CN105153883A - Shape-influenced polythiophene composite metal anticorrosive paint as well as preparation method and application thereof - Google Patents
Shape-influenced polythiophene composite metal anticorrosive paint as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a shape-influenced polythiophene composite metal anticorrosive paint as well as a preparation method and application thereof. The polythiophene composite metal anticorrosive paint comprises the following components by weight: 15mg-110mg of pear-shaped nano-particles of poly(3,4-diethoxyethyl)thiophene or composite nanofibers of poly(3,4-diethoxyethyl)thiophene and carbon nanotube, 1mL-3mL of a polyvinyl butyral solution and 1mL-3mL of absolute ethyl alcohol. According to the preparation method and the application, the pear-shaped nanoparticles of poly(3,4-diethoxyethyl)thiophene or the composite nanofibers of poly(3,4-diethoxyethyl)thiophene and carbon nanotube are prepared through emulsion polymerization and are mixed with an ethanol solution or absolute ethyl alcohol to prepare the conductive composite metal anticorrosive paint, and the composite metal anticorrosive paint is applied to the corrosion prevention of metallic iron. The polythiophene composite metal anticorrosive paint is low in cost and environmental pollution and good in comprehensive performance. Besides, by virtue of a scanning Kelvin probe testing technique, the damage of a coating is avoided, and the anticorrosion condition of the coating on metal can be effectively monitored.
Description
Technical field
The present invention relates to anticorrosive metal Material Field.More specifically, Polythiophene composition metal protective system and the preparation and application thereof of the impact of a kind of pattern are related to.
Background technology
Metallic substance all has in civilian and national defence the critical role do not replaced, and metallic corrosion brings huge financial loss and environmental hazard to social development, therefore address this problem one of important goal becoming development in science and technology, and the anti-corrosion of metal material of development of new, excellent performance is the key of head it off.Usually applying one deck organic anti-corrosive material in metallic surface is effective anti-corrosion of metal means, because the organic coating of metallic surface serves as the role of obstacle, can stop moisture to a certain extent, oxygen and ion etc. enter metal interface generation redox reaction and corroding metal; On the other hand, the redox potential that conductive polymers is higher can make erode metallic surfaces potential polarization effectively, thus improves its current potential, stops corrosion.
The comparatively effective impregnating material major part of tradition is chromic salt, but it is owing to causing very large harm containing virose chromium to environment and human body, is used by the restriction of European legislation regulation now, therefore urgently seeks the impregnating material of new green environment protection.Since conductive polymers was found from 1977, there is due to it physics-chem characteristics such as excellent, electricity, magnetics, and be widely used in different fields.The eighties in 19th century, (the J.Appl.Polym.Sci. such as Mengoli, 1981,26,4247) and (J.Electrochem.Soc., 1985,132 such as DeBerry, 1022) conductive polymer polyanaline is electrochemically-deposited at the bottom of iron-based by reported first, and have studied its anti-corrosion of metal performance.Experimental result shows, polyaniline shows certain antiseptic property, thus has started the application of conductive polymers in anti-corrosion of metal field.Since then, conductive polymers obtains in metal protection field and studies widely, is wherein no lack of commercial conductive polymers protective system.1996, the people such as the Ormecon company Wessling of Germany successfully have developed industrial anticorrosive polyaniline material, as ORMECONTM, and CORRPASIV, Version etc.
CN102703945A discloses a kind of novel electric polypyrrole/polyaniline composite anti-corrosive coating, and is applied to Copper substrate surface, effectively improves the corrosion potential of Copper substrate, reduces corrosion current, show good Anticorrosive Character.But the preparation method that this composite anti-corrosive coating adopts is electrochemical polymerization, therefore its stability and repeatability wayward, can not synthesize on a large scale simultaneously, limit its practical application to a great extent.
Although the antiseptic property research of electrically conductive polyaniline is comparatively extensive at present, also comparatively ripe, there is number of chemical transition structure in polyaniline, wherein certain structures exists certain toxicity, and it has the shortcomings such as sensitivity to acid, causes its performance stable not.And Polythiophene and derivative thereof are due to the environment of its excellence and chemical stability, higher redox potential and embody huge advantage in anti-corrosion of metal field.
Summary of the invention
One object of the present invention is the Polythiophene composition metal protective system providing a kind of pattern to affect.
Second object of the present invention is the preparation method of the Polythiophene composition metal protective system providing a kind of pattern to affect.
3rd object of the present invention is the application of Polythiophene composition metal protective system in metallic iron is anticorrosion providing a kind of pattern to affect.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
A Polythiophene composition metal protective system for pattern impact, comprises the component of following content:
" pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene or the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and carbon nanotube: 15mg ~ 110mg;
Polyvinyl butyral acetal ethanolic soln: 1 ~ 3mL;
Dehydrated alcohol: 1 ~ 3mL.
Preferably, the polyvinyl butyral acetal admittedly containing 7wt% ~ 14wt% in described polyvinyl butyral acetal ethanolic soln.
Preferably, described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
The preparation of " pyriform " nano particle of described poly-(3,4-dioxoethyl) thiophene comprises the steps:
1) polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 0.05 ~ 1mmol/L;
2) to step 1) in add monomer (3,4-dioxoethyl) thiophene in gained mixing solutions, ultrasonic 0.5h ~ 2h, obtains finely dispersed mixing solutions;
3) to step 2) in add the ammonium persulfate oxidizing agent aqueous solution in the finely dispersed mixing solutions of gained, wherein, ammonium persulphate and monomer (3,4-dioxoethyl) thiophene mol ratio is 2:1, Keep agitation, polymerized at normal temperature 48h, obtains the black mixed solution of " pyriform " nano particle containing poly-(3,4-dioxoethyl) thiophene;
4) by step 3) centrifugation of gained black mixed solution, obtain black solid throw out, then this throw out is carried out wash, dry, gathered " pyriform " nano particle of (3,4-dioxoethyl) thiophene.
Preferably, step 4) in, " pyriform " nano particle diameter of described poly-(3,4-dioxoethyl) thiophene is 200nm ~ 500nm.
Preferably, step 4) in, described washing is by described black solid throw out first with deionized water wash and centrifugation, then is that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio, until supernatant liquor is colourless; Finally use deionized water wash again.
The preparation of the composite nano fiber of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube comprises the steps;
1. polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 0.05 ~ 1mmol/L;
2. in step 1. gained mixing solutions, add single wall or multi-walled carbon nano-tubes, ultrasonic disperse 1h, obtain the suspension containing carbon nanotube;
3. in step 2. middle gained suspension, add monomer (3,4-dioxoethyl) thiophene, ultrasonic 0.5h ~ 2h, obtains finely dispersed mixing solutions;
4. in step 3. described mixing solutions, the ammonium persulfate oxidizing agent aqueous solution is added, wherein, ammonium persulphate and monomer (3,4-dioxoethyl) thiophene mol ratio is 2:1, Keep agitation, normal temperature emulsion polymerisation reaction 48h, obtains the black mixed solution containing the composite nano fiber gathering (3,4-dioxoethyl) thiophene and carbon nanotube;
5. by step 4. gained black mixed solution centrifugation, obtain black solid throw out, then this throw out is carried out wash, dry, gathered the composite nano fiber of (3,4-dioxoethyl) thiophene and carbon nanotube.
Preferably, step 5. in, the composite nano fiber diameter of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 10nm ~ 50nm; Preferably, the composite nano fiber long degree of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 1 ~ 10 μm.
Preferably, step 5. in, described washing is by described black solid throw out first with deionized water wash and centrifugation, then is that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio, until supernatant liquor is colourless; Finally use deionized water wash again.
For reaching above-mentioned second object, the present invention adopts following technical proposals:
A preparation method for the Polythiophene composition metal protective system of pattern impact, comprises the steps:
To (3 be gathered, 4-dioxoethyl) " pyriform " nano particle or poly-(3 of thiophene, 4-dioxoethyl) composite nano fiber of thiophene and carbon nanotube, polyvinyl butyral acetal ethanolic soln and dehydrated alcohol mix, and prepares the Polythiophene composition metal protective system of a kind of pattern impact;
Wherein, each component concentration is:
The quality of " pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene or the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 15mg ~ 110mg;
Polyvinyl butyral acetal volumes of aqueous ethanol is 1 ~ 3mL;
Dehydrated alcohol volume is 1 ~ 3mL;
Polyvinyl butyral acetal admittedly containing 7wt% ~ 14wt% in described polyvinyl butyral acetal ethanolic soln;
Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
For reaching above-mentioned 3rd object, the present invention adopts following technical proposals:
A kind of application of Polythiophene composition metal protective system in metallic iron is anticorrosion of pattern impact.The concrete detection method of application comprises the steps:
By described anti-corrosion paint polishing in clean metal iron plate substrate, be placed in the oven drying 1 ~ 2h of 50 ~ 75 DEG C; Again the metal iron plate side pocket knife being coated with protective system being manufactured an area is that the cut of 10mm × 1mm is as defect, itself and another clean, surperficial iron plate without protective system is bonded together, reserve the room of about 0.5cm in defectiveness side, utilize copper foil tape that the two is connected conducting; Finally, sample is placed in the test system of scanningKelvinprobe, tests.
Preferably, be applied to spin coating described in or drip and be coated with.
Preferably, in order to utilize, order number is 400 orders in described polishing, metal iron plate polished successively by 600 orders and 1000 object sand paper, with deionized water wash after polishing, and nitrogen drying, then the oven drying 0.5h ~ 1h being placed in that temperature is 50 DEG C ~ 75 DEG C.
Preferably, described electrolytic solution is sodium chloride aqueous solution or potassium chloride solution.
Compared with the metal anti-corrosive paint only containing polyvinyl butyral acetal ethanolic soln; containing pattern for gathering (3; 4-dioxoethyl) thiophene " pyriform " nano particle or be poly-(3 containing pattern; 4-dioxoethyl) the Polythiophene composition metal protective system of composite nano fiber of thiophene and nanotube, show the more excellent Corrosion Protection to iron.Protective system contains pattern when being Polythiophene pyriform nano particle, it is mixed with polyvinyl butyral acetal ethanolic soln, compared with being only polyvinyl butyral acetal ethanolic soln with protective system, the erosion rate of metallic iron is reduced to 21 μm/h by 900 μm/h, and the range of decrease is about 45 times; When protective system is the composite nano fiber containing poly-(3,4-dioxoethyl) thiophene and nanotube, the erosion rate of metallic iron is 66 ~ 108 μm/h, and the range of decrease is about 9 ~ 15 times, effectively slow down metal and is further corroded.
Wherein, containing pattern for gathering (3,4-dioxoethyl) protective system prepared by thiophene " pyriform " nano particle is than being poly-(3 containing pattern, 4-dioxoethyl) the protective system antiseptic property prepared by composite nano fiber of thiophene and nanotube is better, illustrate that the poly-antiseptic property of (3,4-dioxoethyl) thiophene on metallic iron of different nanostructure has important impact.Infer because poly-(3, 4-dioxoethyl) thiophene " pyriform " nano particle is solid sphere, and gather (3, 4-dioxoethyl) thiophene and carbon mano-tube composite be hollow structure, two kinds of structures are compared, solid construction can provide more effective charge, when dissolving metal, metallic perimeter (interface as metal and material) produces a certain amount of electronics, poly-(3 of oxidation state, 4-dioxoethyl) thiophene can obtain electronics in time and be reduced, the reduction of effective reduction oxygen, thus suppress oxyradical and hydroxide ion (very easily attack metal and polymer interface place, destroy polymer chain, the cementability of polymkeric substance and metal reduces, cause coating shedding, exposed metal/bare metal outside, accelerate corrosion of metal) formation, slow down disbonding, reach anticorrosion object.
Beneficial effect of the present invention is as follows:
1. the Polythiophene composition metal protective system of a kind of pattern impact of the present invention, its preparation method is simple, easy, controlled and be beneficial to scale production.
2. the Polythiophene composition metal protective system of a kind of pattern impact of the present invention has excellent environment and chemical stability, higher redox potential, thus shows excellent anti-corrosion of metal performance.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the stereoscan photograph of poly-(3,4-dioxoethyl) thiophene " pyriform " nano particle of the embodiment of the present invention 1.
Fig. 2 illustrates poly-(3,4-dioxoethyl) thiophene and the multi-walled carbon nano-tubes conjugated fibre stereoscan photograph of the embodiment of the present invention 2.
Fig. 3 illustrates that the Polythiophene composition metal protective system of a kind of pattern impact that the embodiment of the present invention 1,2,3 prepares is applied to the erosion rate figure of the metallic iron surveyed in the protection against corrosion research of iron.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
The preparation of " pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene:
1) be dissolved in by polyvinylpyrrolidone in the water that volume ratio is 4:1 and acetonitrile mixture, stir, preparation concentration is the water/acetonitrile mixing solutions of the polyvinylpyrrolidone of 0.05mmol/L;
2) in above-mentioned solution, add 0.2mL monomer (3,4-dioxoethyl) thiophene, ultrasonic 0.5h, obtains finely dispersed mixing solutions;
3) ammonium persulfate aqueous solution of the certain volume added in above-mentioned solution, wherein ammonium persulphate and monomer (3,4-dioxoethyl) mol ratio of thiophene (EDOT) is 2:1, forming cumulative volume is the polymerization system of 100mL, Keep agitation, normal temperature carries out chemical polymerization 48h, obtains the black mixed solution of " pyriform " nano particle containing poly-(3,4-dioxoethyl) thiophene;
4) by the centrifugation of above-mentioned black mixed solution, black solid throw out is obtained; By this black solid throw out first with deionized water wash and centrifugation, and then be that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio, until supernatant liquor is colourless; Finally use deionized water wash again; By the black solid throw out vacuum-drying at 80 DEG C obtained, obtain black solid, be " pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene, as shown in Figure 1, particle diameter is 200nm ~ 500nm to its stereoscan photograph.
By the preparation of " pyriform " nano particle of above-mentioned poly-(3,4-dioxoethyl) thiophene prepared as the Polythiophene composition metal protective system of a kind of pattern impact of preparation:
Poly-(3,4-dioxoethyl) " pyriform " nanoparticle mass of thiophene is 15mg, Gu be 1mL containing the polyvinyl butyral acetal volumes of aqueous ethanol for 14wt%, dehydrated alcohol volume is 3mL, by three's Homogeneous phase mixing, obtain described metal anti-corrosive paint.
What be applied to by the metal anti-corrosive paint described in above-mentioned preparing metallic iron is anticorrosion:
Utilize that order number is 400 orders, metal iron plate polished successively by 600 orders and 1000 object sand paper, polish complete, deionized water wash, nitrogen drying, is then placed in the oven drying 1h that temperature is 50 DEG C; Protective system is spin-coated in the clean metallic iron substrate of polishing, is placed in the oven drying 2h of 75 DEG C; Then the metal iron plate side pocket knife being coated with protective system being manufactured an area is that the cut of 10mm × 1mm is as defect, then itself and another clean, surperficial iron plate without protective system is bonded together, the room of about 0.5cm is reserved in defectiveness side, to store electrolytic solution, utilize copper foil tape that the two is connected conducting; Finally, sample is placed in the test system of scanningKelvinprobe, utilize liquid-transfering gun to inject 1mol/LKCl electrolytic solution, regulation system temperature is 25 DEG C, and humidity is 92r.h.% ~ 98r.h.%, and parameters, tests.
Compared with the polyvinyl butyral acetal ethanolic soln only containing 14wt% with protective system, containing poly-(3,4-dioxoethyl) protective system of " pyriform " nano particle of thiophene shows excellent Corrosion Protection, the erosion rate of metallic iron reduces to 21 μm/h, the range of decrease is about 45 times, metallic iron is effectively prevented 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 nano-tubes:
1) polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 1mmol/L;
2) in above-mentioned solution, add 0.0162g multi-walled carbon nano-tubes, ultrasonic disperse 1h, obtain the suspension containing multi-walled carbon nano-tubes;
3) in above-mentioned solution, add 0.32mL monomer (3,4-dioxoethyl) thiophene, ultrasonic 2h, obtains finely dispersed mixing solutions;
4) in above-mentioned solution, add the ammonium persulfate aqueous solution of certain volume, wherein the mol ratio of ammonium persulphate and monomer EDOT is 2:1, forming cumulative volume is the polymerization system of 100mL, Keep agitation, normal temperature carries out chemical polymerization 48h, obtain the black mixed solution containing the composite nano fiber gathering (3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes;
5) by the centrifugation of above-mentioned black mixed solution, black solid throw out is obtained; By this black solid throw out first with absolute ethanol washing and centrifugation, and then be that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio, until supernatant liquor is colourless; Finally use deionized water wash again; By the black solid throw out vacuum-drying at 80 DEG C obtained, obtain black solid, be poly-(3,4-dioxoethyl) composite nano fiber of thiophene and multi-walled carbon nano-tubes, as shown in Figure 2, diameter is between 10nm ~ 50nm, and length is 1 ~ 10 μm for its stereoscan photograph.
By the above-mentioned composite nano fiber gathering (3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes prepared as the preparation preparing the Polythiophene composition metal protective system that a kind of pattern affects:
Poly-(3,4-dioxoethyl) quality of composite nano fiber of thiophene and carbon nanotube is 15mg, Gu be 3mL containing the polyvinyl butyral acetal volumes of aqueous ethanol for 14wt%, dehydrated alcohol volume is 1mL, by three's Homogeneous phase mixing, obtain described metal anti-corrosive paint.
What be applied to by the metal anti-corrosive paint described in above-mentioned preparing metallic iron is anticorrosion:
Utilize that order number is 400 orders, metal iron plate polished successively by 600 orders and 1000 object sand paper, polish complete, deionized water wash, nitrogen drying, is then placed in the oven drying 1h that temperature is 50 DEG C; Protective system is spin-coated in the clean metallic iron substrate of polishing, is placed in the oven drying 2h of 75 DEG C; Then the metal iron plate side pocket knife being coated with protective system being manufactured an area is that the cut of 10mm × 1mm is as defect, then itself and another clean, surperficial iron plate without protective system is bonded together, the room of about 0.5cm is reserved in defectiveness side, to store electrolytic solution, utilize copper foil tape that the two is connected conducting; Finally, sample is placed in the test system of scanningKelvinprobe, utilize liquid-transfering gun to inject 1mol/LKCl electrolytic solution, regulation system temperature is 25 DEG C, and humidity is 92r.h.% ~ 98r.h.%, and parameters, tests.
Now, the erosion rate of metallic iron is 52 μm/h, compared with the ethanolic soln being only the polyvinyl butyral acetal of 14wt%, greatly slow down the erosion rate of metallic iron with protective system.
Embodiment 3
The preparation of the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube:
1) polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 1mmol/L;
2) in above-mentioned solution, add 0.0162g Single Walled Carbon Nanotube, ultrasonic disperse 1h, obtain the suspension containing multi-walled carbon nano-tubes;
3) in above-mentioned solution, add 0.32mL monomer (3,4-dioxoethyl) thiophene, ultrasonic 2h, obtains finely dispersed mixing solutions;
4) in above-mentioned solution, add the ammonium persulfate aqueous solution of certain volume, wherein the mol ratio of ammonium persulphate and monomer EDOT is 2:1, forming cumulative volume is the polymerization system of 100mL, Keep agitation, normal temperature carries out chemical polymerization 48h, obtain the black mixed solution containing the composite nano fiber gathering (3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube;
5) by the centrifugation of above-mentioned black mixed solution, black solid throw out is obtained; By this black solid throw out first with absolute ethanol washing and centrifugation, and then be that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio, until supernatant liquor is colourless; Finally use deionized water wash again; By the black solid throw out vacuum-drying at 80 DEG C obtained, obtain black solid, be the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube, diameter is between 10nm ~ 50nm.
By the above-mentioned composite nano fiber gathering (3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube prepared as the preparation preparing the Polythiophene composition metal protective system that a kind of pattern affects:
Poly-(3,4-dioxoethyl) quality of composite nano fiber of thiophene and carbon nanotube is 15mg, Gu be 2mL containing the polyvinyl butyral acetal volumes of aqueous ethanol for 14wt%, dehydrated alcohol volume is 1mL, by three's Homogeneous phase mixing, obtain described metal anti-corrosive paint.
What be applied to by the metal anti-corrosive paint described in above-mentioned preparing metallic iron is anticorrosion:
Utilize that order number is 400 orders, metal iron plate polished successively by 600 orders and 1000 object sand paper, polish complete, deionized water wash, nitrogen drying, is then placed in the oven drying 1h that temperature is 50 DEG C; Protective system is spin-coated in the clean metallic iron substrate of polishing, is placed in the oven drying 2h of 75 DEG C; Then the metal iron plate side pocket knife being coated with protective system being manufactured an area is that the cut of 10mm × 1mm is as defect, then itself and another clean, surperficial iron plate without protective system is bonded together, the room of about 0.5cm is reserved in defectiveness side, to store electrolytic solution, utilize copper foil tape that the two is connected conducting; Finally, sample is placed in the test system of scanningKelvinprobe, utilize liquid-transfering gun to inject 1mol/LKCl electrolytic solution, regulation system temperature is 25 DEG C, and humidity is 92r.h.% ~ 98r.h.%, and parameters, tests.
Now, the erosion rate of metallic iron is 64 μm/h, compared with the ethanolic soln being only the polyvinyl butyral acetal of 14wt%, greatly slow down the erosion rate of metallic iron with protective system.
Embodiment 4
With embodiment 1, unique difference is the preparation process 1 of " pyriform " nano particle gathering (3,4-dioxoethyl) thiophene) in, the concentration of the water/acetonitrile mixing solutions of the polyvinylpyrrolidone of preparation changes 1mmol/L into from 0.05mmol/L.After tested, performance is similar to Example 1.
Embodiment 5
With embodiment 1, unique difference is the preparation process 2 of " pyriform " nano particle gathering (3,4-dioxoethyl) thiophene) in, ultrasonic time changes 1h into.After tested, performance is similar to Example 1.
Embodiment 6
With embodiment 1, unique difference is the preparation process 2 of " pyriform " nano particle gathering (3,4-dioxoethyl) thiophene) in, ultrasonic time changes 2h into.After tested, performance is similar to Example 1.
Embodiment 7
With embodiment 1, unique difference is will prepare poly-(3,4-dioxoethyl) in " pyriform " nano particle of thiophene preparation process as the Polythiophene composition metal protective system of a kind of pattern of preparation impact, " pyriform " nanoparticle mass of poly-(3,4-dioxoethyl) thiophene changes 60mg into.After tested, performance is similar to Example 1.
Embodiment 8
With embodiment 1, unique difference is will prepare poly-(3,4-dioxoethyl) in " pyriform " nano particle of thiophene preparation process as the Polythiophene composition metal protective system of a kind of pattern of preparation impact, " pyriform " nanoparticle mass of poly-(3,4-dioxoethyl) thiophene changes 110mg into.After tested, performance is similar to Example 1.
Embodiment 9
With embodiment 1, unique difference is, to prepare poly-(3,4-dioxoethyl) in " pyriform " nano particle of thiophene preparation process as the Polythiophene composition metal protective system of a kind of pattern of preparation impact, the solid content of polyvinyl butyral acetal ethanolic soln changes 7wt% into.After tested, performance is similar to Example 1.
Embodiment 10
With embodiment 1, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, after changing nitrogen drying into, is placed in the oven drying 0.5h that temperature is 75 DEG C.After tested, performance is similar to Example 1.
Embodiment 11
With embodiment 1, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, changes into protective system to drip to be coated in the clean metallic iron substrate of polishing, is placed in the oven drying 1h of 50 DEG C.After tested, performance is similar to Example 1.
Embodiment 12
With embodiment 1, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, utilizes liquid-transfering gun to inject 1mol/LNaCl electrolytic solution.After tested, performance is similar to Example 1.
Embodiment 13
With embodiment 2, unique difference is to gather (3,4-dioxoethyl) preparation process 1 of composite nano fiber of thiophene and multi-walled carbon nano-tubes) in, the concentration of the water/acetonitrile mixing solutions of the polyvinylpyrrolidone of preparation changes 0.5mmol/L into from 1mmol/L.After tested, performance is similar to Example 2.
Embodiment 14
With embodiment 2, unique difference is the preparation process 3 of the composite nano fiber gathering (3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes) in, ultrasonic time changes 1h into.After tested, performance is similar to Example 2.
Embodiment 15
With embodiment 2, unique difference is the preparation process 3 of the composite nano fiber gathering (3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes) in, ultrasonic time changes 0.5h into.After tested, performance is similar to Example 2.
Embodiment 16
With embodiment 2, unique difference is will prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and multi-walled carbon nano-tubes is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, the composite nano fiber quality of poly-(3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes changes 60mg into.After tested, performance is similar to Example 2.
Embodiment 17
With embodiment 2, unique difference is will prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and multi-walled carbon nano-tubes is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, the composite nano fiber quality of poly-(3,4-dioxoethyl) thiophene and multi-walled carbon nano-tubes changes 110mg into.After tested, performance is similar to Example 2.
Embodiment 18
With embodiment 2, unique difference is, to prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and multi-walled carbon nano-tubes is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, and the solid content of polyvinyl butyral acetal ethanolic soln changes 7wt% into.After tested, performance is similar to Example 2.
Embodiment 19
With embodiment 2, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, after changing nitrogen drying into, is placed in the oven drying 0.5h that temperature is 75 DEG C.After tested, performance is similar to Example 2.
Embodiment 20
With embodiment 2, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, changes into protective system to drip to be coated in the clean metallic iron substrate of polishing, is placed in the oven drying 1h of 50 DEG C.After tested, performance is similar to Example 2.
Embodiment 21
With embodiment 2, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, utilizes liquid-transfering gun to inject 1mol/LNaCl electrolytic solution.After tested, performance is similar to Example 2.
Embodiment 22
With embodiment 3, unique difference is to gather (3,4-dioxoethyl) preparation process 1 of composite nano fiber of thiophene and Single Walled Carbon Nanotube) in, the concentration of the water/acetonitrile mixing solutions of the polyvinylpyrrolidone of preparation changes 0.5mmol/L into from 1mmol/L.After tested, performance is similar to Example 3.
Embodiment 23
With embodiment 3, unique difference is the preparation process 3 of the composite nano fiber gathering (3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube) in, ultrasonic time changes 1h into.After tested, performance is similar to Example 3.
Embodiment 24
With embodiment 3, unique difference is the preparation process 3 of the composite nano fiber gathering (3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube) in, ultrasonic time changes 0.5h into.After tested, performance is similar to Example 3.
Embodiment 25
With embodiment 3, unique difference is will prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and Single Walled Carbon Nanotube is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, the composite nano fiber quality of poly-(3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube changes 60mg into.After tested, performance is similar to Example 3.
Embodiment 26
With embodiment 3, unique difference is will prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and Single Walled Carbon Nanotube is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, the composite nano fiber quality of poly-(3,4-dioxoethyl) thiophene and Single Walled Carbon Nanotube changes 110mg into.After tested, performance is similar to Example 3.
Embodiment 27
With embodiment 3, unique difference is, to prepare poly-(3,4-dioxoethyl) composite nano fiber of thiophene and Single Walled Carbon Nanotube is as preparing in the preparation process of the Polythiophene composition metal protective system that a kind of pattern affects, and the solid content of polyvinyl butyral acetal ethanolic soln changes 7wt% into.After tested, performance is similar to Example 3.
Embodiment 28
With embodiment 3, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, after changing nitrogen drying into, is placed in the oven drying 0.5h that temperature is 75 DEG C.After tested, performance is similar to Example 3.
Embodiment 29
With embodiment 3, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, changes into protective system to drip to be coated in the clean metallic iron substrate of polishing, is placed in the oven drying 1h of 50 DEG C.After tested, performance is similar to Example 3.
Embodiment 30
With embodiment 3, unique difference is, is applied to by metal anti-corrosive paint in the anticorrosion step to metallic iron, utilizes liquid-transfering gun to inject 1mol/LNaCl electrolytic solution.After tested, performance is similar to Example 3.
Comparative example 1
It is anticorrosion that the metal anti-corrosive paint of the polyvinyl butyral acetal ethanolic soln of preparation only containing 14wt% is applied to metallic iron: utilize that order number is 400 orders, metal iron plate polished successively by 600 orders and 1000 object sand paper, polish complete, deionized water wash, nitrogen drying, is then placed in the oven drying 1h that temperature is 50 DEG C; Protective system is spin-coated in the clean metallic iron substrate of polishing, is placed in the oven drying 0.5h of 60 DEG C; Then the metal iron plate side pocket knife being coated with protective system being manufactured an area is that the cut of 10mm × 1mm is as defect, then itself and another clean, surperficial iron plate without protective system is bonded together, the room of about 0.5cm is reserved in defectiveness side, to store electrolytic solution, utilize copper foil tape that the two is connected conducting; Finally, sample is placed in the test system of scanningKelvinprobe, utilize liquid-transfering gun to inject 1mol/LKCl electrolytic solution, regulation system temperature is 25 DEG C, and humidity is 92r.h.%, and parameters, tests, and the erosion rate of metallic iron is 900 μm/h.
Test result shows containing poly-(3,4-dioxoethyl) thiophene " pyriform " nanometer full particle is better than containing poly-(3,4-dioxoethyl) the composition metal protective system of thiophene/carbon nanotube composite hollow fiber to the anti-corrosion capability of iron, simultaneously far away higher than the resistance to corrosion had containing simple polyvinyl butyral acetal ethanolic soln.
Illustrate that poly-(3,4-dioxoethyl) thiophene is a kind of excellent anti-corrosion of metal corrosion material, and the poly-antiseptic property of (3,4-dioxoethyl) thiophene to metallic iron of different nanostructure is different.Infer because poly-(3,4-dioxoethyl) thiophene " pyriform " nano particle is solid sphere, and gather (3,4-dioxoethyl) thiophene and carbon mano-tube composite be hollow structure, two kinds of structures are compared, and solid construction can provide more effective charge, more effectively polarizing coatings and metal interface, improve corrosion potential, slowing down corrosion.When dissolving metal, metallic perimeter (interface as metal and material) produces a certain amount of electronics, poly-(3 of oxidation state, 4-dioxoethyl) thiophene can obtain electronics in time and be reduced, the reduction of effective reduction oxygen, thus suppress oxyradical and hydroxide ion (very easily attack metal and polymer interface place, destroy polymer chain, the cementability of polymkeric substance and metal reduces, cause coating shedding, exposed metal/bare metal outside, accelerate corrosion of metal) formation, slow down disbonding, reach anticorrosion object.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. a Polythiophene composition metal protective system for pattern impact, is characterized in that, comprise the component of following content:
" pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene or the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and carbon nanotube: 15mg ~ 110mg;
Polyvinyl butyral acetal ethanolic soln: 1 ~ 3mL;
Dehydrated alcohol: 1 ~ 3mL;
Wherein, the polyvinyl butyral acetal admittedly containing 7wt% ~ 14wt% in described polyvinyl butyral acetal ethanolic soln; Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
2. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 1, is characterized in that, the preparation of " pyriform " nano particle of described poly-(3,4-dioxoethyl) thiophene comprises the steps:
1) polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 0.05 ~ 1mmol/L;
2) to step 1) in add monomer (3,4-dioxoethyl) thiophene in gained mixing solutions, ultrasonic 0.5h ~ 2h, obtains finely dispersed mixing solutions;
3) to step 2) in add the ammonium persulfate oxidizing agent aqueous solution in the finely dispersed mixing solutions of gained, wherein, ammonium persulphate and monomer (3,4-dioxoethyl) thiophene mol ratio is 2:1, Keep agitation, polymerized at normal temperature 48h, obtains the black mixed solution of " pyriform " nano particle containing poly-(3,4-dioxoethyl) thiophene;
4) by step 3) centrifugation of gained black mixed solution, obtain black solid throw out, then this throw out is carried out wash, dry, gathered " pyriform " nano particle of (3,4-dioxoethyl) thiophene.
3. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 2, is characterized in that, step 4) in, " pyriform " nano particle diameter of described poly-(3,4-dioxoethyl) thiophene is 200nm ~ 500nm.
4. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 2, it is characterized in that, step 4) in, described washing is first with deionized water wash and centrifugation by described black solid throw out, be that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio again, until supernatant liquor is colourless; Finally use deionized water wash again.
5. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 1, is characterized in that, the preparation of the composite nano fiber of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube comprises the steps:
1. polyvinylpyrrolidone is dissolved in the water that volume ratio is 4:1 and acetonitrile mixture, stirs, obtain water/acetonitrile mixing solutions that concentration is the polyvinylpyrrolidone of 0.05 ~ 1mmol/L;
2. in step 1. gained mixing solutions, add single wall or multi-walled carbon nano-tubes, ultrasonic disperse 1h, obtain the suspension containing carbon nanotube;
3. in step 2. middle gained suspension, add monomer (3,4-dioxoethyl) thiophene, ultrasonic 0.5h ~ 2h, obtains finely dispersed mixing solutions;
4. in step 3. described mixing solutions, the ammonium persulfate oxidizing agent aqueous solution is added, wherein, ammonium persulphate and monomer (3,4-dioxoethyl) thiophene mol ratio is 2:1, Keep agitation, normal temperature emulsion polymerisation reaction 48h, obtains the black mixed solution containing the composite nano fiber gathering (3,4-dioxoethyl) thiophene and carbon nanotube;
5. by step 4. gained black mixed solution centrifugation, obtain black solid throw out, then this throw out is carried out wash, dry, gathered the composite nano fiber of (3,4-dioxoethyl) thiophene and carbon nanotube.
6. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 5, in it is characterized in that step is 5., the composite nano fiber diameter of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 10nm ~ 50nm; The composite nano fiber long degree of described poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 1 ~ 10 μm.
7. the Polythiophene composition metal protective system of a kind of pattern impact according to claim 5, it is characterized in that, step 5. in, described washing is first with deionized water wash and centrifugation by described black solid throw out, be that the water of 1:1 and the mixed solvent of ethanol wash by volume ratio again, until supernatant liquor is colourless; Finally use deionized water wash again.
8. the preparation method of the Polythiophene composition metal protective system of the pattern impact according to claim arbitrary in claim 1-7, is characterized in that, comprise the steps:
To (3 be gathered, 4-dioxoethyl) " pyriform " nano particle or poly-(3 of thiophene, 4-dioxoethyl) composite nano fiber of thiophene and carbon nanotube, polyvinyl butyral acetal ethanolic soln and dehydrated alcohol mix, and prepares the Polythiophene composition metal protective system of a kind of pattern impact;
Wherein, each component concentration is:
The quality of " pyriform " nano particle of poly-(3,4-dioxoethyl) thiophene or the composite nano fiber of poly-(3,4-dioxoethyl) thiophene and carbon nanotube is 15mg ~ 110mg;
Polyvinyl butyral acetal volumes of aqueous ethanol is 1 ~ 3mL;
Dehydrated alcohol volume is 1 ~ 3mL;
Polyvinyl butyral acetal admittedly containing 7wt% ~ 14wt% in described polyvinyl butyral acetal ethanolic soln;
Described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
9. the application of Polythiophene composition metal protective system in metallic iron is anticorrosion of a kind of pattern impact as claimed in claim 8.
10. application according to claim 9, is characterized in that: the testing method of described application comprises the steps: the anti-corrosion paint for preparing in the clean metal iron plate substrate of polishing, is placed in the oven drying 1 ~ 2h of 50 ~ 75 DEG C; Again this metal iron plate side pocket knife is manufactured an area be the cut of 10mm × 1mm as defect, itself and another clean, surface is bonded together without the iron plate of protective system, reserves the room of 0.5cm in defectiveness side, be used for storage electrolytic solution; With copper foil tape, above-mentioned two metal iron plates are connected conducting, make sample; Finally, sample is placed in the test system of scanningKelvinprobe, tests; Preferably, be applied to spin coating described in or drip and be coated with; Described electrolytic solution is sodium chloride aqueous solution or potassium chloride solution; In order to utilize, order number is 400 orders in described polishing, metal iron plate polished successively by 600 orders and 1000 object sand paper, with deionized water wash after polishing, and nitrogen drying, then the oven drying 0.5h ~ 1h being placed in that temperature is 50 DEG C ~ 75 DEG C.
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