CN107434805A - A kind of graphene-supported thiadiazoles corrosion inhibitor of active group containing furtural and its application - Google Patents

A kind of graphene-supported thiadiazoles corrosion inhibitor of active group containing furtural and its application Download PDF

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CN107434805A
CN107434805A CN201611151668.1A CN201611151668A CN107434805A CN 107434805 A CN107434805 A CN 107434805A CN 201611151668 A CN201611151668 A CN 201611151668A CN 107434805 A CN107434805 A CN 107434805A
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graphene
furtural
thiadiazoles
compound
supported
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田惠文
李伟华
侯磊
侯保荣
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Institute of Oceanology of CAS
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Institute of Oceanology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom

Abstract

The present invention relates to corrosion inhibitor, the graphene-supported thiadiazoles corrosion inhibitor of specifically a kind of active group containing furtural and its application.Compound is that furtural [sulfydryl of 5 (p-methylphenyl) 1,3,4 thiadiazoles 2] acetyl hydrazone carries out chemical load, the compound of formation in graphene molecules layer oxygen-containing functional group avtive spot.Compound is applied in concrete alkaline environment or under corresponding alkalescence condition, the Cathodic oxygen reduction of load corrosion inhibitor and carbon steel effect electrochemical process is catalyzed by graphene molecules layer, corrosion protection is carried out to the carbon steel material in seawater or sodium chloride medium and its reinforcing bar product, using the corrosion inhibitor of the present invention, wide material sources, it is easy to volume production, dosage is few, performance efficiency, and continuous action ability is strong, the corrosion failure of carbon steel can effectively be suppressed, there are significant application value and wide market prospects.

Description

A kind of graphene-supported thiadiazoles corrosion inhibitor of the active group containing furtural and its Using
Technical field
The present invention relates to corrosion inhibitor, the graphene-supported thiadiazoles resistance of specifically a kind of active group containing furtural Rust agent and its application.
Background technology
Armored concrete is the material of main part of coastal and offshore engineering construction, under marine corrosion environment, by high concentration cl from The steel bar corrosion that son infiltration triggers, it is the primary factor for causing concrete structure to deteriorate.The method for completely cutting off Chloride Attack is a lot, Reinforcing steel bar corrosion inhibitor is most simple and direct, economic and efficient aseptic technic.
The focusing focus of reinforcing steel bar corrosion inhibitor research at present and application field is organic migration-type corrosion inhibitor (MCI), and it both may be used It is used for new construction as concrete additive, existing structure can be coated on again, is carried out by strongly moving to up to rebar surface Deep layer is protected, however, making a general survey of academic report and market product as emerging rapidly in large numbersBamboo shoots after a spring rain, still slowly having no can be with doped nitrite The scientific and technological achievement that the protective efficacy of reinforcing bar passivator compares favourably comes out.Efficient anticorrosion performance with regard to this become can not with it is environment-friendly The technology short slab that property and strength migration get both, seriously constrains development and application prospects of the MCI in Maritime Corrosion Control field, There is an urgent need to its research and development realize from based on environment-friendly to green and the transformation efficiently gone forward side by side.
Steel bar corrosion destroys and two kinds of negative electrode coupled reactions of corrosion inhibitor and reinforcing bar effect generation diaphragm are all 4 electricity of oxygen Sub- reduction process, different from traditional nitrous acid, benzoate Anodic Type corrosion inhibitor, MCI is to suppress reinforcing bar anode activity simultaneously Corrosion dissolution and the mixed type corrosion inhibitor of two kinds of negative electrodes coupling hydrogen reduction, and the reaction speed of cathodic oxygen reduction is just and reinforcing bar The speed of surface corrosion inhibitor effect generation diaphragm is proportional, therefore improves the key of MCI resistance rust efficiency, in that improves The reaction speed of corrosion inhibitor and cathodic oxygen reduction in the electrochemical process of reinforcing bar effect.
Graphene exists extensively and is easy to produce, and is to have highly conductive, high surface, the two dimensional surface of high rim defect characteristics Monolayer, it is excellent cathodic oxygen reduction electrochemical catalyst.Aza graphene prepared by low temperature process and silicon substrate method, price It is cheap, be easy to volume production, the catalytic activity of microorganism fuel cell cathode hydrogen reduction is urged in traditional Pt/C costly shoulder to shoulder Agent；In alkali electrochemical catalytic sensor, graphene can make the dynamics electric current of Cathodic oxygen reduction improve 7 times and protect Hold long-acting durability；C-N, C-O covalent bond, the growth cores as hybrid or organic matter are implanted on graphene honeycomb framework The heart, the active catalyst sites in netted lattice can be activated, make the catalytic efficiency of Cathodic oxygen reduction with geometric growth. Chitosan-coated graphene shows the high-efficiency catalytic activity of similar enzyme to the electronic reduction reaction of negative electrode oxygen 4 of glucose.
Therefore, using graphene molecules layer as substrate, the corrosion inhibitor molecule containing active group is object, prepares chemical load Self-catalysis corrosion inhibitor, by being catalyzed the Cathodic oxygen reduction of corrosion inhibitor molecule and carbon steel surface action, MCI is improved to carbon steel Antiseptic property, possess sufficient theoretical foundation and technical feasibility.
The content of the invention
Present invention aims at the graphene-supported thiadiazoles corrosion inhibitor for providing a kind of active group containing furtural and its Using.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of graphene-supported thiadiazoles compound of active group containing furtural, compound are furtural-[5- (p-methylphenyl) -1,3,4 thiadiazoles -2- sulfydryls]-acetyl hydrazone is in graphene molecules layer oxygen-containing functional group avtive spot Learn load, the compound of formation.
The furtural-[5- (p-methylphenyl) -1,3,4 thiadiazoles -2- sulfydryls]-acetyl hydrazone, its structural formula are：
Its preparation reaction equation is：
1) p-methylbenzoic acid is mixed with methanol equimolar, reaction dehydration obtains methyl p-methyl benzoate (I)；
2) product (I) is mixed with excess hydrazine hydrate, 1-3h is reacted in 60-90 DEG C of oil bath, obtains to toluyl hydrazine (II)；
3) product (II) and excessive carbon disulfide are reacted into generation compound (III) under alkaline environment；
4) product (III) 60-90 DEG C of cyclization 1-2h of oil bath temperature, obtains 2- sulfydryl -5- benzene under sulphuric acid catalysis Methyl-[1,3,4] thiadiazoles (IV), then (IV) obtains (V) with excess chlorine for acetic acid ethyl reaction in the basic conditions；
5) product (V) and excess hydrazine hydrate are reacted to obtain (VI), product (VI) reacts with excessive furtural to be produced Thing furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl hydrazone (VII).
A kind of preparation of the graphene-supported thiadiazoles compound of the active group containing furtural：By furtural-[5- (p-methylphenyl) -1,3,4 thiadiazoles -2- sulfydryls]-acetyl hydrazone and graphene by way of oxidation-grafting-reduction, obtain The graphene-supported thiadiazoles compound of the active group containing furtural.
Specially：
1) to the dense H that graphite flake mass fraction is 35%2SO4It is 1 to be added in mixed system with graphite flake mass ratio:1.1 KMnO4, through SO4 2-Intercalation is peeled off and MnO4 -Oxidative activation, the monolayer graphene oxide water slurry of acquisition；
2) will be with graphite flake mass ratio 1:4 furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4] - Acetyl hydrazone adds the graphene oxide water slurry of above-mentioned acquisition, is grafted through protonation, adds excessive glucose reduction, obtains The graphene-supported thiadiazoles compound of the active group containing furtural.
A kind of application of the graphene-supported thiadiazoles compound of the active group containing furtural, it is described to be lived containing furtural The compound of the graphene-supported thiadiazoles of property group can be protected seawater corrosion medium as corrosion inhibitor.
The seawater corrosion inhibitor can be applied under concrete alkaline environment or corresponding alkalescence condition.
The concrete alkaline environment or corresponding alkalescence condition refer to that pH value is 9.5-13.5 in seawater or sodium chloride medium.
It is 9.5-13.5 that the graphene-supported thiadiazoles compound for referring to the active group containing furtural, which acts on pH value, Seawater or sodium chloride medium in application in corrosion protection is carried out to concrete mild steel material and its reinforcing bar product.
In concrete environment or under corresponding alkalescence condition, the steel (carbon steel) suppressed in seawater or sodium chloride solution are rotten Erosion, the graphene-supported thiadiazoles of specifically a kind of active group containing furtural is as seawater corrosion inhibitor in concrete alkali Application under property environment or corresponding alkalescence condition.
Before, corrosion inhibitor compound is dissolved in cyclohexanone, the weight ratio of itself and cyclohexanone is 1:20, then in room temperature It is lower that ultrasonic disperse is carried out 20 minutes to mixed solution with ultrasonic disperser, it is allowed to be completely dissolved；Then, it is molten by what is fully dissolved Liquid is added in OP-10 emulsifying agents, and the addition of OP-10 emulsifying agents and the weight ratio of cyclohexanone are 1:1, stir at room temperature Obtain the microemulsion of corrosion inhibitor, you can use.
The corrosion inhibitor is applied in concrete alkaline environment or under corresponding alkalescence condition, in seawater or sodium chloride medium Carbon steel material and its reinforcing bar product carry out corrosion protection.
The pH scopes of the concrete alkaline environment or corresponding alkalescence condition are 9.5-13.5, and the seawater or sodium chloride are situated between Matter is the sodium chloride solution that mass fraction is 3.5%.
Carbon steel material and its reinforcing bar product are immersed in and added in the alkaline seawater solution of corrosion inhibitor, bath temperature 15- 55 DEG C, the amount wherein containing corrosion inhibitor compound in microemulsion is 0.2-1.5mg/L, preferably 0.5mg/L.
The beneficial effects of the invention are as follows：
Gained corrosion inhibitor of the invention is from improving corrosion inhibitor with negative electrode oxygen in carbon steel effect generation diaphragm electrochemical process also The theoretical critical of former reaction speed is started with, and uses graphene molecules layer as catalytic substrate material, and the resistance containing active group is become rusty Agent molecule carries out chemical load, and it is an object of the present invention to provide a kind of dosage is trickle, and performance protrudes, and the active ingredient of stability and durability is containing furan Mutter the graphene-supported thiadiazoles compound reinforcing steel bar corrosion inhibitor of formaldehyde activity group, to suppress under alkalescence condition carbon in concrete The corrosion of steel and its bar material product in seawater or sodium chloride medium；Specifically：
1. cost is low.The active ingredient of corrosion inhibitor of the present invention is furtural-[thiophenes two of 5- (p-methylphenyl) -1,3,4 Azoles -2- sulfydryls]-acetyl hydrazone and graphene complex, the compound synthesis material be widespread in nature, and in industry Upper a large amount of productions, preparation method is simple, and yield is high, and tret is trickle, therefore integrated application cost is cheap.
2. environment Small side effects.Corrosion inhibitor of the present invention and the inorganic corrosion inhibitor and amine for occupying dominant contribution in the market Corrosion inhibitor is compared, have be exposed to strong light under or the degradable advantage for innocuous substance in soil and organism, ring will not be given Load is brought in border, meets the trend of green corrosion inhibitor development.
3. strong applicability.Corrosion inhibitor of the present invention it is applied widely, in higher salinity, higher temperature and wider alkali Excellent anticorrosion performance is respectively provided with the range of property pH.
4. high efficiency.Present invention addition is extremely trickle, is the 1% of the similar corrosion inhibitor conventional amount used of main flow in the market, It is sufficient to effectively suppress carbon steel material or its destruction of corresponding reinforcing bar product in corrosive medium.
5. good endurance.Corrosion inhibiter of the present invention has long-acting duration of action, can be protected for a long time in alkaline environment Hold higher resistance rust efficiency.
Brief description of the drawings
Fig. 1 be furtural provided in an embodiment of the present invention-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4] - The synthetic route of acetyl hydrazone.
Fig. 2 is the synthetic route of corrosion inhibitor compound provided in an embodiment of the present invention.
Embodiment
For the present invention using graphene molecules layer as self-catalysis substrate, the thiadiazoles of the active group containing furtural is chemical load The seawater corrosion inhibitor of object, the application under concrete alkaline environment or corresponding alkalescence condition.Corrosion inhibitor is applied to concrete alkali Property environment in or corresponding alkalescence condition under, pass through graphene molecules layer catalysis load corrosion inhibitor and act on electrochemical process with carbon steel Cathodic oxygen reduction, corrosion protection is carried out to the carbon steel material in seawater or sodium chloride medium and its reinforcing bar product, using this The corrosion inhibitor of invention, wide material sources, it is easy to volume production, dosage is few, and performance efficiency, continuous action ability is strong, can effectively suppress The corrosion failure of carbon steel, there are significant application value and wide market prospects.
The present invention is according to GB10124-88《Uniform Corrosion Method of Laboratory Immersion Test method》Carry out zero-G test, And carry out anticorrosion performance sign using two kinds of electrochemical methods of electrochemical alternate impedance spectrum and potentiodynamic polarization.Although three kinds of methods Obtained resistance rust efficiency has different, and what it is mainly due to weight-loss method test is average corrosion rate, and electrochemical method is tested Be corrosion efficiency in transient process, but the general morphologictrend of various methods is consistent, it can be seen that in different salinity, resistance rust The compound is respectively provided with excellent anticorrosion performance under agent concentration, temperature, pH value condition.Used experimental test procedures come from text Offer：【1】W.Li,L.Hu,S.Zhang,B.Hou,Effects of two fungicides on the corrosion Resistance of copper in 3.5%NaCl solution under various conditions [J], Corros.Sci.2011,53:735-745【2】H.Tian,W.Li,B.Hou.Novel application of a hormone biosynthetic inhibitor for the corrosion resistance enhancement of copper in synthetic seawater[J].Corros.Sci.2011,53:3435–3445。
Embodiment 1
The preparation of the graphene-supported thiadiazoles compound of the active group containing furtural.
The first step：Referring to Fig. 1, furtural-[5- (p-methylphenyl) -1,3,4 thiadiazoles -2- sulfydryls]-acetyl is synthesized Hydrazone, or obtained referring to the mode described in prior art；Specially：
First, p-methylbenzoic acid is mixed with methanol equimolar, reaction dehydration obtains methyl p-methyl benzoate (I). Product (I) is mixed with excess hydrazine hydrate, 2h is reacted in 80 DEG C of oil baths, obtains to toluyl hydrazine (II).
Then, product (II) and excessive carbon disulfide are reacted into generation compound (III) under KOH alkaline environments.Will production Thing (III) 80 DEG C of cyclization 1.5h of oil bath temperature, obtains 2- sulfydryl -5- benzyls-[1,3,4] thiophene under sulphuric acid catalysis Diazole (IV).Product (IV) obtains (V) with excess chlorine for acetic acid ethyl reaction under KOH alkalescence conditions.
Finally, product (V) and excess hydrazine hydrate are reacted to obtain (VI), product (VI) reacts with excessive furtural To furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl hydrazone (VII).
Second step：Referring to Fig. 2, the graphene-supported thiadiazoles compound of the active group containing furtural is synthesized.
First, to the dense H that graphite flake mass fraction is 35%2SO4It is 1 to be added in mixed system with graphite flake mass ratio: 1.1 KMnO4, through SO4 2-Intercalation is peeled off and MnO4 -Oxidative activation, the monolayer graphene oxide water slurry (A) of acquisition.
Then, will be with graphite flake mass ratio 1:The 4 furtural-[thiadiazoles -2- mercaptos of 5- (p-methylphenyl) -1,3,4 Base]-acetyl hydrazone adds the graphene oxide water slurry of above-mentioned acquisition, and it is grafted through protonation, adds excessive glucose reduction, Obtain the graphene-supported thiadiazoles compound (B) of the active group containing furtural.
Embodiment 2
Corrosion inhibitor compound is obtained to above-described embodiment and is measured its resistance rust efficiency, is specially：
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 20mg, and temperature is 35 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 90.8% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 92.8%, electrokinetic potential pole Change curve 93.5%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 3
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 35 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 93.7% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 95.6%, electrokinetic potential pole Change curve 96.5%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 3
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 100mg, and temperature is 35 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 92.4% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 93.7%, electrokinetic potential pole Change curve 94.5%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 4
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 150mg, and temperature is 35 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 92.9% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 95.3%, electrokinetic potential pole Change curve 96.8%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 5
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), corrosion inhibitor composition is imitated For the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, The effective content for adding corrosion inhibitor compound is 50mg, and temperature is 15 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 93.6% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 95.7%, electrokinetic potential pole Change curve 96.5%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 6
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), corrosion inhibitor composition is imitated For the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, The effective content for adding corrosion inhibitor compound is 50mg, and temperature is 25 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 94.7% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 96.6%, electrokinetic potential pole Change curve 97.2%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 7
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), corrosion inhibitor composition is imitated For the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, The effective content for adding corrosion inhibitor compound is 50mg, and temperature is 45 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 92.5% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 93.6%, electrokinetic potential pole Change curve 94.5%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 8
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 55 DEG C, pH=11.5, and Immersion time is 60 days.
It is respectively weightlessness 92.1% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 93.5%, electrokinetic potential pole Change curve 94.4%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 9
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 35 DEG C, pH=9.5, and Immersion time is 60 days.
It is respectively weightlessness 92.2% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 94.6%, electrokinetic potential pole Change curve 95.3%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 10
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 35 DEG C, pH=10.5, and Immersion time is 60 days.
It is respectively weightlessness 93.5% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 95.1%, electrokinetic potential pole Change curve 96.8%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 11
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 35 DEG C, pH=12.5, and Immersion time is 60 days.
It is respectively weightlessness 94.5% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 96.2%, electrokinetic potential pole Change curve 97.4%, show compound for dosage is low, corrosion inhibitor of efficiency high.
Embodiment 12
Condition：Experiment material is carbon steel (Fe：99.5%, Mn：0.4-0.5%, C：0.1-0.2%), effective corrosion inhibitor into It is divided into the graphene-supported thiadiazoles compound of the active group containing furtural, medium is 3.5% sodium chloride solution, dosage 100L, the effective content for adding corrosion inhibitor compound are 50mg, and temperature is 35 DEG C, pH=13.5, and Immersion time is 60 days.
It is respectively weightlessness 93.2% to obtain resistance rust efficiency by experiment test, electrochemical impedance spectroscopy 95.3%, electrokinetic potential pole Change curve 95.7%, show compound for dosage is low, corrosion inhibitor of efficiency high.

Claims (9)

  1. A kind of 1. graphene-supported thiadiazoles compound of active group containing furtural, it is characterised in that：Compound is furans Formaldehyde-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl hydrazone is in graphene molecules layer oxygen-containing functional group active sites Point carries out chemical load, the compound of formation.
  2. 2. the graphene-supported thiadiazoles compound of the active group containing furtural as described in claim 1, it is characterised in that： Furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl hydrazone and graphene are passed through into oxidation-grafting-also Former mode, obtain the graphene-supported thiadiazoles compound of the active group containing furtural.
  3. 3. the graphene-supported thiadiazoles compound of the active group containing furtural as described in claim 1, it is characterised in that： The graphene molecules layer of the oxygen-containing functional group avtive spot is to graphite flake and dense H2SO4KMnO is added in mixed system4, warp SO4 2-Intercalation is peeled off and MnO4 -Oxidative activation, the monolayer graphene oxide water slurry of acquisition.
  4. 4. a kind of graphene-supported thiadiazoles compound of the active group containing furtural described in claim 1, its feature exist In：By furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl hydrazone and monolayer graphene oxide By way of protonating grafting and glucose reduction, the graphene-supported thiadiazoles for obtaining the active group containing furtural is compound Thing.
  5. 5. the preparation method of the graphene-supported thiadiazoles compound of the active group containing furtural as described in claim 1, It is characterized in that：
    1) to the dense H that graphite flake mass fraction is 35%2SO4It is 1 to be added in mixed system with graphite flake mass ratio:1.1 KMnO4, through SO4 2-Intercalation is peeled off and MnO4 -Oxidative activation, the monolayer graphene oxide water slurry of acquisition；
    2) will be with graphite flake mass ratio 1:4 furtural-[thiadiazoles -2- sulfydryls of 5- (p-methylphenyl) -1,3,4]-acetyl Hydrazone adds the graphene oxide water slurry of above-mentioned acquisition, is grafted through protonation, adds excessive glucose reduction, and acquisition contains furan Mutter the graphene-supported thiadiazoles compound of formaldehyde activity group.
  6. 6. a kind of application of the graphene-supported thiadiazoles compound of the active group containing furtural described in claim 1, its It is characterised by：The compound of the graphene-supported thiadiazoles of the active group containing furtural can be used as corrosion inhibitor rotten to seawater Erosion medium is protected.
  7. 7. the application of the compound of the graphene-supported thiadiazoles of the active group containing furtural as described in claim 6, its It is characterised by：The seawater corrosion inhibitor can be applied under concrete alkaline environment or corresponding alkalescence condition.
  8. 8. the application of the compound of the graphene-supported thiadiazoles of the active group containing furtural as described in claim 7, its It is characterised by：The concrete alkaline environment or corresponding alkalescence condition refer to that pH value is 9.5- in seawater or sodium chloride medium 13.5。
  9. 9. the application of the compound of the graphene-supported thiadiazoles of the active group containing furtural as described in claim 8, its It is characterised by：It is 9.5-13.5 that the graphene-supported thiadiazoles compound for referring to the active group containing furtural, which acts on pH value, Seawater or sodium chloride medium in application in corrosion protection is carried out to concrete mild steel material and its reinforcing bar product.
CN201611151668.1A 2016-12-14 2016-12-14 A kind of graphene-supported thiadiazoles corrosion inhibitor of active group containing furtural and its application Pending CN107434805A (en)

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