CN105153883B - A kind of polythiophene composition metal anticorrosive paint of pattern influence, preparation method and applications - Google Patents
A kind of polythiophene composition metal anticorrosive paint of pattern influence, preparation method and applications Download PDFInfo
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Abstract
The present invention discloses a kind of polythiophene composition metal anticorrosive paint of pattern influence and preparation method and application.The component and content of composite anticorrosion coating of the present invention be：" pyriform " nano particle of poly- (3,4 dioxoethyl) thiophene or the composite nano fiber of poly- (3,4 dioxoethyl) thiophene and CNT：15~110mg；Polyvinyl butyral resin ethanol solution：1~3mL；1~3mL of absolute ethyl alcohol.In the present invention; first poly- (3 are prepared using emulsion polymerization; 4 dioxoethyls) thiophene " pyriform " nano particle or poly- (3; 4 dioxoethyls) thiophene and CNT composite nano fiber; it is mixed with the ethanol solution and absolute ethyl alcohol of polyvinyl butyral resin again, conducting composite metal anticorrosive paint is prepared and applied in metallic iron anti-corrosion.Coating of the present invention is with low cost, environmental pollution is small, combination property is good.In addition, the scanning Kelvin probe measuring technologies selected avoid the destruction to coating, anti-corrosion situation of the coating to metal can be effectively monitored.
Description
Technical field
The present invention relates to anticorrosive metal Material Field.The compound gold of polythiophene influenceed more particularly, to a kind of pattern
Belong to anticorrosive paint and its preparation and application.
Background technology
Metal material all has the critical role do not replaced in civilian and national defence, and metal erosion is sent out to society
Exhibition brings huge economic loss and environmental hazard, therefore solves one of the important goal of this problem as development in science and technology,
And it is the key for solving this problem to develop new, excellent performance anti-corrosion of metal material.Generally coating one layer in metal surface has
Machine anti-corrosion material is effective anti-corrosion of metal means, can be with one because the organic coating of metal surface serves as the role of barrier
Determine to prevent moisture in degree, oxygen and ion etc., which enter metal interface, to be occurred redox reaction and corrode metal；On the other hand,
The higher oxidation-reduction potential of conducting polymer can effectively make corrosion metal surface potential polarization, so that its current potential is improved,
Prevent corrosion.
Tradition more effective anti-corrosion material is largely chromate, but its due to containing virose chromium to environment and people
Body causes very big harm, is used by the limitation of European legislation regulation now, therefore urgently seek the preserving timber of new green environment protection
Material.Since conducting polymer was found from 1977, because it has the physicochemical characteristics such as excellent, electric, magnetics, and it is wide
It is general to apply in different fields.The eighties in 19th century, Mengoli etc. (J.Appl.Polym.Sci., 1981,26,4247) and
DeBerry etc. (J.Electrochem.Soc., 1985,132,1022) is reported conductive polymer polyanaline electrochemistry first
It is deposited on iron-based bottom, and have studied its anti-corrosion of metal performance.Test result indicates that, polyaniline shows certain anti-corrosive properties
Can, so as to start application of the conducting polymer in anti-corrosion of metal field.Since then, conducting polymer is obtained in metal protection field
Extensive research, wherein be no lack of the conducting polymer anticorrosive paint of commercialization., German Ormecon companies in 1996
Wessling et al. successfully have developed industrial anticorrosive polyaniline material, such as ORMECONTM, CORRPASIV, Version
Deng.
CN 102703945A disclose a kind of new electric polypyrrole/polyaniline composite anti-corrosive coating, and are applied
In Copper substrate surface, the corrosion potential of Copper substrate is effectively increased, corrosion current is reduced, show preferable Anticorrosive Character.
But the preparation method that this composite anti-corrosive coating is used is electrochemical polymerization, therefore its stability and repeatability are whard to control, together
Shi Buneng is synthesized on a large scale, largely limits its practical application.
Although the antiseptic property research of current electrically conductive polyaniline is relatively broad, also more ripe, polyaniline exists many
Chemical transition structure is planted, some of which structure has certain toxicity, and it has the shortcomings that sensitivity to acid, causes its performance
It is not sufficiently stable.And polythiophene and its derivative due to its excellent environment and chemical stability, higher oxidation-reduction potential and
Huge advantage is embodied in anti-corrosion of metal field.
The content of the invention
It is an object of the present invention to provide a kind of polythiophene composition metal anticorrosive paint of pattern influence.
Second object of the present invention is to provide a kind of preparation of the polythiophene composition metal anticorrosive paint of pattern influence
Method.
Third object of the present invention is to provide a kind of polythiophene composition metal anticorrosive paint of pattern influence in metal
Application in iron anti-corrosion.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of polythiophene composition metal anticorrosive paint of pattern influence, includes the component of following content:
" pyriform " nano particle or poly- (3,4- dioxoethyl) thiophene and CNT of poly- (3,4- dioxoethyl) thiophene
Composite nano fiber：15mg~110mg；
Polyvinyl butyral resin ethanol solution：1~3mL；
Absolute ethyl alcohol：1~3mL.
Preferably, the solid polyvinyl butyral resin containing 7wt%~14wt% in the polyvinyl butyral resin ethanol solution.
Preferably, the CNT is single-walled carbon nanotube or multi-walled carbon nanotube.
The preparation of " pyriform " nano particle of poly- (3, the 4- dioxoethyl) thiophene comprises the following steps：
1) it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio:In 1 water and acetonitrile mixture, stir, obtain concentration
For water/acetonitrile mixed solution of 0.05~1mmol/L polyvinylpyrrolidone；
2) to step 1) in add monomer (3,4- dioxoethyl) thiophene in gained mixed solution, ultrasonic 0.5h~2h obtains
To finely dispersed mixed solution；
3) to step 2) in add the ammonium persulfate oxidizing agent aqueous solution in the finely dispersed mixed solution of gained, wherein, mistake
Ammonium sulfate is 2 with monomer (3,4- dioxoethyl) thiophene mol ratio：1, lasting stirring, polymerized at normal temperature 48h obtains containing poly- (3,4-
Dioxoethyl) thiophene " pyriform " nano particle black mixed liquor；
4) by step 3) the mixed liquor centrifugation of gained black, black solid sediment is obtained, then this sediment is carried out
Wash, dry, obtain " pyriform " nano particle of poly- (3,4- dioxoethyl) thiophene.
Preferably, step 4) in, " pyriform " nano particle diameter of poly- (3, the 4- dioxoethyl) thiophene for 200nm~
500nm。
Preferably, step 4) in, the washing is that the black solid sediment is first washed with deionized and centrifuged
Separation, then with volume ratio be 1:1 water and the mixed solvent of ethanol are washed, until supernatant is colourless；Finally spend again
Ion water washing.
The preparation of the composite nano fiber of poly- (3, the 4- dioxoethyl) thiophene and CNT comprises the following steps；
1. it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio:In 1 water and acetonitrile mixture, stir, obtain concentration
For water/acetonitrile mixed solution of 0.05~1mmol/L polyvinylpyrrolidone；
2. single wall or multi-walled carbon nanotube are added into step 1. gained mixed solution, ultrasonic disperse 1h, acquisition contains carbon
The suspension of nanotube；
3. monomer (3,4- dioxoethyl) thiophene is added into step 2. middle gained suspension, ultrasonic 0.5h~2h is obtained
Finely dispersed mixed solution；
4. the ammonium persulfate oxidizing agent aqueous solution is added into the step 3. mixed solution, wherein, ammonium persulfate and monomer
(3,4- dioxoethyl) thiophene mol ratio is 2：1, lasting stirring, normal temperature emulsion polymerisation reaction 48h obtains containing poly- (3,4- bis-
Oxygen ethyl) thiophene and CNT composite nano fiber black mixed liquor；
5. by step, 4. gained black mixed liquor is centrifuged, and obtains black solid sediment, then this sediment is carried out
Wash, dry, obtain the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and CNT.
Preferably, step 5. in, the composite nano fiber diameter of poly- (3, the 4- dioxoethyl) thiophene and CNT
For 10nm~50nm；Preferably, the composite nano fiber long degree of poly- (3, the 4- dioxoethyl) thiophene and CNT be 1~
10μm。
Preferably, step 5. in, the washing is that the black solid sediment is first washed with deionized and centrifuged
Separation, then with volume ratio be 1:1 water and the mixed solvent of ethanol are washed, until supernatant is colourless；Finally spend again
Ion water washing.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of the polythiophene composition metal anticorrosive paint of pattern influence, comprises the following steps：
By " pyriform " nano particle or poly- (3,4- dioxoethyl) thiophene of poly- (3,4- dioxoethyl) thiophene and carbon nanometer
Composite nano fiber, polyvinyl butyral resin ethanol solution and the absolute ethyl alcohol of pipe are well mixed, prepare a kind of pattern shadow
Loud polythiophene composition metal anticorrosive paint；
Wherein, each component content is：
" pyriform " nano particle or poly- (3,4- dioxoethyl) thiophene and CNT of poly- (3,4- dioxoethyl) thiophene
Composite nano fiber quality be 15mg~110mg；
Polyvinyl butyral resin volumes of aqueous ethanol is 1~3mL；
Absolute ethyl alcohol volume is 1~3mL；
The solid polyvinyl butyral resin containing 7wt%~14wt% in the polyvinyl butyral resin ethanol solution；
The CNT is single-walled carbon nanotube or multi-walled carbon nanotube.
To reach above-mentioned 3rd purpose, the present invention uses following technical proposals：
A kind of application of polythiophene composition metal anticorrosive paint of pattern influence in metallic iron anti-corrosion.The specific inspection of application
Survey method comprises the following steps：
The anti-corrosion paint is being polished in clean metallic iron piece substrate, 50~75 DEG C of oven drying 1 is placed in
~2h；The metal iron plate side for being coated with anticorrosive paint again manufactures cut that an area is 10mm × 1mm with pocket knife as lacking
Fall into, it is bonded together with another clean, iron plate of the surface without anticorrosive paint, about 0.5cm sky is reserved in defective side
Position, is turned on the two connection using copper foil tape；Finally, sample is placed in scanning Kelvin probe test system
In, tested.
Preferably, it is described to be applied to spin coating or drop coating.
Preferably, the polishing is to be polished successively metallic iron using the sand paper that mesh number is 400 mesh, 600 mesh and 1000 mesh
Piece, polishing finish after be washed with deionized, nitrogen dry, then be placed in temperature be 50 DEG C~75 DEG C oven drying 0.5h~
1h。
Preferably, the electrolyte is sodium-chloride water solution or potassium chloride solution.
It is poly- (3,4- bis- containing pattern compared with comprising only the metal anti-corrosive paint of polyvinyl butyral resin ethanol solution
Oxygen ethyl) thiophene " pyriform " nano particle or to contain the composite Nano that pattern is poly- (3,4- dioxoethyl) thiophene and nanotube fine
The polythiophene composition metal anticorrosive paint of dimension, shows the more excellent Corrosion Protection to iron.Anticorrosive paint contains pattern
During for polythiophene pyriform nano particle, it is mixed with polyvinyl butyral resin ethanol solution, is only polyethylene with anticorrosive paint
Butyral ethanol solution is compared, and the corrosion rate of metallic iron is reduced to 21 μm/h by 900 μm/h, and the range of decrease is about 45 times；When anti-
When rotten coating is the composite nano fiber containing poly- (3,4- dioxoethyl) thiophene and nanotube, the corrosion rate of metallic iron is 66
~108 μm/h, the range of decrease is about 9~15 times, effectively slow down metal and is further corroded.
Wherein, the anticorrosive paint ratio containing pattern prepared by poly- (3,4- dioxoethyl) thiophene " pyriform " nano particle contains
Have pattern for the anticorrosive paint antiseptic property prepared by the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and nanotube more
Good, illustrating poly- (3, the 4- dioxoethyl) thiophene of different nanostructureds has important influence to the antiseptic property of metallic iron.Push away
Survey because poly- (3,4- dioxoethyl) thiophene " pyriform " nano particle is medicine ball, and poly- (3,4- dioxoethyl) thiophene is received with carbon
Mitron compound is hollow-core construction, and two kinds of structures are compared, and solid construction can provide more effective charges, work as dissolving metal
When, metallic perimeter (interface of such as metal and material) produces a certain amount of electronics, poly- (3, the 4- dioxoethyl) thiophene of oxidation state
Fen can obtain electronics in time and be reduced, effectively the reduction of reduction oxygen, so as to suppress oxygen radical and hydroxide ion (pole
Easy attack metal causes coating shedding with polymer interface, destroying polymer chain, the cementability reduction of polymer and metal,
Exposed metal/bare metal outside, accelerate corrosion of metal) formation, slow down disbonding, reach anti-corrosion purpose.
Beneficial effects of the present invention are as follows：
1. a kind of polythiophene composition metal anticorrosive paint of pattern influence of the present invention, its preparation method is simple, easy, can
Control and beneficial to large-scale production.
2. a kind of polythiophene composition metal anticorrosive paint of pattern influence of the present invention has excellent environment and chemistry steady
Qualitative, higher oxidation-reduction potential, so as to show excellent anti-corrosion of metal performance.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows that the ESEM of poly- (3,4- dioxoethyl) thiophene " pyriform " nano particle of the embodiment of the present invention 1 shines
Piece.
Fig. 2 shows that poly- (3, the 4- dioxoethyl) thiophene of the embodiment of the present invention 2 and multi-walled carbon nanotube composite fibre are scanned
Electromicroscopic photograph.
Fig. 3 shows that a kind of polythiophene composition metal anti-corrosion for pattern influence that the embodiment of the present invention 1,2,3 is prepared is applied
Corrosion rate figure of the material applied to the metallic iron surveyed in the anticorrosion research of iron.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
The preparation of " pyriform " nano particle of poly- (3,4- dioxoethyl) thiophene：
1) it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio：In 1 water and acetonitrile mixture, stir, prepare concentration
For water/acetonitrile mixed solution of 0.05mmol/L polyvinylpyrrolidone；
2) 0.2mL monomers (3,4- dioxoethyl) thiophene is added in above-mentioned solution, ultrasonic 0.5h obtains finely dispersed
Mixed solution；
3) ammonium persulfate aqueous solution of the certain volume added in above-mentioned solution, wherein ammonium persulfate and monomer (3,4-
Dioxoethyl) thiophene (EDOT) mol ratio be 2:1, the polymerization system that cumulative volume is 100mL is formed, lasting stirring, normal temperature enters
Row chemical polymerization 48h, obtains the black mixed liquor of " pyriform " nano particle containing poly- (3,4- dioxoethyl) thiophene；
4) above-mentioned black mixed liquor is centrifuged, obtains black solid sediment；This black solid sediment is first used
Deionized water is washed and centrifuged, and then uses volume ratio to be 1 again:1 water and the mixed solvent of ethanol are washed, Zhi Daoshang
Clear liquid is colourless；Finally it is washed with deionized again；Obtained black solid sediment is dried in vacuo at 80 DEG C, obtains black
Color solid, " pyriform " nano particle of as poly- (3,4- dioxoethyl) thiophene, its stereoscan photograph is as shown in figure 1, particle diameter
For 200nm~500nm.
By " pyriform " nano particle of above-mentioned poly- (3, the 4- dioxoethyl) thiophene prepared as preparing a kind of pattern
The preparation of the polythiophene composition metal anticorrosive paint of influence：
" pyriform " nanoparticle mass of poly- (3,4- dioxoethyl) thiophene is 15mg, Gu containing the polyvinyl alcohol for 14wt%
Butyral volumes of aqueous ethanol is 1mL, and absolute ethyl alcohol volume is 3mL, and three is uniformly mixed, and obtains described anti-corrosion of metal and applies
Material.
Metal anti-corrosive paint described in above-mentioned prepare is applied to the anti-corrosion to metallic iron：
Polished successively metal iron plate for the sand paper of 400 mesh, 600 mesh and 1000 mesh using mesh number, polishing is finished, deionization
Water washing, nitrogen is dried, and is subsequently placed in the oven drying 1h that temperature is 50 DEG C；Anticorrosive paint is spin-coated on clean metal of polishing
On iron-based bottom, 75 DEG C of oven drying 2h is placed in；Then the metal iron plate side for being coated with anticorrosive paint manufactures one with pocket knife
Then it is bonded in one by the cut that area is 10mm × 1mm as defect with another clean, iron plate of the surface without anticorrosive paint
Rise, about 0.5cm room is reserved in defective side, to store electrolyte, turned on the two connection using copper foil tape；Most
Afterwards, sample is placed in scanning Kelvin probe test system, injecting 1mol/L KCl using liquid-transfering gun is electrolysed
Liquid, regulation system temperature is 25 DEG C, and humidity is 92r.h.%~98r.h.%, and arrange parameter is tested.
Compared with polyvinyl butyral resin ethanol solution of the anticorrosive paint only containing 14wt%, contain poly- (3,4- dioxy second
Base) anticorrosive paint of " pyriform " nano particle of thiophene shows excellent Corrosion Protection, and the corrosion rate of metallic iron is reduced to
21 μm/h, the range of decrease is about 45 times, effectively prevents metallic iron to be further corroded, as shown in Figure 3.
Embodiment 2
The preparation of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube：
1) it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio：In 1 water and acetonitrile mixture, stir, obtain concentration
For water/acetonitrile mixed solution of 1mmol/L polyvinylpyrrolidone；
2) 0.0162g multi-walled carbon nanotubes are added in above-mentioned solution, ultrasonic disperse 1h, acquisition contains multi-walled carbon nanotube
Suspension；
3) 0.32mL monomers (3,4- dioxoethyl) thiophene is added in above-mentioned solution, ultrasonic 2h obtains finely dispersed
Mixed solution；
4) ammonium persulfate aqueous solution of certain volume is added in above-mentioned solution, wherein ammonium persulfate and monomer EDOT rubs
You are than being 2:1, the polymerization system that cumulative volume is 100mL is formed, lasting stirring, normal temperature carries out chemical polymerization 48h, contained
There is the black mixed liquor of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube；
5) above-mentioned black mixed liquor is centrifuged, obtains black solid sediment；This black solid sediment is first used
Absolute ethyl alcohol is washed and centrifuged, and then uses volume ratio to be 1 again:1 water and the mixed solvent of ethanol are washed, Zhi Daoshang
Clear liquid is colourless；Finally it is washed with deionized again；Obtained black solid sediment is dried in vacuo at 80 DEG C, obtains black
Color solid, the composite nano fiber of as poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube, its stereoscan photograph is such as
Shown in Fig. 2, diameter is between 10nm~50nm, and length is 1~10 μm.
By the composite nano fiber conduct of above-mentioned poly- (3, the 4- dioxoethyl) thiophene and multi-walled carbon nanotube prepared
Prepare a kind of preparation of the polythiophene composition metal anticorrosive paint of pattern influence：
The quality of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and CNT is 15mg, Gu it is 14wt% to contain
Polyvinyl butyral resin volumes of aqueous ethanol be 3mL, absolute ethyl alcohol volume is 1mL, and three is uniformly mixed, and obtains described
Metal anti-corrosive paint.
Metal anti-corrosive paint described in above-mentioned prepare is applied to the anti-corrosion to metallic iron：
Polished successively metal iron plate for the sand paper of 400 mesh, 600 mesh and 1000 mesh using mesh number, polishing is finished, deionization
Water washing, nitrogen is dried, and is subsequently placed in the oven drying 1h that temperature is 50 DEG C；Anticorrosive paint is spin-coated on clean metal of polishing
On iron-based bottom, 75 DEG C of oven drying 2h is placed in；Then the metal iron plate side for being coated with anticorrosive paint manufactures one with pocket knife
Then it is bonded in one by the cut that area is 10mm × 1mm as defect with another clean, iron plate of the surface without anticorrosive paint
Rise, about 0.5cm room is reserved in defective side, to store electrolyte, turned on the two connection using copper foil tape；Most
Afterwards, sample is placed in scanning Kelvin probe test system, injecting 1mol/L KCl using liquid-transfering gun is electrolysed
Liquid, regulation system temperature is 25 DEG C, and humidity is 92r.h.%~98r.h.%, and arrange parameter is tested.
Now, the corrosion rate of metallic iron is 52 μm/h, is only 14wt% polyvinyl butyral resin with anticorrosive paint
Ethanol solution is compared, and the corrosion rate of metallic iron is slow down significantly.
Embodiment 3
The preparation of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube：
1) it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio：In 1 water and acetonitrile mixture, stir, obtain concentration
For water/acetonitrile mixed solution of 1mmol/L polyvinylpyrrolidone；
2) 0.0162g single-walled carbon nanotubes are added in above-mentioned solution, ultrasonic disperse 1h, acquisition contains multi-walled carbon nanotube
Suspension；
3) 0.32mL monomers (3,4- dioxoethyl) thiophene is added in above-mentioned solution, ultrasonic 2h obtains finely dispersed
Mixed solution；
4) ammonium persulfate aqueous solution of certain volume is added in above-mentioned solution, wherein ammonium persulfate and monomer EDOT rubs
You are than being 2:1, the polymerization system that cumulative volume is 100mL is formed, lasting stirring, normal temperature carries out chemical polymerization 48h, contained
There is the black mixed liquor of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube；
5) above-mentioned black mixed liquor is centrifuged, obtains black solid sediment；This black solid sediment is first used
Absolute ethyl alcohol is washed and centrifuged, and then uses volume ratio to be 1 again:1 water and the mixed solvent of ethanol are washed, Zhi Daoshang
Clear liquid is colourless；Finally it is washed with deionized again；Obtained black solid sediment is dried in vacuo at 80 DEG C, obtains black
Color solid, the composite nano fiber of as poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube, diameter is in 10nm~50nm
Between.
By the composite nano fiber conduct of above-mentioned poly- (3, the 4- dioxoethyl) thiophene and single-walled carbon nanotube prepared
Prepare a kind of preparation of the polythiophene composition metal anticorrosive paint of pattern influence：
The quality of the composite nano fiber of poly- (3,4- dioxoethyl) thiophene and CNT is 15mg, Gu it is 14wt% to contain
Polyvinyl butyral resin volumes of aqueous ethanol be 2mL, absolute ethyl alcohol volume is 1mL, and three is uniformly mixed, and obtains described
Metal anti-corrosive paint.
Metal anti-corrosive paint described in above-mentioned prepare is applied to the anti-corrosion to metallic iron：
Polished successively metal iron plate for the sand paper of 400 mesh, 600 mesh and 1000 mesh using mesh number, polishing is finished, deionization
Water washing, nitrogen is dried, and is subsequently placed in the oven drying 1h that temperature is 50 DEG C；Anticorrosive paint is spin-coated on clean metal of polishing
On iron-based bottom, 75 DEG C of oven drying 2h is placed in；Then the metal iron plate side for being coated with anticorrosive paint manufactures one with pocket knife
Then it is bonded in one by the cut that area is 10mm × 1mm as defect with another clean, iron plate of the surface without anticorrosive paint
Rise, about 0.5cm room is reserved in defective side, to store electrolyte, turned on the two connection using copper foil tape；Most
Afterwards, sample is placed in scanning Kelvin probe test system, injecting 1mol/L KCl using liquid-transfering gun is electrolysed
Liquid, regulation system temperature is 25 DEG C, and humidity is 92r.h.%~98r.h.%, and arrange parameter is tested.
Now, the corrosion rate of metallic iron is 64 μm/h, is only 14wt% polyvinyl butyral resin with anticorrosive paint
Ethanol solution is compared, and the corrosion rate of metallic iron is slow down significantly.
Embodiment 4
Be the same as Example 1, unique difference is the preparation process of " pyriform " nano particle of poly- (3,4- dioxoethyl) thiophene
1) in, the concentration of water/acetonitrile mixed solution of the polyvinylpyrrolidone of preparation is changed to 1mmol/L from 0.05mmol/L.Through surveying
Examination, performance is similar to Example 1.
Embodiment 5
Be the same as Example 1, unique difference is the preparation process of " pyriform " nano particle of poly- (3,4- dioxoethyl) thiophene
2) in, ultrasonic time is changed to 1h.After tested, performance is similar to Example 1.
Embodiment 6
Be the same as Example 1, unique difference is the preparation process of " pyriform " nano particle of poly- (3,4- dioxoethyl) thiophene
2) in, ultrasonic time is changed to 2h.After tested, performance is similar to Example 1.
Embodiment 7
Be the same as Example 1, unique difference is " pyriform " nanometer for poly- (3, the 4- dioxoethyl) thiophene that will be prepared
Grain is as in the preparation process for preparing the polythiophene composition metal anticorrosive paint that a kind of pattern influences, poly- (3,4- dioxoethyl) thiophene
" pyriform " nanoparticle mass of fen is changed to 60mg.After tested, performance is similar to Example 1.
Embodiment 8
Be the same as Example 1, unique difference is " pyriform " nanometer for poly- (3, the 4- dioxoethyl) thiophene that will be prepared
Grain is as in the preparation process for preparing the polythiophene composition metal anticorrosive paint that a kind of pattern influences, poly- (3,4- dioxoethyl) thiophene
" pyriform " nanoparticle mass of fen is changed to 110mg.After tested, performance is similar to Example 1.
Embodiment 9
Be the same as Example 1, unique difference is, by " pyriform " nanometer of poly- (3, the 4- dioxoethyl) thiophene prepared
Grain is as in the preparation process for preparing the polythiophene composition metal anticorrosive paint that a kind of pattern influences, polyvinyl butyral resin ethanol
The solid content of solution is changed to 7wt%.After tested, performance is similar to Example 1.
Embodiment 10
Be the same as Example 1, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
After nitrogen is dried, the oven drying 0.5h that temperature is 75 DEG C is placed in.After tested, performance is similar to Example 1.
Embodiment 11
Be the same as Example 1, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
Anticorrosive paint drop coating is being polished in clean metallic iron substrate, 50 DEG C of oven drying 1h is placed in.After tested, performance is with implementing
Example 1 is similar.
Embodiment 12
Be the same as Example 1, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, utilizing
Liquid-transfering gun injects 1mol/L NaCl electrolyte.After tested, performance is similar to Example 1.
Embodiment 13
Be the same as Example 2, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube is fine
The preparation process 1 of dimension) in, the concentration of water/acetonitrile mixed solution of the polyvinylpyrrolidone of preparation is changed to from 1mmol/L
0.5mmol/L.After tested, performance is similar to Example 2.
Embodiment 14
Be the same as Example 2, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube is fine
The preparation process 3 of dimension) in, ultrasonic time is changed to 1h.After tested, performance is similar to Example 2.
Embodiment 15
Be the same as Example 2, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and multi-walled carbon nanotube is fine
The preparation process 3 of dimension) in, ultrasonic time is changed to 0.5h.After tested, performance is similar to Example 2.
Embodiment 16
Be the same as Example 2, unique difference is poly- (3, the 4- dioxoethyl) thiophene and multi-walled carbon nanotube that will be prepared
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, it is poly- (3,
4- dioxoethyls) the composite nano fiber quality of thiophene and multi-walled carbon nanotube is changed to 60mg.After tested, performance and embodiment 2
It is similar.
Embodiment 17
Be the same as Example 2, unique difference is poly- (3, the 4- dioxoethyl) thiophene and multi-walled carbon nanotube that will be prepared
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, it is poly- (3,
4- dioxoethyls) the composite nano fiber quality of thiophene and multi-walled carbon nanotube is changed to 110mg.After tested, performance and embodiment 2
It is similar.
Embodiment 18
Be the same as Example 2, unique difference is, by poly- (3, the 4- dioxoethyl) thiophene and multi-walled carbon nanotube that prepare
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, polyethylene
The solid content of butyral ethanol solution is changed to 7wt%.After tested, performance is similar to Example 2.
Embodiment 19
Be the same as Example 2, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
After nitrogen is dried, the oven drying 0.5h that temperature is 75 DEG C is placed in.After tested, performance is similar to Example 2.
Embodiment 20
Be the same as Example 2, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
Anticorrosive paint drop coating is being polished in clean metallic iron substrate, 50 DEG C of oven drying 1h is placed in.After tested, performance is with implementing
Example 2 is similar.
Embodiment 21
Be the same as Example 2, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, utilizing
Liquid-transfering gun injects 1mol/L NaCl electrolyte.After tested, performance is similar to Example 2.
Embodiment 22
Be the same as Example 3, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube is fine
The preparation process 1 of dimension) in, the concentration of water/acetonitrile mixed solution of the polyvinylpyrrolidone of preparation is changed to from 1mmol/L
0.5mmol/L.After tested, performance is similar to Example 3.
Embodiment 23
Be the same as Example 3, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube is fine
The preparation process 3 of dimension) in, ultrasonic time is changed to 1h.After tested, performance is similar to Example 3.
Embodiment 24
Be the same as Example 3, unique difference is that the composite Nano of poly- (3,4- dioxoethyl) thiophene and single-walled carbon nanotube is fine
The preparation process 3 of dimension) in, ultrasonic time is changed to 0.5h.After tested, performance is similar to Example 3.
Embodiment 25
Be the same as Example 3, unique difference is poly- (3, the 4- dioxoethyl) thiophene and single-walled carbon nanotube that will be prepared
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, it is poly- (3,
4- dioxoethyls) the composite nano fiber quality of thiophene and single-walled carbon nanotube is changed to 60mg.After tested, performance and embodiment 3
It is similar.
Embodiment 26
Be the same as Example 3, unique difference is poly- (3, the 4- dioxoethyl) thiophene and single-walled carbon nanotube that will be prepared
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, it is poly- (3,
4- dioxoethyls) the composite nano fiber quality of thiophene and single-walled carbon nanotube is changed to 110mg.After tested, performance and embodiment 3
It is similar.
Embodiment 27
Be the same as Example 3, unique difference is, by poly- (3, the 4- dioxoethyl) thiophene and single-walled carbon nanotube that prepare
Preparation process of the composite nano fiber as the polythiophene composition metal anticorrosive paint for preparing a kind of influence of pattern in, polyethylene
The solid content of butyral ethanol solution is changed to 7wt%.After tested, performance is similar to Example 3.
Embodiment 28
Be the same as Example 3, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
After nitrogen is dried, the oven drying 0.5h that temperature is 75 DEG C is placed in.After tested, performance is similar to Example 3.
Embodiment 29
Be the same as Example 3, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, being changed to
Anticorrosive paint drop coating is being polished in clean metallic iron substrate, 50 DEG C of oven drying 1h is placed in.After tested, performance is with implementing
Example 3 is similar.
Embodiment 30
Be the same as Example 3, unique difference is, metal anti-corrosive paint is applied to in the anti-corrosion step of metallic iron, utilizing
Liquid-transfering gun injects 1mol/L NaCl electrolyte.After tested, performance is similar to Example 3.
Comparative example 1
The metal anti-corrosive paint for preparing the polyvinyl butyral resin ethanol solution for comprising only 14wt% is applied to metallic iron
Anti-corrosion：Polished successively metal iron plate for the sand paper of 400 mesh, 600 mesh and 1000 mesh using mesh number, polishing is finished, deionization
Water washing, nitrogen is dried, and is subsequently placed in the oven drying 1h that temperature is 50 DEG C；Anticorrosive paint is spin-coated on clean metal of polishing
On iron-based bottom, 60 DEG C of oven drying 0.5h is placed in；Then the metal iron plate side for being coated with anticorrosive paint is manufactured with pocket knife
Then it be bonded in by the cut that one area is 10mm × 1mm as defect with another clean, iron plate of the surface without anticorrosive paint
Together, about 0.5cm room is reserved in defective side, to store electrolyte, is turned on the two connection using copper foil tape；
Finally, sample is placed in scanning Kelvin probe test system, injecting 1mol/L KCl using liquid-transfering gun is electrolysed
Liquid, regulation system temperature is 25 DEG C, and humidity is 92r.h.%, and arrange parameter is tested, and the corrosion rate of metallic iron is 900 μ
m/h。
Test result shows to be better than containing poly- (3,4- containing poly- (3,4- dioxoethyl) thiophene " pyriform " nanometer full particle
Dioxoethyl) thiophene/CNT composite hollow fiber composition metal anticorrosive paint to the anti-corrosion capability of iron, while much
Higher than the resistance to corrosion having containing simple polyvinyl butyral resin ethanol solution.
It is a kind of excellent anti-corrosion of metal corrosion material to illustrate poly- (3,4- dioxoethyl) thiophene, and different nanostructureds
Poly- (3,4- dioxoethyl) thiophene is different to the antiseptic property of metallic iron.Speculate because poly- (3,4- dioxoethyl) thiophene
" pyriform " nano particle is medicine ball, and poly- (3,4- dioxoethyl) thiophene and carbon mano-tube composite are hollow-core construction, two
Plant structure to compare, solid construction can provide more effective charges, more effectively polarizing coatings and metal interface, improve rotten
Current potential is lost, slows down corrosion.When dissolving metal, metallic perimeter (interface of such as metal and material) produces a certain amount of electronics,
Poly- (3, the 4- dioxoethyl) thiophene of oxidation state can obtain electronics in time and be reduced, effectively the reduction of reduction oxygen, so as to press down
(easily attack metal is with polymer interface, destroying polymer chain, polymer and metal for oxygen radical and hydroxide ion processed
Cementability reduction, cause coating shedding, exposed metal/bare metal outside, accelerates corrosion of metal) formation, slow down disbonding, reach
To anti-corrosion purpose.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (9)
1. a kind of polythiophene composition metal anticorrosive paint of pattern influence, it is characterised in that include the component of following content：
It is poly-（3,4- dioxoethyls）" pyriform " nano particle of thiophene is poly-（3,4- dioxoethyls）Thiophene and CNT are answered
Close nanofiber：15 mg~110 mg；
Polyvinyl butyral resin ethanol solution：1~3 mL；
Absolute ethyl alcohol：1~3 mL；
Wherein, 7wt% ~ 14wt% polyvinyl butyral resin is contained in the polyvinyl butyral resin ethanol solution admittedly；The carbon is received
Mitron is single-walled carbon nanotube or multi-walled carbon nanotube；
It is described poly-（3,4- dioxoethyls）The preparation of " pyriform " nano particle of thiophene comprises the following steps：
1）It is 4 that polyvinylpyrrolidone is dissolved in into volume ratio:In 1 water and acetonitrile mixture, stir, obtaining concentration is
Water/acetonitrile mixed solution of 0.05 ~ 1 mmol/L polyvinylpyrrolidone；
2）To step 1）Monomer is added in middle gained mixed solution（3,4- dioxoethyls）Thiophene, the h of ultrasonic 0.5 h ~ 2, is divided
Dissipate uniform mixed solution；
3）To step 2）The ammonium persulfate oxidizing agent aqueous solution is added in the middle finely dispersed mixed solution of gained, wherein, persulfuric acid
Ammonium and monomer（3,4- dioxoethyls）Thiophene mol ratio is 2：1, lasting stirring, the h of polymerized at normal temperature 48 is obtained containing poly-（3,4- dioxies
Ethyl）The black mixed liquor of " pyriform " nano particle of thiophene；
4）By step 3）Gained black mixed liquor is centrifuged, and obtains black solid sediment, then this sediment is washed,
Dry, gathered（3,4- dioxoethyls）" pyriform " nano particle of thiophene；
It is described poly-（3,4- dioxoethyls）The preparation of the composite nano fiber of thiophene and CNT comprises the following steps：
1. it is 4 polyvinylpyrrolidone to be dissolved in into volume ratio:In 1 water and acetonitrile mixture, stir, obtaining concentration is
Water/acetonitrile mixed solution of 0.05 ~ 1 mmol/L polyvinylpyrrolidone；
2. single wall or multi-walled carbon nanotube are added into step 1. gained mixed solution, the h of ultrasonic disperse 1, acquisition is received containing carbon
The suspension of mitron；
3. monomer is added into step 2. middle gained suspension（3,4- dioxoethyls）Thiophene, the h of ultrasonic 0.5 h ~ 2, is divided
Dissipate uniform mixed solution；
4. the ammonium persulfate oxidizing agent aqueous solution is added into the step 3. mixed solution, wherein, ammonium persulfate and monomer（3,
4- dioxoethyls）Thiophene mol ratio is 2：1, lasting stirring, normal temperature emulsion polymerisation reacts 48 h, obtains containing poly-（3,4- dioxies
Ethyl）The black mixed liquor of the composite nano fiber of thiophene and CNT；
5. by step, 4. gained black mixed liquor is centrifuged, and obtains black solid sediment, then this sediment is washed
Wash, dry, gathered（3,4- dioxoethyls）The composite nano fiber of thiophene and CNT.
2. a kind of polythiophene composition metal anticorrosive paint of pattern influence according to claim 1, it is characterised in that step
4）In, it is described poly-（3,4- dioxoethyls）" pyriform " nano particle diameter of thiophene is the nm of 200 nm~500.
3. a kind of polythiophene composition metal anticorrosive paint of pattern influence according to claim 1, it is characterised in that step
4）In, the washing is that the black solid sediment is first washed with deionized and centrifuged, then with volume ratio be 1:1
Water and the mixed solvent of ethanol washed, until supernatant is colourless；Finally it is washed with deionized again.
4. a kind of polythiophene composition metal anticorrosive paint of pattern influence according to claim 1, it is characterised in that step
5. it is described poly- in（3,4- dioxoethyls）The nm of a diameter of 10 nm of composite nano fiber of thiophene and CNT~50；It is described
It is poly-（3,4- dioxoethyls）The composite nano fiber long degree of thiophene and CNT is 1 ~ 10 μm.
5. a kind of polythiophene composition metal anticorrosive paint of pattern influence according to claim 1, it is characterised in that step
5. in, the washing is that the black solid sediment is first washed with deionized and centrifuged, then with volume ratio be 1:1
Water and the mixed solvent of ethanol washed, until supernatant is colourless；Finally it is washed with deionized again.
6. the preparation of the polythiophene composition metal anticorrosive paint of pattern influence according to any one of claims 1 to 5
Method, it is characterised in that comprise the following steps：
Will be poly-（3,4- dioxoethyls）" pyriform " nano particle of thiophene is poly-（3,4- dioxoethyls）Thiophene and CNT
Composite nano fiber, polyvinyl butyral resin ethanol solution and absolute ethyl alcohol are well mixed, prepare a kind of pattern influence
Polythiophene composition metal anticorrosive paint；
Wherein, each component content is：
It is poly-（3,4- dioxoethyls）" pyriform " nano particle of thiophene is poly-（3,4- dioxoethyls）Thiophene and CNT are answered
It is the mg of 15 mg ~ 110 to close the quality of nanofiber；
Polyvinyl butyral resin volumes of aqueous ethanol is 1 ~ 3 mL；
Absolute ethyl alcohol volume is 1 ~ 3 mL；
Admittedly 7wt% ~ 14wt% polyvinyl butyral resin is contained in the polyvinyl butyral resin ethanol solution；
The CNT is single-walled carbon nanotube or multi-walled carbon nanotube.
7. a kind of polythiophene composition metal anticorrosive paint the answering in metallic iron anti-corrosion of pattern influence as claimed in claim 1
With.
8. application according to claim 7, it is characterised in that：The method of testing of the application comprises the following steps：Will system
Standby obtained anti-corrosion paint is being polished in clean metallic iron piece substrate, is placed in 50 ~ 75 DEG C of the h of oven drying 1 ~ 2；Again
It is the mm of 10 mm × 1 cut as defect that this metal iron plate side is manufactured to an area with pocket knife, by itself and another clean, table
Iron plate of the face without anticorrosive paint is bonded together, and 0.5 cm room is reserved in defective side, for storing electrolyte；Use copper
Above-mentioned two metal iron plate is connected and turned on by foil belt, and sample is made；Finally, sample is placed in scanning Kelvin
In probe test system, tested；The electrolyte is sodium-chloride water solution or potassium chloride solution；The polishing is
Polished successively metal iron plate for the sand paper of 400 mesh, 600 mesh and 1000 mesh using mesh number, polishing is washed with deionized water after finishing
Wash, nitrogen is dried, then be placed in the h of the h of oven drying 0.5 ~ 1 that temperature is 50 DEG C ~ 75 DEG C.
9. application according to claim 8, it is characterised in that：It is described to be applied to spin coating or drop coating.
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