CN103289007B - A kind of zinc acrylate resin/resin of copper preparation method of improvement - Google Patents
A kind of zinc acrylate resin/resin of copper preparation method of improvement Download PDFInfo
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Abstract
The invention belongs to marine antifouling coating technical field, the zinc acrylate resin/resin of copper preparation method of a kind of improvement specifically.Using the mixed system of water, organic solvent as dispersion medium, metal salt solution and alkaline solution are reacted and generates zinc hydroxide/copper, and fully disperse in dispersion agent, filtration drying after dispersion, the zinc hydroxide/copper of the loose property that secures satisfactory grades; At a constant temperature vinylformic acid soft or hard monomer is generated the acrylic polymer containing carboxyl by initiator generation Raolical polymerizable; Zinc hydroxide/copper after the acrylic polymer of above-mentioned steps and dispersion is reacted the zinc acrylate resin/resin of copper made and have hydrolysis properties by steady temperature under organic acid effect; Zinc hydroxide/copper that the present invention obtains, in reacting with acrylic polymer, good dispersity, soilless sticking phenomenon, the reaction times is short, and cost is low, and does not need to improve existing equipment.
Description
Technical field
The invention belongs to marine antifouling coating technical field, the zinc acrylate resin/resin of copper preparation method of a kind of improvement specifically.
Background technology
Marine fouling organism mainly refers to animal and plant on attachment hull bottom, buoy and all Artificial facilities and the general name of microorganism, is one of important factor affecting 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 marine culture mollusc.
The common method solving biodeterioration is brushing antifouling paint.Organotin rises in 20 century 70s from polishing antifouling technology, organotin self-polishing coating is that a kind of multipolymer by Tributyl Tin Methacrylate and methyl methacrylate and Red copper oxide combine, this kind of antifouling paint effectively can prevent the attachment of marine fouling organism, its mechanism is that methylmethacrylate copolymer is constantly hydrolyzed with sea water immersion, tributyl tin (TBT) discharges and plays antifouling effect, has broad spectrum, high efficiency, effect length of antifouling phase, low cost and other advantages.After the eighties, it is found that the TBT that this coating discharges can be deposited on ooze for a long time and be accumulated in biology, serious harm is caused to the marine eco-environment.International Maritime Organizaton in 2003 requires to prohibit the use organotin as marine antifoulant, and within 2008, all boats and ships prohibit the use Organotin antifouling paints.Therefore, development tin-free self-polishing type antifouling paint is a kind of environmental protection, economy, and can meet a kind of low toxicity of current environment requirement, free of contamination antifouling paint.
In recent years, the poisonous stain control agent substitutes such as research organotin are all being set about by each state, and make great efforts the novel Tin-free Spc Anti-fouling Paint of development research, and wherein, vinylformic acid copper/zinc becomes one of study hotspot.Nineteen ninety, US Patent No. 5080892 described the method for acrylic acid synthesizing zinc/resin of copper, and the method by the carboxylic acrylic resin of synthesis, then obtains zinc acrylate resin/resin of copper with zinc hydroxide/copper, organic acid reaction.Within 2004, Chinese patent CN1544488A first synthesizes basic zinc carboxylate/mantoquita, and the acrylate copolymer of resynthesis band carboxyl, both are obtained by reacting zinc acrylate resin/copper.The first acrylic acid synthesizing zinc/copper small molecule monomer of Chinese patent CN102167775 in 2011, then generates zinc acrylate resin/resin of copper with the radical polymerization of vinylformic acid soft or hard monomer initiator.In zinc acrylate resin in aforesaid method/copper generative process, easily there is agglomeration in metal base (alkali formula organic acid salt), or is deposited in device bottom, causes zinc acrylate resin/resin of copper stability low, anti-fouling effect poor repeatability.
Summary of the invention
The object of this invention is to provide a kind of zinc acrylate resin/resin of copper preparation method of improvement.
For achieving the above object, the technical solution used in the present invention is:
A kind of zinc acrylate resin/resin of copper preparation method of improvement, using the mixed system of water, organic solvent as dispersion medium, metal salt solution and alkaline solution are reacted and generates zinc hydroxide/copper, and fully disperse in dispersion agent, filtration drying after dispersion, the zinc hydroxide/copper of the loose property that secures satisfactory grades;
At a constant temperature vinylformic acid soft or hard monomer is generated the acrylic polymer containing carboxyl by initiator generation Raolical polymerizable;
Zinc hydroxide/copper after the acrylic polymer of above-mentioned steps and dispersion is reacted the zinc acrylate resin/resin of copper made and have hydrolysis properties by steady temperature under organic acid effect;
Detailed process is as follows:
Wherein: R=H or CH
3; R
1=CH
3, C
2h
5, C
4h
9or C
8h
17;
R
2=C
6h
5or C
5h
9(CH
2)
n; M=Cu or Zn.
Using the mixed system of water, organic solvent as dispersion medium, the inorganic zinc/copper salt solution of solubility and inorganic alkali solution are reacted and generates zinc hydroxide/copper, and fully disperse in dispersion agent, filtration drying after dispersion, the zinc hydroxide/copper of the loose 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 described dispersion medium, between water and organic solvent, volume ratio is 100:0.2-6.
Organic solvent in described dispersion medium is the mixed solution of alcohol and ketone, and wherein alcohol and ketone are by volume for the ratio of 1-5:1 mixes;
Described alcohol is methyl alcohol, ethanol, propyl alcohol or butanols; Ketone is methylethylketone, acetone or butanone; The volume ratio of described zinc hydroxide/between copper and dispersion medium is 1:2-5.
Described dispersion agent is the one 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 ester, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, hexenyl bis-stearamides, polyoxyethylene glycol; Wherein the mass ratio of dispersion agent and zinc hydroxide/copper is 0.1%-1%.
Zinc hydroxide/the copper of generation is carried out dispersed with stirring in dispersion system, and jitter time is 1-3h, and dispersion temperature is 40-50 DEG C, and stirring velocity is 100-500r/min.
Be there is Raolical polymerizable in presence of organic solvent by initiator in vinylformic acid soft or hard monomer at a constant temperature and generate the acrylic polymer containing carboxyl; Described polymeric reaction temperature is 70-90 DEG C; 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 n-octyl;
Methacrylic ester is methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, Octyl methacrylate, Isooctyl methacrylate or n octyl methacrylate;
Described organic solvent is that organic solution and dimethylbenzene form, and wherein dimethylbenzene mixes with the volume ratio of organic solution by 4:1; 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 the one in azo-initiator, peroxide type initiators, 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); Peroxide type initiators can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
Described at a constant temperature by the acrylic polymer of above-mentioned steps with dispersion after zinc hydroxide/copper and organic acid under the effect of organic solvent, under the stirring velocity of 70-110 DEG C, 100-500r/min, react the zinc acrylate resin/resin of copper made and there is hydrolysis properties; 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 between dimethylbenzene and propyl carbinol, volume ratio is 4:1.
Described zinc acrylate resin/resin of copper as resin and 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.
In described coating, organic solvent is the one in propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone, ethylene glycol monomethyl ether, and massfraction is 40-60%; Described stain control agent is capsicine, BIT, 4,5-dichloro-s-Kathon, triphenylboron pyridine alkane, Zinc Pyrithione or pyrithione ketone; Described pigment is the one in ferric oxide, titanium dioxide, zinc oxide, carbon black, iron oxide black, calcium carbonate, Calucium Silicate powder, talcum powder; Described filler is tetrafluoroethylene, paraffin oil or fluorographite; Described auxiliary agent is flow agent, dispersion agent, defoamer, wetting agent, anti-settling agent; Described help that to ooze out agent be rosin.
The present invention has the following advantages:
1. zinc hydroxide/copper adopts water and organic solvent to be dispersion medium, and after dispersant, its dispersion effect is good, can reach nano level;
2. the method for zinc acrylate resin or acrylate resin synthetic method employing both at home and abroad comparatively before, the method is without the need to increasing equipment cost, and due to the high dispersing of zinc hydroxide/copper, the reaction times shortens, thus production cost is reduced, and 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, antifouling property is high, and can effectively suppress marine fouling organism to adhere to and growth, and pollution-free to the marine eco-environment.
Embodiment
Following examples further illustrate of the present invention, but the present invention is not limited thereto.
Zinc acrylate resin/resin of copper the preparation method improved:
The first step metal salt solution and alkaline solution react and generate zinc hydroxide/copper, the mixed system of Qi Zhongshui, organic solvent as dispersion medium, after dispersant, filtration drying, the zinc hydroxide/copper of the loose property that secures satisfactory grades;
Second step at a constant temperature vinylformic acid soft or hard monomer generates by the Raolical polymerizable of initiator the acrylic polymer containing carboxyl;
Under 3rd step steady temperature, acrylic polymer and the zinc hydroxide/copper after disperseing, organic acid reaction make 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 DEG C; Described stirring velocity is 100-500r/min.With above-mentioned resin for film forming matter, make self polishing copolymer antifouling paint.
Embodiment 1
1) preparation of zinc hydroxide
32.2g sodium hydroxide is added in the solution containing 2.5ml ethanol, 0.5ml acetone, 97ml water, constantly be stirred to sodium hydroxide to dissolve completely, using 0.2g Sodium hexametaphosphate 99 as dispersion agent, at 40 DEG C, 500r/min fully stirs 0.5 hour, slow dropping 4.0mol/L zinc nitrate 100ml, aobvious neutral to pH value of solution.Insulation dispersion 1 hour, vacuum filtration, distilled water 100ml divide 3 washings, drain, 80 DEG C of dryings 12 hours.
2) preparation of acrylic polymer
Be equipped with in 500ml tri-mouthfuls of round-bottomed flasks of stirring, condenser, constant pressure funnel, add 100g mixed solvent (dimethylbenzene and propyl carbinol mass ratio are 4:1), 80 DEG C, 400r/min, drip Acrylic Acid Monomer mixture (23g vinylformic acid, 31g methyl methacrylate, the 41g butyl acrylate) 100g containing 4g Diisopropyl azodicarboxylate (AIBN), 1g n-dodecyl mereaptan in 3h, the process that drips keeps reflux state.Be incubated 1 hour, add the mixed solvent 25g containing 4%AIBN in half an hour wherein, insulation 2h, reaction terminates, and obtains the acrylic polymer of micro-yellow clear.
3) synthesis of zinc acrylate resin
To be equipped with in 250ml tri-mouthfuls of round-bottomed flasks 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 DEG C, 400r/min, react 6 hours, question response mixture is to vitreous state, intensification heating 105 DEG C dewaters to exclusion and only distillates, and obtains the zinc acrylate resin of yellow transparent.
4) preparation (preparing antifouling paint in a conventional manner) of zinc acrylate resin antifouling paint,
Take 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 is ground to fineness and reaches less than 25 μm.
For testing the performance of marine antifouling coating, carry out sticking power mensuration with reference to standard GB/T/T1720 " paint film adhesion assay method ".This experiment is by the tinplate of spraying one priming paint, middle paint and antifouling varnish, and soak 48 hours in artificial seawater, taking-up is dried, and measures paint film adhesion with drawing circle method.Paint film adhesion is divided into 1-7 seven grades, and 1 grade of sticking power is best, and 7 grades the poorest.
For testing the antifouling property of antifouling paint obtained, with reference to standard GB/T-5370-2007, by 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 trough of belt rectangular batten two ends bolt to fix, and carries out shallow sea immersion test.This test in fouling organism nursery stage-May carries out, choose coastal seawater culture zone, Yantai and carry out marine link plate, 3 months link plate time, regularly model is checked, the stained situation of mode record model adopting word and take pictures.Remove the ooze on model during observation with seawater gently, remove the region of template edge 20mm to eliminate edge effect simultaneously.Meanwhile, shorten model as early as possible and take out and observing time, immediately model is immersed in seawater after observation, avoid settled organism death to affect result.The fouling organism area occupied in model is calculated according to result of taking pictures.Experimental result is as shown in table 1
Embodiment 2
Difference from Example 1 is, the preparation of copper hydroxide:
32.2g sodium hydroxide is added in the solution containing 2.5ml ethanol, 0.5ml acetone, 97ml water, constantly be stirred to sodium hydroxide to dissolve completely, using 0.2g Sodium hexametaphosphate 99 as dispersion agent, under 40C, 500r/min fully stirs 0.5 hour, slow dropping 4.0mol/L copper hydroxide 100ml, aobvious neutral to pH value of solution.Insulation dispersion 1 hour, vacuum filtration, distilled water 100ml divide 3 washings, drain, 80 DEG C of dryings 12 hours.
The operational instances of other steps, with example 1, namely obtains vinylformic acid copper antifouling paint, the results are shown in Table 1.
Embodiment 3
Difference from Example 1 is, the preparation of copper hydroxide:
32.0g sodium hydroxide is added in the solution containing 2.0ml ethanol, 1.0ml methylethylketone, 97ml water, constantly be stirred to sodium hydroxide to dissolve completely, using 0.2g polyacrylamide as dispersion agent, at 40 DEG C, 500r/min fully stirs 0.5 hour, slow dropping 4.0mol/L zinc chloride 100ml, aobvious neutral to pH value of solution.Insulation dispersion 1 hour, vacuum filtration, distilled water are washed till and can't detect chlorion, drain, 80 DEG C of dryings 12 hours.
The operational instances of other steps is with example 1, and namely obtain zinc acrylate resin antifouling paint, link plate the results are shown in Table 1.
Zinc acrylate resin/resin of copper antifouling paint performance comparison that table 1 improves
Note: 1. blank model is except epoxy primer, is not coated with marine anti-fouling paint
2. make zinc acrylate resin by oneself, not containing stain control agent
3. chlorinated rubber resin refers to chlorinated rubber resin to be film forming matter, adds antifouling paint prepared by BIT.
Claims (8)
1. zinc acrylate resin/resin of copper the preparation method improved, it is characterized in that: using the mixed system of water, organic solvent as dispersion medium, inorganic zinc/the copper salt solution of solubility and inorganic alkali solution are reacted and generates zinc hydroxide/copper, and fully disperse in dispersion agent, filtration drying after dispersion, the zinc hydroxide/copper of the loose 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 described dispersion medium, between water and organic solvent, volume ratio is 100:0.2-6;
Organic solvent in described dispersion medium is the mixed solution of alcohol and ketone, and wherein alcohol and ketone are by volume for the ratio of 1-5:1 mixes; Described alcohol is methyl alcohol, ethanol, propyl alcohol or butanols; Ketone is methylethylketone, acetone or butanone; The volume ratio of described zinc hydroxide/between copper and dispersion medium is 1:2-5;
At a constant temperature vinylformic acid soft or hard monomer is generated the acrylic polymer containing carboxyl by initiator generation Raolical polymerizable;
Zinc hydroxide/copper after the acrylic polymer of above-mentioned steps and dispersion is reacted the zinc acrylate resin/resin of copper made and have hydrolysis properties by steady temperature under organic acid effect;
Detailed process is as follows:
Wherein: R=H or CH
3; R
1=CH
3, C
2h
5, C
4h
9or C
8h
17;
R
2=C
6h
5or
m=Cu or Zn.
2., by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 1, it is characterized in that: described dispersion agent is the one 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 ester, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, hexenyl bis-stearamides, polyoxyethylene glycol; Wherein the mass ratio of dispersion agent and zinc hydroxide/copper is 0.1%-1%.
3. by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 1, it is characterized in that: the zinc hydroxide/copper of generation is carried out dispersed with stirring in dispersion system, jitter time is 1-3h, and dispersion temperature is 40-50 DEG C, and stirring velocity is 100-500r/min.
4. by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 1, it is characterized in that: at a constant temperature vinylformic acid soft or hard monomer, by initiator, Raolical polymerizable is occurred in presence of organic solvent and generate the acrylic polymer containing carboxyl; Described polymeric reaction temperature is 70-90 DEG C; Polymerization reaction time is 4-8h;
Described vinylformic acid soft or hard monomer is acrylate or methacrylic ester and vinylformic acid; Wherein, acrylate is methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate or Octyl acrylate;
Methacrylic ester is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate or Octyl methacrylate;
Described organic solvent is made up of the dimethylbenzene of volume ratio 4:1 and propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone or ethylene glycol monomethyl ether.
5., by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 4, it is characterized in that: described initiator is the one in azo-initiator, peroxide type initiators, 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); Peroxide type initiators can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide.
6. by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 1, it is characterized in that: described at a constant temperature by the acrylic polymer of above-mentioned steps with dispersion after zinc hydroxide/copper and organic acid under the effect of organic solvent, under the stirring velocity of 70-110 DEG C, 100-500r/min, react the zinc acrylate resin/resin of copper made and there is hydrolysis properties; 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 between dimethylbenzene and propyl carbinol, volume ratio is 4:1.
7. by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 1, it is characterized in that: described zinc acrylate resin/resin of copper as resin and 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.
8. by the zinc acrylate resin/resin of copper preparation method of improvement according to claim 7, it is characterized in that: in described coating, organic solvent is the one in propyl carbinol, isopropylcarbinol, the trimethyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene, normal hexane, pimelinketone, acetone, ethylene glycol monomethyl ether, massfraction is 40-60%; Described stain control agent is capsicine, BIT, 4,5-dichloro-s-Kathon, triphenylboron pyridine alkane, Zinc Pyrithione or pyrithione ketone; Described pigment is the one in ferric oxide, titanium dioxide, zinc oxide, carbon black, iron oxide black, calcium carbonate, Calucium Silicate powder, talcum powder; Described filler is tetrafluoroethylene, paraffin oil or fluorographite.
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| 稳定态氢氧化铜的制备;鲁伶兰等;《天津化工》;20070531;第21卷(第3期);40-41 * |
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