CN1073608C - Method for preparing conductive antifouling corrosion-resistant poly-aniline paint - Google Patents
Method for preparing conductive antifouling corrosion-resistant poly-aniline paint Download PDFInfo
- Publication number
- CN1073608C CN1073608C CN97115977A CN97115977A CN1073608C CN 1073608 C CN1073608 C CN 1073608C CN 97115977 A CN97115977 A CN 97115977A CN 97115977 A CN97115977 A CN 97115977A CN 1073608 C CN1073608 C CN 1073608C
- Authority
- CN
- China
- Prior art keywords
- paint
- hour
- antifouling
- coating
- polyaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 31
- 239000003973 paint Substances 0.000 title claims abstract description 23
- 238000005260 corrosion Methods 0.000 title claims description 7
- 230000007797 corrosion Effects 0.000 title claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims description 5
- 238000000034 method Methods 0.000 title description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 229920000767 polyaniline Polymers 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002019 doping agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000002525 ultrasonication Methods 0.000 claims description 7
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 1
- 229940112669 cuprous oxide Drugs 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 14
- 239000013535 sea water Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- -1 functional groups organic acid Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FTOZMXOHOKRHNL-UHFFFAOYSA-N ethyl 2,3-dihydroxypropanoate Chemical compound CCOC(=O)C(O)CO FTOZMXOHOKRHNL-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention belongs to a preparation method for conductive antifouling anticorrosive polyaniline paint. In the present invention, an organic solvent or water is used as a medium and functional protonic acid is used as a doping agent to prepare a conductive dispersion liquid, which is blended with copolymers, such as epoxy resin, polyurethane, chlorinated rubber, etc. or water-soluble silicate, alcohol-soluble partially-hydrolysable tetraethyl orthosilicate, cuprous oxide, etc. to obtain the conductive paint with the solid content of 5 to 85 wt%. A coating of the paint has the electric conductivity of 10<-6> to 10<0> S/cm, and in the marine environment, has the electric conduction maintaining stable for more than one year. The conductive antifouling anticorrosive polyaniline paint can be used as both antifouling paint and anticorrosive paint for ships.
Description
The invention belongs to the preparation method of conductive antifouling corrosion-resistant poly-aniline paint
Prevent that sea marine organism pollution and marine corrosion from being one of important difficult problem facing of shipping industry always.Existing anti-fouling ship paint mainly is made up of toxicants such as Red copper oxide or organotins, utilizes oozing out of poison material to suppress adhering to and grow and reaching antifouling purpose of marine life.Because the poison material high concentration severe contamination ocean environment that coating discharges, people extremely pay close attention to the prospect of this class antifouling paint.Developed country worked out or worked out the use of corresponding regulation limitations toxicity antifouling paint Europe, the United States, day etc.Therefore nontoxic antifouling paint such as biological anti-fouling paint, low surface energy anti-fouling paint and conduction antifouling paint comes into one's own just day by day.On the other hand, because existing boats and ships protective system is mainly the organic or inorganic zinc-rich paint, be to rely on the mass consumption heavy metal zinc to reach the rot-resistant purpose, not only be subjected to the restriction of the resource of zinc, also ocean environment is caused severe contamination.Therefore seeking novel pollution-free protective system has been inevitable.
The clear 58-11564 report of Japanese Patent can be used as the conduction antifouling paint with the electrically conducting coating that is mixed with metal-powder or conductive carbon black under logical weak current, but metal-powder density is big and not corrosion-resistant, conductive carbon black is moved to the surface easily and is escaped in the seawater and reduce volume conductance, has therefore influenced the life-time service effect.Day disclosure special permission communique JP62,249,906 to adopt chlorinated rubbers be base-material, the doped hydrochloride polyaniline is that stain control agent has prepared the conduction antifouling paint, to marine alga and some under water microorganism certain resistivity is arranged.But, limited its life-time service effect because the specific conductivity of the polyaniline of doped hydrochloride descends very soon in time in seawater.
A kind of preparation method who dissolves in the electrically conductive polyaniline of ordinary organic solvents is disclosed among the International Patent WO92/22911.Its core is to make doping agent with the specific functional groups organic acid, but need to use excessive acid just can make electrically conductive polyaniline solvable at organic solvents such as dimethylbenzene, chloroforms, and superacid existence can have a strong impact on the final performance of product in the coating.Chinese patent 96122196.8 discloses a kind of direct doped polyaniline of protonic acid with the band hydrophilic functional groups and has prepared the method for the aqueous solution or the aqueous dispersion of electrically conductive polyaniline, but does not wherein relate to the preparation method of water system marine finish.
The present invention provide a kind of that form by electrically conductive polyaniline, Red copper oxide, dispersion medium, base material, defrother each component, obtain to have the preparation method that long-term electricity is led stability, the electrically conducting coating of antifouling or antiseptic property is arranged through stirring, grinding, vibration, ultrasonication.The composition and the preparation method of conductive antifouling corrosion-resistant poly-aniline paint of the present invention are as follows: 1) polyaniline, and structure is as follows:
R wherein
1, R
2, R
1', R
2'=H, C
kH
2k+1K=0-18, OC
kH
2k+1K=0-18 or-SO
3H k=0-4, y are between 0-1, and n is an integer;
2) dispersion medium: dimethylbenzene, butanols, ethanol or water;
3) base material: solid content is at the urethane of 20-50%, Resins, epoxy, chlorination rubber
Glue, high chlorinated rubber, water glass, potassium silicate or the positive silicic acid of partial hydrolysis alcohol dissolubility
Ethyl ester;
4) defrother: lipid acid C
3～C
10Alkyl ester or ethylene oxide oligopolymer;
5) antifouling auxiliary agent: Red copper oxide;
6) doping agent mainly is divided into two classes,
The doping agent that organic system conduction antifouling paint is used has following general formula:
C
nH
2n+1-SO
3H or
N is between 1-18;
Water system is conducted electricity the doping agent that antifouling protective system uses and is had one of structure of general formula (1)-(3):
R=R
1(OCH
2CH
2)
nOr R
1(OCH
2)
n=1-100, wherein R
1=C
mH
2m+1M=0-12 or C
mH
2m+1C
6H
4M=0-12;
Mol ratio (the N/H of polyaniline/doping agent
+) 1: between the 0.1-1.5, the defrother consumption accounts for coating solid content 0.01-5wt%, total solid content 5-85wt%, the content of each component can be regulated as required;
The preparation method can choose following one or both wantonly and use:
1) magnetic stirrer stirs and uses ultrasonication 0.5-12 hour after 2-24 hour, at 40-95 ℃ of following thermal treatment 0.5-10 hour, in the container of granulated glass sphere or porcelain ball, with vibrator vibration 2-24 hour;
2) magnetic stirrer or mortar stirred or grind after 2-24 hour, again at 40-95 ℃ of following thermal treatment 0.5-10 hour, processed 0.5-12 hour at ball mill or colloidal mill.
The present invention can prepare solid content 5-85wt% by regulating the each component ratio under the prerequisite that does not need complicated technology and equipment, the coating specific conductivity is between 10
-6～10
0The antifouling protective system of the conduction of S/cm.
Method of the present invention can have the coating of different specific conductivity through the preparation of means such as spraying, brushing.
Embodiment provided by the invention is as follows:
Embodiment 1:
With 8.0g polyaniline, 14.46g Witco 1298 Soft Acid (purity 97%) (N/H
+Than being 1: 0.5) in 77.54g dimethylbenzene, to mix, ultrasonication 2 hours is made the electrically conductive polyaniline dispersion liquid.Get above-mentioned dispersion liquid 50g, with 50g 685 type polyurethane component Bs (solid content 45wt%), 0.1g ethyl butyrate, under ultrasonic wave, handled 1 hour, add 50g685 type polyurethane first component (solidifying agent subsequently, solid content 45wt%), make electrically conducting coating after ground and mixed on the colloidal mill, the coating specific conductivity is 0.5S/cm.Be coated on the 45# steel plate and be immersed in the seawater, through busy season in the marine life growth, the coating specific conductivity remains unchanged substantially, the marine life of surface attachment only for do not add conduct electricity component reference examples 20%, surface of steel plate has one deck compact oxide, after removing zone of oxidation, surface of steel plate light as new shows that coating also has good preservative effect.
Embodiment 2
With 8.0g polyaniline, 2.35g butyl sulfonic acid (purity 97%) (N/H
+Than being 1: 0.2) in 40g dimethylbenzene, mix, induction stirring 12 hours, ultrasonication 6 hours refluxed 1 hour down at 85 ℃ again, made the electrically conductive polyaniline dispersion liquid.Get above-mentioned dispersion liquid 25g, with 50g urethane component B (solid content 25wt%), 0.1g ethyl octylate, under ultrasonic wave, handled 1 hour, add 15g 685 type polyurethane first components (solid content 25wt%) subsequently, make electrically conducting coating after ground and mixed on the colloidal mill, the coating specific conductivity is 4.2x10
-4S/cm.Be coated in 45
#Be immersed on the steel plate in the seawater, through the busy season of growing at marine life, the coating specific conductivity remains unchanged substantially, but the marine life of surface attachment for do not add conduct electricity component reference examples 50%, surface of steel plate has zone of oxidation, remove zone of oxidation after, can find out that still steel plate partly is corroded.
Embodiment 3:
With 8.0g polyaniline, 34.26g Witco 1298 Soft Acid (purity 97%) (N/H
+Than being 1: 1.5) in 77.54g dimethylbenzene, to mix, ultrasonication 6 hours refluxed 10 hours down at 40 ℃ again, made the electrically conductive polyaniline dispersion liquid.Get above-mentioned dispersion liquid 50g, with 50g Resins, epoxy E6101,50g dimethylbenzene, 50g butanols, 0.5g ethyl hexanoate was handled 1 hour under ultrasonic wave, after ground and mixed on the colloidal mill, the adding tung oil acid anhydride is a solidifying agent, makes electrically conducting coating, and the coating specific conductivity is 0.5S/cm.Be coated in 45
#Be immersed on the steel plate in the seawater, through the busy season of growing at marine life, the coating specific conductivity remains unchanged substantially, the marine life of surface attachment only for do not add conduct electricity component reference examples 15%, surface of steel plate has zone of oxidation, remove zone of oxidation after, still can find out the steel plate deep layer also the part be corroded.
Embodiment 4
With 8.0g polyaniline, 14.46g Witco 1298 Soft Acid (purity 97%) (N/H
+Than being 1: 0.5) in mortar, mix, electrically conductive polyaniline is made in 60 ℃ of following thermal treatment 5 hours.This electrically conductive polyaniline 11.23g is joined 50g 685 type polyurethane component Bs (solid content 50wt%), 0.1g in the ethyl butyrate, under ultrasonic wave, handled 1 hour, add 50g 685 type polyurethane first component (solidifying agent subsequently, solid content 50wt%), make electrically conducting coating after ground and mixed on the colloidal mill, the coating specific conductivity is 0.5S/cm.Be coated in 45
#Be immersed in the seawater on the steel plate, through busy season (annual March is to September) in the marine life growth, the coating specific conductivity remains unchanged substantially, the marine life of surface attachment only for do not add conduct electricity component reference examples 20%, surface of steel plate has one deck compact oxide, after removing zone of oxidation, surface of steel plate light as new shows that coating also has good preservative effect.
Embodiment 5:
With 4g polyaniline, 19.35g (CH
3(OCH
2CH
2)
7O)
2PO (OH) and 0.5g glycerol fatty acid ester grind well in mortar, and this mixture is added in the 100ml there-necked flask, divide the washing mortar three times with 50ml ethanol, and mix in the adding there-necked flask.Get this mixed solution 18.6g, in mixed solution, add 50g partial hydrolysis tetraethoxy ethanolic soln (concentration is 30%), vibrated 2 hours after adding granulated glass sphere, obtain the heavy-gravity dispersion liquid, be added dropwise to hydrochloric acid soln (consumption be the partial hydrolysis tetraethoxy mole number 0.2%), specific conductivity is 1.2 * 10 behind the coating curing
-1S/cm.Busy season in the marine life growth soaks in seawater, and the accompanying marine life of coatingsurface only is about 30% of reference example (the partial hydrolysis tetraethoxy solidified coating that does not add electrically conductive polyaniline).Coating remains unchanged substantially 6 months internal conductance rates, removes coating and finds one deck to be arranged than compact oxide at surface of steel plate, remove the floating rust of zone of oxidation after, surface of steel plate light as new shows that coating still has good preservative effect.
Embodiment 6:
With 4g polyaniline, 6.88g (CH
3(OCH
2CH
2)
2O)
2PO (OH) and 0.5g glycerol fatty acid ester grind well in mortar, and this mixture is added in the 100ml there-necked flask, with three washings of 30ml moisture mortar, and mix in the adding there-necked flask.Get this mixed solution 20g, mix with 45g sodium silicate solution (solid content 30%), vibration is 24 hours behind the adding granulated glass sphere.With a certain amount of hydrochloric acid soln acidifying and as coating curing agent.The coating specific conductivity is 4.0 * 10
-3S/cm, coating is soaked 6 months specific conductivity in the marine life growth busy season and is remained unchanged substantially in seawater, and has certain antifouling and preservative effect.
Embodiment 7:
With 4g polyaniline, 8.1g (CH
3(OCH
2CH
2)
16O) PO (OH)
2With the 0.5g molecular weight be 500 ethylene oxide oligomer, in mortar, grind well, this mixture is added in the 100ml there-necked flask, with three washings of 30ml moisture mortar, and add in the there-necked flask and mix.Get this mixed solution 20g, mix with 45g potassium silicate solution (solid content 30%), vibration is 24 hours behind the adding granulated glass sphere.Add a certain amount of hydrochloric acid soln acidifying and as coating curing agent.The coating specific conductivity is about 4.0 * 10
-4S/cm, coating is soaked 6 months specific conductivity in the marine life growth busy season and is remained unchanged substantially in seawater, and has certain antifouling and preservative effect.
Embodiment 8:
8.0g polyaniline, 4.38g tosic acid are mixed in 38.62g dimethylbenzene, and ultrasonication 2 hours refluxed 5 hours down at 60 ℃ again, made the electrically conductive polyaniline dispersion liquid.Get above-mentioned dispersion liquid 25g, with 25g 685 type polyurethane component Bs (solid content 50wt%), 0.1g ethyl glycerate, under ultrasonic wave, handled 6 hours, add 25g 685 type polyurethane first components (solid content 50wt%) subsequently, make electrically conducting coating after ground and mixed on the colloidal mill, the coating specific conductivity is 0.02S/cm.Be coated in 45
#Be immersed on the steel plate in the seawater, through the busy season of growing at marine life, the coating specific conductivity remains unchanged substantially, the marine life of surface attachment for do not add conduct electricity component reference examples 40%, surface of steel plate has a zone of oxidation, remove zone of oxidation after, surface of steel plate have the part be corroded.
Embodiment 9:
With sulfonated polyaniline 6g, chlorinated rubber 12g, Red copper oxide 0.6g, ultrasonic wave is mixed in 50g dimethylbenzene, refluxes 1 hour down at 95 ℃.The coating specific conductivity is 3.2 * 10
-2S/cm soaks 6 months specific conductivity still 10 in marine life growth busy season coating in seawater
-2About S/cm, the surface does not have marine life substantially and adheres to, and removes the floating rust in surface, and the surface of steel plate light is as newly, and preservative effect is better.
Embodiment 10:
With the 6g polyaniline, the 3.1g methylsulphonic acid, 0.1g Red copper oxide, 41.8g dimethylbenzene were handled 2 hours under ultrasonic wave, behind the high chlorinated rubber of adding 12g, mixed 10 hours in colloidal mill, and gained coating specific conductivity is 3.0 * 10
-2S/cm.In seawater, soak 6 months specific conductivity still 10 in marine life growth busy season coating
-2About S/cm, coatingsurface does not have marine life substantially and adheres to, and anti-fouling effect is good.Remove the floating rust in surface, surface of steel plate light as new, preservative effect is better.
Embodiment 11:
With 4g polyortho methylaniline, 20g CH
3O (CH
2CH
2O)
20SO
3H and 0.5g glycerol fatty acid ester grind well in mortar, and this mixture is added in the 100ml there-necked flask, with three washings of 50ml moisture mortar, and mix in the adding there-necked flask.Get this mixed solution 25g, mix with 45g sodium silicate solution (solid content 30%), vibration is 24 hours behind the adding granulated glass sphere.Add a certain amount of hydrochloric acid soln acidifying and as coating curing agent.The coating specific conductivity is about 4.0 * 10
-3S/cm, coating is soaked 6 months specific conductivity in the marine life growth busy season and is remained unchanged substantially in seawater, and has certain antifouling and preservative effect.
Embodiment 12
With the poly-o ethyl aniline of 8g, 21.26g CH
3O (CH
2O)
10SO
3H, 1.2g capric acid acetoacetic ester and 50ml water were handled 4 hours under ultrasonic wave.Get this mixed solution 25g, add the 30g water glass, 60ml water adds granulated glass sphere subsequently 650 ℃ of following thermal treatments 6 hours, vibrates 24 hours.Add a certain amount of hydrochloric acid soln acidifying and as coating curing agent.The coating specific conductivity is about 4.0 * 10
-4S/cm, coating is soaked 6 months specific conductivity in the marine life growth busy season and is remained unchanged substantially in seawater, and has certain antifouling and preservative effect.
Claims (1)
1, a kind of preparation method of conductive antifouling corrosion-resistant poly-aniline paint is characterized in that this coating is made up of following component:
1) polyaniline, structure is as follows:
R wherein
1, R
2, R
1', R
2'=H, C
kH
2k+1K=0-18, OC
kH
2k+1K=0-18 or-SO
3H k=0-4, y are between 0-1, and n is an integer;
2) dispersion medium: dimethylbenzene, butanols, ethanol or water;
3) base material: solid content is at the urethane of 20-50%, Resins, epoxy, chlorination rubber
Glue, high chlorinated rubber, water glass, potassium silicate or the positive silicic acid of partial hydrolysis alcohol dissolubility
Ethyl ester;
4) defrother: lipid acid C
3～C
10Alkyl ester or ethylene oxide oligopolymer;
5) antifouling auxiliary agent: Red copper oxide;
6) doping agent mainly is divided into two classes,
The doping agent that organic system conduction antifouling paint is used has following general formula:
C
nH
2n+1-SO
3H or
N is between 1-18;
Water system is conducted electricity the doping agent that antifouling protective system uses and is had one of structure of general formula (1)-(3):
R=R
1(OCH
2CH
2)
nOr R
1(OCH
2)
n, n=1-100, wherein R
1=C
mH
2m+1M=0-12 or C
mH
2m+1C
6H
4M=0-12;
Mol ratio (the N/H of polyaniline/doping agent
+) 1: between the 0.1-1.5, the defrother consumption accounts for coating solid content 0.01-5wt%, total coating solid content 5-85wt%, the content of each component can be regulated as required;
The preparation method can choose following one or both wantonly and use:
1) magnetic stirrer stirs and uses ultrasonication 0.5-12 hour after 2-24 hour, at 40-95 ℃ of following thermal treatment 0.5-10 hour, in the container of granulated glass sphere or porcelain ball, with vibrator vibration 2-24 hour;
2) magnetic stirrer or mortar stirred or grind after 2-24 hour, again at 40-95 ℃ of following thermal treatment 0.5-10 hour, processed 0.5-12 hour at ball mill or colloidal mill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115977A CN1073608C (en) | 1997-10-25 | 1997-10-25 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115977A CN1073608C (en) | 1997-10-25 | 1997-10-25 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1215744A CN1215744A (en) | 1999-05-05 |
| CN1073608C true CN1073608C (en) | 2001-10-24 |
Family
ID=5173588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97115977A Expired - Fee Related CN1073608C (en) | 1997-10-25 | 1997-10-25 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1073608C (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393839C (en) * | 2004-11-26 | 2008-06-11 | 吉林正基科技开发有限责任公司 | Polyaniline conducting adhesive |
| CN100358964C (en) * | 2004-12-08 | 2008-01-02 | 吉林正基科技开发有限责任公司 | Polyaniline corrosion proof sealant |
| CN100336863C (en) * | 2005-08-26 | 2007-09-12 | 重庆大学 | Preparation method of epoxy/polyaniline composite base-material for anticorrosion paint |
| CN100363445C (en) * | 2005-09-29 | 2008-01-23 | 武汉理工大学 | Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof |
| CN101157800B (en) * | 2007-09-26 | 2010-07-14 | 华东理工大学 | Preparation method of self-dispersion type conductive polyaniline/silicon composite material |
| CN101333350B (en) * | 2008-07-02 | 2010-06-02 | 大连海事大学 | Conductive anti-pollution paint for sea and method for preparing same |
| CN102108241B (en) * | 2010-11-01 | 2014-04-16 | 中国科学院长春应用化学研究所 | Phosphate doped polyaniline anticorrosive paint and preparation method thereof |
| EP2705000A4 (en) * | 2011-05-06 | 2014-11-05 | Trojan Techn Inc | Anti-fouling surface. and radiation source assembly and fluid treatment system comprising same |
| CN102702467B (en) * | 2012-06-27 | 2014-08-06 | 中国科学院长春应用化学研究所 | Waterborne polyurethane resin, waterborne polyaniline anticorrosive paint and preparation methods thereof |
| CN103992721B (en) * | 2014-05-07 | 2016-08-24 | 河海大学 | A kind of polyaniline-modified many carboxyls epoxy resin base material for Treatment of Metal Surface |
| CN106349663A (en) * | 2016-08-29 | 2017-01-25 | 佛山市高明区尚润盈科技有限公司 | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch |
| CN106317386A (en) * | 2016-08-29 | 2017-01-11 | 佛山市高明区尚润盈科技有限公司 | Preparing method of antibacterial polylactic acid material |
| CN106279645A (en) * | 2016-08-29 | 2017-01-04 | 佛山市高明区尚润盈科技有限公司 | A kind of preparation method of photochromic poly-lactic acid material |
| CN106366591A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material |
| CN109135500A (en) * | 2018-07-05 | 2019-01-04 | 常州五荣化工有限公司 | A kind of preparation method of antifouling anticorrosive paint peculiar to vessel |
| CN109161342A (en) * | 2018-08-29 | 2019-01-08 | 江苏赛达电子科技有限公司 | A kind of fire-fighting equipment corrosion-inhibiting coating and preparation method thereof |
| CN116333320A (en) * | 2023-03-31 | 2023-06-27 | 武汉理工大学 | Novel organosilicon block copolymer containing polyaniline block, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5811564A (en) * | 1981-07-15 | 1983-01-22 | Chiyouri Kk | Electrically conductive coating material and stainproof and corrosionproof apparatus |
| JPS62249906A (en) * | 1986-04-24 | 1987-10-30 | Showa Denko Kk | Underwater antifouling material |
| CN1141310A (en) * | 1995-07-27 | 1997-01-29 | 中国科学院长春应用化学研究所 | Preparation of full-soluble polyaniline with different molecular weights and derivatives thereof |
-
1997
- 1997-10-25 CN CN97115977A patent/CN1073608C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5811564A (en) * | 1981-07-15 | 1983-01-22 | Chiyouri Kk | Electrically conductive coating material and stainproof and corrosionproof apparatus |
| JPS62249906A (en) * | 1986-04-24 | 1987-10-30 | Showa Denko Kk | Underwater antifouling material |
| CN1141310A (en) * | 1995-07-27 | 1997-01-29 | 中国科学院长春应用化学研究所 | Preparation of full-soluble polyaniline with different molecular weights and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1215744A (en) | 1999-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1073608C (en) | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint | |
| KR100904174B1 (en) | Antifouling Paint Composition Comprising Zinc pyrithione | |
| CN102719174B (en) | Epoxy anticorrosive paint for underwater steel | |
| CN109181490B (en) | Water-based epoxy anticorrosive paint and preparation method thereof | |
| CN1242019C (en) | Cooling agents for cooling systms in fuel cell drives containing azole derivatives | |
| CN1552771A (en) | Mixed silicon sol water inorganic zinc enriching paint | |
| CN103555137A (en) | Doped polyaniline-epoxy-zinc powder composite coating and preparation method thereof | |
| CN1831062A (en) | Infrared, invisible and anti-corrosion coating and its prepn. method | |
| CN114907773A (en) | Environment-friendly marine antifouling paint and preparation method thereof | |
| KR101254723B1 (en) | Environmental-friendly antifouling paint composition comprising zinc undecylenate | |
| CN103627299A (en) | Anti-corrosive ship paint, and preparation method and application of paint | |
| CN1261506C (en) | Water moistening type non-toxic antifouling paint and its preparation method | |
| CN112251141B (en) | Graphene modified nano silver-copper-zinc-aluminum composite coating and preparation method and application thereof | |
| CN109266172B (en) | Marine antifouling paint and preparation method and application thereof | |
| CN1055940A (en) | Antifouling paint compositions | |
| CN104449172B (en) | A kind of antifouling paint containing bioantifouling agent and preparation method thereof | |
| KR20040035519A (en) | Antifouling Paint Composition Comprising Zinc pyrithione | |
| CN101831232B (en) | Rare earth compound epoxy zinc-rich paint for preventing microorganism attachment and preparation method thereof | |
| CN1170020A (en) | Low surface energy antifouling coating for seas | |
| KR100904175B1 (en) | Antifouling Paint Composition | |
| CN109880102B (en) | Penetration type protective agent for coating protection of ocean engineering concrete structure and preparation method thereof | |
| CN102876196B (en) | Not containing the electrically conductive polyaniline solvent free corrosion prevention erosion coating of rust-stabilising pigment | |
| CN104710902A (en) | Solvent-free epoxy coating | |
| US2389229A (en) | Antifouling composition | |
| CN111826033A (en) | Water-based ship biological antifouling industrial coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HUNAN ZHONGKEBENAN NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20070817 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070817 Address after: 410126 No. 1, Ya DA Road, Hunan, Changsha Patentee after: Hunan Anxin Cobain Material Co. Ltd. Address before: 130022 No. 159 Renmin Street, Jilin, Changchun Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |