CN105001759B - Molybdate Doped polypyrrole/epoxy resin self-healing coatings and its preparation and application - Google Patents
Molybdate Doped polypyrrole/epoxy resin self-healing coatings and its preparation and application Download PDFInfo
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- CN105001759B CN105001759B CN201510426979.3A CN201510426979A CN105001759B CN 105001759 B CN105001759 B CN 105001759B CN 201510426979 A CN201510426979 A CN 201510426979A CN 105001759 B CN105001759 B CN 105001759B
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- polypyrrole
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- 238000000576 coating method Methods 0.000 title claims abstract description 78
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- 229920006334 epoxy coating Polymers 0.000 claims abstract description 19
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 239000002019 doping agent Substances 0.000 claims description 10
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- 239000012065 filter cake Substances 0.000 claims description 5
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- 238000001291 vacuum drying Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- -1 anion Molybdate Chemical class 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000010426 asphalt Substances 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
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- 238000003760 magnetic stirring Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 6
- 241000968591 Haemanthus albiflos Species 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
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- 206010011224 Cough Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention relates to a kind of molybdate Doped polypyrrole/epoxy resin self-healing coatings and its preparation and application, belong to anti-corrosive metal coating field.The coating is made up of following two component：Component one is polypyrrole/epoxy-resin systems mother liquor, including molybdate Doped polypyrrole, epoxy resin, anti-settling agent, defoamer, levelling agent, organic solvent；Component two is polyamide curing agent.Molybdate Doped polypyrrole is taken, adds organic solvent to be uniformly dispersed in ultrasonic wave separating apparatus, be separately added into anti-settling agent, defoamer, levelling agent, stirred on magnetic stirring apparatus；Epoxy resin is subsequently adding, finely dispersed polypyrrole/epoxy-resin systems mother liquor is formed；Polyamide curing agent is added in the mother liquor for preparing, dispersed with stirring is uniform, both obtains molybdate Doped polypyrrole/epoxy coating.Coating is sprayed or brushed on 2024 aluminium alloys through oil removal treatment, molybdate Doped polypyrrole/epoxy resin coatings are formed after air drying solidification.
Description
Technical field
The present invention relates to a kind of molybdate Doped polypyrrole/epoxy resin self-healing coatings and its preparation and application, belong to
Anti-corrosive metal coating field.
Background technology
Metal erosion is always for a long time the key subjects of urgent need to resolve in industrial production, therefore research and development is effective
Corrosion protection steps have great importance.Most widely used method is anti-in metal surface coating in metal protection method
Rotten coating, because film-forming resin only has barrier properties, is usually added into rust resisting pigment such as chromate to improve coating in coating
Antiseptic property.When coating is destroyed, the chromate in coating can form passivating film in metal surface, suppress sprouting for corrosion
It is raw.But chromate has carcinogenicity, therefore research and development replace the filler of chromate, realize that the long-acting of coating uses i.e. coatings
As needing the target to be realized badly.
Recently as the further investigation to conducting polymer, researchers have found mistake of the electric polypyrrole in oxidation polymerization
Cheng Zhong, can be doped into the electrical neutralization that anion keeps polypyrrole.And when polypyrrole obtains electronics generation reduction reaction, will can mix
Miscellaneous anion is discharged.Using this doping property of polypyrrole, polypyrrole as the carrier of metal sustained release agent can be incited somebody to action
Polypyrrole after doping is used as in filler addition coating.When coating is destroyed, there is corrosion betatopic, polypyrrole conduct in metal
Negative electrode obtains electronics and discharges sustained release agent, so as to play the effect of selfreparing.Meanwhile, pyrrole monomer is carcinogenic, polypyrrole
Synthesis is convenient, good stability.Therefore, polypyrrole is considered as most to be hopeful that the material for preparing coatings of chromate can be replaced
One of material.
At present, the coatings on polypyrrole have been reported.G.Paliwoda-Porebska et al. have developed applicable
In the coatings of iron-based body, phosphomolybdate Doped polypyrrole is added in organic coating as filler.Chinese invention is special
Sharp (A of publication number CN 103642365) reports a kind of marine aluminium alloy coatings, with nano silicon as core, system
The polypyrrole of the fluorine titanium of standby core shell structure/zirconate ion doping, using the silica of preparation/polypyrrole composite particles as filling out
Material is added in marine aluminium alloy priming paint.But above-mentioned polypyrrole filler preparation technology is cumbersome, there is a kind of preparation technology to be developed
Simple polypyrrole coatings.The coatings are applied to the protection of space flight aluminium alloy 2024, polypyrrole selfreparing
Application of the coating on space flight aluminium alloy is also without related document report.
The content of the invention
It is an object of the invention to provide a kind of preparation method of molybdate Doped polypyrrole/epoxy resin coatings,
The preparation technology of coating is simple, workable, with good physical and mechanical properties and coating self-healing properties, hence it is evident that improve
The corrosion resistance and service life of coating.
The technical scheme is that：
A kind of molybdate Doped polypyrrole/epoxy resin self-healing coatings, the coating is made up of following two component：
Component one is polypyrrole/epoxy-resin systems mother liquor, according to the mass fraction, including following components and content：
8~20 parts of molybdate Doped polypyrrole, 140~160 parts of epoxy resin, 0.7~1 part of anti-settling agent, defoamer 0.7~
1 part, 0.7~1 part of levelling agent, 70~80 parts of organic solvent；
Component two is polyamide curing agent；
Epoxy resin is 1 with the mass ratio of polyamide curing agent:(0.8~1).
Described molybdate Doped polypyrrole/epoxy resin self-healing coatings, molybdate Doped polypyrrole used reviews one's lessons by oneself
Multiple component account for the polypyrrole-epoxy resin coating system quality of molybdate Doped polypyrrole and epoxy coating composition 2~
5%.
Described molybdate Doped polypyrrole/epoxy resin self-healing coatings, molybdate in molybdate Doped polypyrrole
Doping is 3~12wt% (preferably 5~10wt%).
Described molybdate Doped polypyrrole/epoxy resin self-healing coatings, molybdate used is sodium molybdate.
Described molybdate Doped polypyrrole/epoxy resin self-healing coatings, epoxy resin is E-44 bisphenol type epoxy trees
Fat, polyamide curing agent is polyamide 6 50.
Described molybdate Doped polypyrrole/epoxy resin self-healing coatings, organic solvent is dimethylbenzene and n-butanol
The mass ratio of mixed solvent, dimethylbenzene and n-butanol is (5~7):(3~5).
The preparation method of described molybdate Doped polypyrrole/epoxy resin self-healing coatings, comprises the following steps that：
(1) preparation of molybdate Doped polypyrrole：4~8 mass parts dopant sodium molybdates are taken with deionized water by 1:(45~
70) mass ratio mixing, and magnetic agitation forms the aqueous solution of dopant；Whole temperature of reaction system is kept at 0~2 DEG C,
To the pyrrole monomer that 1~3 mass parts are added dropwise in reaction system, the oxidant persulfuric acid that will be prepared in advance afterwards under nitrogen atmosphere
The mass parts of aqueous ammonium 50~60 are dropwise instilled；After magnetic agitation is polymerized 5~6 hours, stop reaction, products therefrom filtered,
Filter cake is washed with deionized totally；Product obtains the molybdenum of black after 50~70 DEG C of vacuum drying chamber is dried 5~10 hours
Sour natrium doping polypyrrole, its particle size range is 50nm~100nm；
(2) preparation of polypyrrole/epoxy-resin systems mother liquor：The molybdate Doped polypyrrole of 8~20 mass parts preparation is taken,
Powder is ground to agate mortar, adds 70~80 mass parts organic solvents to be uniformly dispersed in ultrasonic wave separating apparatus；Take respectively
Each 0.7~1 mass parts of anti-settling agent, defoamer, levelling agent, are added in the polypyrrole dispersion soln of above-mentioned steps preparation, in magnetic
Stirred 5~15 minutes on power agitator；The mass parts of epoxy resin 140~160 are subsequently adding, are uniformly mixed in high speed ball mill
Close, make epoxy resin by organic solvent diluting, form finely dispersed polypyrrole/epoxy-resin systems mother liquor；
Polyamide curing agent is added in the mother liquor for preparing, dispersed with stirring is uniform, both obtains molybdate Doped polypyrrole/ring
Oxygen tree grease coating material.
The preparation method of described molybdate Doped polypyrrole/epoxy resin self-healing coatings, oxidant ammonium persulfate water
In solution, ammonium persulfate is with deionized water with 1:The mass ratio of (7~20) is prepared.
The application of described molybdate Doped polypyrrole/epoxy resin self-healing coatings, coating is sprayed or brushed in warp
On 2024 aluminium alloys of oil removal treatment, molybdate Doped polypyrrole/epoxy resin coatings are formed after air drying solidification.
Advantages of the present invention and beneficial effect are：
1st, the present invention is added in epoxy coating using molybdate Doped polypyrrole as filler, the coating pair of preparation
2024 aluminium alloys have preferable self-healing properties.When coating is destroyed, alloy matrix aluminum corrodes, the poly- pyrrole in coating
Cough up and obtain electronics as negative electrode, dedoping reaction occurs, discharge inhibitor anion molybdate, can effectively suppress metal enters one
Step corrosion, so as to play a part of selfreparing.
2nd, molybdate Doped polypyrrole preparation process is simple prepared by the present invention, easy to operate.Molybdate Doped polypyrrole has
There is excellent electro-chemical activity, corrosion inhibiter can be discharged under reduction potential.Meanwhile, the polypyrrole of doping has in the epoxy
Good chemical compatibility and dispersiveness, coating crosslinking degree are higher, and compactness is good.
3rd, molybdate Doped polypyrrole-epoxy coating excellent combination property of the present invention, the attachment between metallic matrix
Power is 2~3 times of adhesive force between epoxy resin varnish coating and metallic matrix.In neutral salt spray, polypyrrole-epoxy based coatings
With preferable corrosion resistance, antiseptic property is greatly improved than epoxy resin varnish coating.
Brief description of the drawings
Fig. 1 is photo of the coating of embodiment 1 after 720 hours salt fogs after scribing cut.
Fig. 2 is photo of the coating of comparative example 1 after 720 hours salt fogs after scribing cut.
Fig. 3 is photo of the coating of comparative example 2 after 720 hours salt fogs after scribing cut.
Specific embodiment
In a specific embodiment, molybdate Doped polypyrrole/epoxy resin self-healing coatings of the present invention and its preparation side
Method and application, it is specific as follows：
(1) preparation (mass parts) of molybdate Doped polypyrrole：1~3 part is added dropwise in 4~8 parts of aqueous solution of sodium molybdate
Pyrrole monomer, is dropwise added dropwise 50~60 parts of oxidant ammonium persulfate aqueous solution, and magnetic force is stirred under the conditions of 0~2 DEG C in the nitrogen atmosphere
Mix polymerization 5~6 hours, through filtering, washing, 50~70 DEG C are vacuum dried 5~10 hours, obtain the black poly- pyrrole of molybdic acid salt dopping
Cough up.
(2) preparation (mass parts) of polypyrrole-epoxy coating：8~20 parts of the molybdate Doped polypyrrole of preparation is taken,
(anti-settling agent, defoamer, levelling agent are to add 70~80 parts of organic solvent, anti-settling agent and defoamer and each 0.7~1 part of levelling agent
Epoxy coating usual auxiliaries, such as：Anti-settling agent is modified hydrogenated castor oil, and defoamer is methyl-silicone oil or fatty acid alkyl
Ester, levelling agent is silane or acrylate), 140~160 parts of epoxy resin, form finely dispersed polypyrrole/epoxy resin body
It is mother liquor.Polyamide curing agent is added in the mother liquor for preparing, molybdate Doped polypyrrole/epoxy coating is obtained.
Coating is sprayed or brushed on 2024 aluminium alloys through oil removal treatment, forming molybdate after air drying solidification mixes
Heteromeric pyrroles/epoxy resin coatings.
The present invention is described in more detail by the following examples, but embodiments of the present invention not limited to this.
Embodiment 1
3.5 parts of dopant sodium molybdate is taken, 1 is pressed with deionized water：45 mass ratioes mix, and magnetic agitation forms dopant
The aqueous solution.Whole temperature of reaction system is kept at 2 DEG C, in nitrogen atmosphere to reaction system in 2 parts of pyrrole monomer is added dropwise, so
(ammonium persulfate is 1 with the mass ratio of deionized water to the aqueous solution of the oxidant ammonium persulfate that will be prepared in advance afterwards:17) 54 parts
Dropwise instill.After magnetic agitation is polymerized 6 hours, stop reaction, products therefrom is filtered, filter cake deionized water is repeatedly washed.
Product obtains the sodium molybdate Doped polypyrrole of black after 60 DEG C of vacuum drying chamber is dried 8 hours, the present embodiment sodium molybdate
Doping is 10wt%.
8 parts of sodium molybdate Doped polypyrroles are taken, 80 parts of organic solvents are uniformly dispersed in ultrasonic disperse instrument.Take respectively anti-settling
Agent, defoamer, each 1 part of levelling agent, add the polypyrrole dispersion soln of above-mentioned preparation, are stirred 10 minutes on magnetic stirring apparatus
Afterwards, 153 parts of epoxy resin are added, is uniformly mixed in high speed ball mill, obtain finely dispersed polypyrrole/epoxy-resin systems
Mother liquor.
It is 1 by the mass ratio of epoxy resin and curing agent:0.8, polyamide curing agent is added in the mother liquor for preparing,
Dispersed with stirring is uniform, both obtains sodium molybdate Doped polypyrrole/epoxy coating.Paint brush is coated in through 2024 aluminium of oil removal treatment
On alloy, sodium molybdate Doped polypyrrole/epoxy coating is formed after air drying solidification.
Comparative example 1
Difference from Example 1 is：
2 parts of sodium molybdate Doped polypyrroles are taken, 80 parts of organic solvents are uniformly dispersed in ultrasonic disperse instrument.Take respectively anti-settling
Agent, defoamer, each 1 part of levelling agent, add the polypyrrole dispersion soln of above-mentioned preparation, are stirred 10 minutes on magnetic stirring apparatus
Afterwards, 153 parts of epoxy resin are added, is uniformly mixed in high speed ball mill, obtain finely dispersed polypyrrole/epoxy-resin systems
Mother liquor.
It is 1 by the mass ratio of epoxy resin and curing agent:0.8, polyamide curing agent is added in the mother liquor for preparing,
Dispersed with stirring is uniform, both obtains sodium molybdate Doped polypyrrole/epoxy coating.Paint brush is coated in through 2024 aluminium of oil removal treatment
On alloy, sodium molybdate Doped polypyrrole/epoxy coating is formed after air drying solidification.
Comparative example 2
Difference from Example 1 is：
4 parts of sodium molybdate Doped polypyrroles are taken, 80 parts of organic solvents are uniformly dispersed in ultrasonic disperse instrument.Take respectively anti-settling
Agent, defoamer, each 1 part of levelling agent, add the polypyrrole dispersion soln of above-mentioned preparation, are stirred 10 minutes on magnetic stirring apparatus
Afterwards, 153 parts of epoxy resin are added, is uniformly mixed in high speed ball mill, obtain finely dispersed polypyrrole/epoxy-resin systems
Mother liquor.
It is 1 by the mass ratio of epoxy resin and curing agent:0.8, polyamide curing agent is added in the mother liquor for preparing,
Dispersed with stirring is uniform, both obtains sodium molybdate Doped polypyrrole/epoxy coating.Paint brush is coated in through 2024 aluminium of oil removal treatment
On alloy, sodium molybdate Doped polypyrrole/epoxy coating is formed after air drying solidification.
Embodiment 2
3.5 parts of dopant sodium molybdate is taken, 1 is pressed with deionized water：50 mass ratioes mix, and magnetic agitation forms dopant
The aqueous solution.Whole temperature of reaction system is kept at 2 DEG C, in nitrogen atmosphere to reaction system in 2 parts of pyrrole monomer is added dropwise, so
(ammonium persulfate is 1 with the mass ratio of deionized water to the aqueous solution of the oxidant ammonium persulfate that will be prepared in advance afterwards:7) 60 parts by
Drop is instilled.After magnetic agitation is polymerized 6 hours, stop reaction, products therefrom is filtered, filter cake deionized water is repeatedly washed.Produce
Thing obtains the sodium molybdate Doped polypyrrole of black after 60 DEG C of vacuum drying chamber is dried 8 hours, and the present embodiment sodium molybdate is mixed
Miscellaneous amount is 12wt%.
12 parts of sodium molybdate Doped polypyrroles are taken, 70 parts of organic solvents are uniformly dispersed in ultrasonic disperse instrument.Take respectively anti-settling
Agent, defoamer, each 0.8 part of levelling agent, add the polypyrrole dispersion soln of above-mentioned preparation, are stirred 10 minutes on magnetic stirring apparatus
Afterwards, 145 parts of epoxy resin are added, is uniformly mixed in high speed ball mill, obtain finely dispersed polypyrrole/epoxy-resin systems
Mother liquor.
It is 1 by the mass ratio of epoxy resin and curing agent:1, polyamide curing agent is added in the mother liquor for preparing, stir
Mix and be uniformly dispersed, both obtain sodium molybdate Doped polypyrrole/epoxy coating.Paint brush is coated in and is closed through 2024 aluminium of oil removal treatment
Jin Shang, sodium molybdate Doped polypyrrole/epoxy coating is formed after air drying solidification.
Embodiment 3
3.5 parts of dopant sodium molybdate is taken, 1 is pressed with deionized water：55 mass ratioes mix, and magnetic agitation forms dopant
The aqueous solution.Whole temperature of reaction system is kept at 2 DEG C, in nitrogen atmosphere to reaction system in 3 parts of pyrrole monomer is added dropwise, so
(ammonium persulfate is 1 with the mass ratio of deionized water to the aqueous solution of the oxidant ammonium persulfate that will be prepared in advance afterwards:18) 57 parts
Dropwise instill.After magnetic agitation is polymerized 6 hours, stop reaction, products therefrom is filtered, filter cake deionized water is repeatedly washed.
Product obtains the sodium molybdate Doped polypyrrole of black after 60 DEG C of vacuum drying chamber is dried 8 hours, the present embodiment sodium molybdate
Doping is 3wt%.
16 parts of sodium molybdate Doped polypyrroles are taken, 75 parts of organic solvents are uniformly dispersed in ultrasonic disperse instrument.Take respectively anti-settling
Agent, defoamer, each 0.9 part of levelling agent, add the polypyrrole dispersion soln of above-mentioned preparation, are stirred 10 minutes on magnetic stirring apparatus
Afterwards, 158 parts of epoxy resin are added, is uniformly mixed in high speed ball mill, obtain finely dispersed polypyrrole/epoxy-resin systems
Mother liquor.
It is 1 by the mass ratio of epoxy resin and curing agent:0.8, polyamide curing agent is added in the mother liquor for preparing,
Dispersed with stirring is uniform, both obtains sodium molybdate Doped polypyrrole/epoxy coating.Paint brush is coated in through 2024 aluminium of oil removal treatment
On alloy, sodium molybdate Doped polypyrrole/epoxy coating is formed after air drying solidification.
The coating of embodiment 1, comparative example 1 and comparative example 2, is scribing the two vertical cuts i.e. condition of breakdown of coating
Under, by the coating photo after 720 hours salt spray tests as shown in Figure 1, Figure 2 and Fig. 3.From the figure, it can be seen that the coating of embodiment 1
Bubble and get rusty and be substantially fewer than comparative example 1 and the coating of comparative example 2 a lot, show excellent salt spray resistance and coating selfreparing
Performance.Embodiment result shows that molybdate Doped polypyrrole used, i.e. selfreparing component account for polypyrrole-epoxy coating body
When being the 2~5% of quality, antiseptic effect is optimal.
Claims (7)
1. a kind of molybdate Doped polypyrrole/epoxy resin self-healing coatings, it is characterised in that the coating is by following two components structure
Into：
Component one is polypyrrole/epoxy-resin systems mother liquor, according to the mass fraction, including following components and content：
8~20 parts of molybdate Doped polypyrrole, 140~160 parts of epoxy resin, 0.7~1 part of anti-settling agent, 0.7~1 part of defoamer,
0.7~1 part of levelling agent, 70~80 parts of organic solvent；
Component two is polyamide curing agent；
Epoxy resin is 1 with the mass ratio of polyamide curing agent:（0.8~1）；
Molybdate Doped polypyrrole used, i.e. selfreparing component account for the poly- of molybdate Doped polypyrrole and epoxy coating composition
The 2~5% of pyrroles-epoxy resin coating system quality；
The doping of molybdate is 3~12wt% in molybdate Doped polypyrrole；
The polypyrrole that the coating is formed in coating obtains electronics as negative electrode, and dedoping reaction occurs, and discharges inhibitor anion
Molybdate, can effectively suppress the further corrosion of metal, so as to play a part of selfreparing.
2. according to the molybdate Doped polypyrrole/epoxy resin self-healing coatings described in claim 1, it is characterised in that：It is used
Molybdate is sodium molybdate.
3. according to the molybdate Doped polypyrrole/epoxy resin self-healing coatings described in claim 1, it is characterised in that：Epoxy
Resin is E-44 bisphenol A type epoxy resins, and polyamide curing agent is polyamide 6 50.
4. according to the molybdate Doped polypyrrole/epoxy resin self-healing coatings described in claim 1, it is characterised in that：It is organic
Solvent is the mixed solvent of dimethylbenzene and n-butanol, and the mass ratio of dimethylbenzene and n-butanol is（5~7）:（3~5）.
5. a kind of preparation method of the molybdate Doped polypyrrole/epoxy resin self-healing coatings described in claim 1, its feature
It is to comprise the following steps that：
（1）The preparation of molybdate Doped polypyrrole：4~8 mass parts dopant sodium molybdates are taken with deionized water by 1:（45~70）
Mass ratio mixing, and magnetic agitation formed dopant the aqueous solution；Whole temperature of reaction system is kept at 0~2 DEG C, in nitrogen
To the pyrrole monomer that 1~3 mass parts are added dropwise in reaction system, the oxidant ammonium persulfate water that will be prepared in advance afterwards under atmosphere
The mass parts of solution 50~60 are dropwise instilled；After magnetic agitation is polymerized 5~6 hours, stop reaction, products therefrom is filtered, filter cake
It is washed with deionized clean；Product obtains the sodium molybdate of black after 50~70 DEG C of vacuum drying chamber is dried 5~10 hours
Doped polypyrrole, its particle size range is 50nm~100nm；
（2）The preparation of polypyrrole/epoxy-resin systems mother liquor：The molybdate Doped polypyrrole of 8~20 mass parts preparation is taken, agate is used
Nao mortar grinders add 70~80 mass parts organic solvents to be uniformly dispersed in ultrasonic wave separating apparatus to powder；Take respectively anti-settling
Agent, defoamer, each 0.7~1 mass parts of levelling agent, are added in the polypyrrole dispersion soln of above-mentioned steps preparation, are stirred in magnetic force
Mix and stirred 5~15 minutes on device；The mass parts of epoxy resin 140~160 are subsequently adding, are uniformly mixed in high speed ball mill, made
Epoxy resin forms finely dispersed polypyrrole/epoxy-resin systems mother liquor by organic solvent diluting；
Polyamide curing agent is added in the mother liquor for preparing, dispersed with stirring is uniform, both obtains molybdate Doped polypyrrole/asphalt mixtures modified by epoxy resin
Grease coating material.
6. the preparation method of molybdate Doped polypyrrole/epoxy resin self-healing coatings according to claim 5, its feature
It is that in oxidant ammonium persulfate aqueous solution, ammonium persulfate is with deionized water with 1:（7~20）Mass ratio prepare.
7. a kind of application of the molybdate Doped polypyrrole/epoxy resin self-healing coatings described in claim 1, its feature exists
In, coating is sprayed or brushed on 2024 aluminium alloys through oil removal treatment, forming molybdic acid salt dopping after air drying solidification gathers
Pyrroles/epoxy resin coatings.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634266A (en) * | 2012-04-27 | 2012-08-15 | 天津翔盛粉末涂料有限公司 | Weather-resistant heavy-duty anticorrosive powder coating |
| CN104098984A (en) * | 2014-06-27 | 2014-10-15 | 国家电网公司 | Inhibitor-loaded montmorillonite/epoxy self-healing coating |
-
2015
- 2015-07-21 CN CN201510426979.3A patent/CN105001759B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634266A (en) * | 2012-04-27 | 2012-08-15 | 天津翔盛粉末涂料有限公司 | Weather-resistant heavy-duty anticorrosive powder coating |
| CN104098984A (en) * | 2014-06-27 | 2014-10-15 | 国家电网公司 | Inhibitor-loaded montmorillonite/epoxy self-healing coating |
Non-Patent Citations (1)
| Title |
|---|
| 钼酸盐掺杂的复合型导电高分子对不锈钢的保护作用;潘文燕等;《2014年全国腐蚀电化学及测试方法学术交流会摘要集》;20140721;第90页 * |
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