citrate, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, fatty acid polyglycol ester, hexadecyl phosphoric acid fat, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, hexenyl bis-stearamides, the polyoxyethylene glycol; Wherein the mass ratio of dispersion agent and zinc hydroxide/copper is 0.1%-1%.
5. by the described improved zinc acrylate resin of claim 2/resin of copper preparation method, it is characterized in that: the zinc hydroxide/copper that generates is carried out dispersed with stirring in dispersion system, jitter time is 1-3h, and dispersion temperature is 40-50 ℃, and stirring velocity is 100-500r/min.
6. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: under steady temperature, vinylformic acid soft or hard monomer is issued the acrylic polymer that living Raolical polymerizable generation contains carboxyl by initiator in the existence of organic solvent; Described polymeric reaction temperature is 70-90 ℃; Polymerization reaction time is 4-8h;
Described vinylformic acid soft or hard monomer is acrylate or methacrylic ester; Wherein, acrylate is vinylformic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Octyl acrylate, Isooctyl acrylate monomer or vinylformic acid n-octyl;
Methacrylic ester is methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, Octyl methacrylate, Isooctyl methacrylate or n octyl methacrylate;
Described organic solvent is that organic solution and dimethylbenzene are formed, and wherein dimethylbenzene mixes by the volume ratio of 4:1 with organic solution; Organic solution is propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone or ethylene glycol monomethyl ether.
7. by the described improved zinc acrylate resin of claim 6/resin of copper preparation method, it is characterized in that: described initiator is a kind of in azo-initiator, the peroxide initiator, and wherein initiator accounts for the 0.1-5% of polymerization system quality; Wherein azo-initiator can be Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN); The peroxide initiator can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
8. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: described under steady temperature with the acrylic polymer of above-mentioned steps with disperse after zinc hydroxide/copper and organic acid under the effect of organic solvent at 70-110 ℃, the zinc acrylate resin/resin of copper with hydrolysis properties is made in reaction under the stirring velocity of 100-500r/min; Wherein, organic acid is phenylformic acid or naphthenic acid; Organic acid is 1.0-1.5:1 with the amount of substance ratio of zinc hydroxide/copper; Described organic solvent is the mixed solvent of dimethylbenzene and propyl carbinol, and volume ratio is 4:1 between dimethylbenzene and the propyl carbinol.
9. by the described improved zinc acrylate resin of claim 1/resin of copper preparation method, it is characterized in that: described zinc acrylate resin/resin of copper as resin with softening agent, pigment, filler, stain control agent, auxiliary agent, help and ooze out agent and organic solvent mixes, namely obtain marine antifouling coating; By weight percentage, 20-30% resin, 1-10% softening agent, 5-10% pigment, 5-10% filler, 5-10% stain control agent, 0.1-0.5% auxiliary agent, 4-10% help ooze out agent, surplus is organic solvent.
10. by the described improved zinc acrylate resin of claim 9/resin of copper preparation method, it is characterized in that: organic solvent is a kind of in propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone, the ethylene glycol monomethyl ether in the described coating, and massfraction is 40-60%; Described stain control agent is capsicine, 1,2-benzisothiazole-3-ketone, 4,5-dichloro--2-n-octyl-4-isothiazoline-3-ketone, pyridine triphenylborane, Zinc Pyrithione or pyrithione ketone; Described pigment is a kind of in ferric oxide, titanium dioxide, zinc oxide, carbon black, iron oxide black, calcium carbonate, Calucium Silicate powder, the talcum powder; Described filler is tetrafluoroethylene, paraffin oil or fluorographite.
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| CN104725551A (en) * | 2013-12-23 | 2015-06-24 | 浙江省海洋开发研究院 | Synthetic method of copper/zinc acrylate self-polishing antifouling resin |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080892A (en) * | 1985-05-17 | 1992-01-14 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
| US5199977A (en) * | 1990-07-19 | 1993-04-06 | Nippon Paint Company, Ltd. | Antifouling paint compositions |
| JP2002138108A (en) * | 2000-11-02 | 2002-05-14 | Kansai Paint Co Ltd | Method of producing metal-containing resin and composition thereof |
| US20020112407A1 (en) * | 2001-02-12 | 2002-08-22 | Olivier Anthony | Preparation of particles by hydrolysis of a metal cation in the presence of a polymer |
| CN1544488A (en) * | 2003-11-10 | 2004-11-10 | 中国海洋大学 | Method for preparation of zinc or copper containing acrylic acid resin |
| US7105136B2 (en) * | 2001-09-28 | 2006-09-12 | Spiess-Urania Chemicals Gmbh | Controlled morphogenesis of copper salts |
-
2013
- 2013-04-12 CN CN201310125508.XA patent/CN103289007B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080892A (en) * | 1985-05-17 | 1992-01-14 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
| US5199977A (en) * | 1990-07-19 | 1993-04-06 | Nippon Paint Company, Ltd. | Antifouling paint compositions |
| JP2002138108A (en) * | 2000-11-02 | 2002-05-14 | Kansai Paint Co Ltd | Method of producing metal-containing resin and composition thereof |
| US20020112407A1 (en) * | 2001-02-12 | 2002-08-22 | Olivier Anthony | Preparation of particles by hydrolysis of a metal cation in the presence of a polymer |
| US7105136B2 (en) * | 2001-09-28 | 2006-09-12 | Spiess-Urania Chemicals Gmbh | Controlled morphogenesis of copper salts |
| CN1544488A (en) * | 2003-11-10 | 2004-11-10 | 中国海洋大学 | Method for preparation of zinc or copper containing acrylic acid resin |
Non-Patent Citations (1)
| Title |
|---|
| 鲁伶兰等: "稳定态氢氧化铜的制备", 《天津化工》 * |
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| CN103992447A (en) * | 2014-06-05 | 2014-08-20 | 上海众取化工有限公司 | Synthesis method of zinc acrylate resin |
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| CN115368767B (en) * | 2022-08-03 | 2023-06-20 | 中海油常州涂料化工研究院有限公司 | Water-based fireproof paint |
| CN115895375A (en) * | 2022-11-26 | 2023-04-04 | 夜视丽新材料(仙居)有限公司 | Waterproof antifouling coating resin |
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