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:
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.