CN108017305A - A kind of thiadiazoles corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification and its application - Google Patents
A kind of thiadiazoles corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification and its application Download PDFInfo
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- CN108017305A CN108017305A CN201711223230.4A CN201711223230A CN108017305A CN 108017305 A CN108017305 A CN 108017305A CN 201711223230 A CN201711223230 A CN 201711223230A CN 108017305 A CN108017305 A CN 108017305A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- C04B2103/61—Corrosion inhibitors
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Abstract
The present invention relates to corrosion inhibitor, the specifically a kind of thiadiazoles corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification and its application.Assembled by chlorion probe modification and intercalation, in the chlorion trigger switch of the controllable thiadiazole of active group containing the cinnamic acid corrosion inhibitor release of zinc-aluminum hydrotalcite intercalation, the compound of formation.Corrosion inhibitor compound using the present invention, can volume production, can accomplish to corrosive environment respond release and repair corrosion carbon steel, and there is long-term protective action, can effectively to carbon steel progress corrosion protection, have significant application value and vast market prospect.
Description
Technical field
The present invention relates to corrosion inhibitor, and specifically a kind of hydrotalcite intercalation chlorion probe modification is active containing cinnamic acid
Group thiadiazoles corrosion inhibitor compound 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 diffusion and infiltration trigger, is the very crux for causing concrete material deterioration and Deterioration of Structural Performance.Using
Organic migration-type corrosion inhibitor (Migrating Corrosion Inhibitor, MCI) is as a kind of simple and direct, economic, efficient steel
Muscle anti-corrosion material, is the prefered method for completely cutting off Chloride Attack.
Traditional corrosion inhibitor research and development thinking sticks to the isolating and protecting to rebar surface, and is not yet conceived to corruption
The improvement of medium and adaptation to concrete body environment are lost, has seriously undermined the application stability of corrosion inhibitor and long-acting lasting
Property, make the performance stream of high efficiency in empty talk.Function, green, structure effect, are three bases of the development of MCI basic research at this stage
Essentiality, and realize the integrated and collaboration of reinforcing bar protection, chlorion improvement and environment adaptive functions, become " passive protection " to be " main
It is dynamic to launch an attack ", the breach that will be crossed over as next step MCI from feature to intelligence.
Hydrotalcite-based compound (Layered Double Hydroxide, LDH) is by the assembling of functional molecular by linear
Docking introduces the three-dimensional to link work at selected spots with that in entire areas, is the flagship material of new generation in Supramolecular Receptors series.LDH is light environmentally friendly, honest and clean
Valency is easy to get, and collects the stability of layer structure, controllability, the adjustability of laminate spacing, the interlayer anion of laminate composition are handed over
It is transsexual to possess the natural attribute as cell reservoirs and ion exchange platform in one, can carry out diversification structure of modification and
Functions expanding, is widely used in stabilizing active intermediate, ion trapping, drug delivery and corrosion protection research.
The content of the invention
Present invention aims at provide a kind of thiophene of active group containing cinnamic acid two of hydrotalcite intercalation chlorion probe modification
Azoles corrosion inhibitor compound and its application.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of thiadiazole corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification, leads to
Chlorion probe modification and intercalation assembling are crossed, in the controllable thiadiazole of active group containing cinnamic acid of zinc-aluminum hydrotalcite intercalation
The chlorion trigger switch of corrosion inhibitor release, the compound of formation.
Further：The thiadiazole of active group containing cinnamic acid of chlorion probe modification is prepared by protonation techniques
Corrosion inhibitor [cinnamic acid [5- (p-methylphenyl) -1,3,4- thiadiazoles -2- sulfydryls]-acetyl hydrazone] corrosion inhibitor intercalation precursor, then
It is embedded into zinc-aluminum hydrotalcite interlayer；Wherein, the dosage molar ratio between precursor and zinc-aluminum hydrotalcite is 6-8:1.
The precursor is that 4-(Metylamino)-benzoic acid is pressed [N+- H ... O] hydrogen bond formed mole metering than add contain cinnamic acid
(1-3 × 10 in active group thiadiazoles corrosion inhibitor aqueous solution-3Mol/L), protonation titration is carried out using the HBr of 2.2 equivalents, made
The corrosion inhibitor intercalation precursor of standby chlorion probe modification.
A kind of preparation method of zinc-aluminum hydrotalcite intercalation chlorion probe modification corrosion inhibitor compound：Carried out by following reactions
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.165Na2CO3=[Zn0.67Al0.33(OH)2][(CO3)0.165·
mH2O]+0.33NaOH (3)
First, at room temperature by zinc nitrate and aluminum nitrate (mole ratio 2:1) mixing, obtains mixed solution A, will mix molten
Liquid A is slowly dropped in sodium carbonate liquor B that (sodium carbonate and zinc nitrate molar equivalent are than 1:1), and using NaOH its pH is maintained to exist
10 ± 0.5, then suspension is crystallized in 65-70 DEG C of heating water bath 24-32h, obtains zinc-aluminum hydrotalcite；
Wherein, mixed solution A is slowly dropped in sodium carbonate liquor B, time for adding 1.5h, during which strong agitating solution
B；Crystallized product is cleaned for several times by centrifuging with distilled water, and vacuum drying is simultaneously ground, stand-by.
The corrosion inhibitor intercalation precursor of chlorion probe modification is added in the zinc-aluminum hydrotalcite solution of preparation, is shelled by ultrasound
From, condensing reflux, back-mixing precipitation is carried out, obtains the zinc-aluminum hydrotalcite compound of the corrosion inhibitor of intercalation chlorion probe modification.
The precursor is that 4-(Metylamino)-benzoic acid is pressed [N+- H ... O] hydrogen bond formed mole metering than add contain cinnamic acid
(1-3 × 10 in active group thiadiazoles corrosion inhibitor aqueous solution-3Mol/L), protonation titration is carried out using the HBr of 2.2 equivalents, made
The corrosion inhibitor intercalation presoma of standby chlorion probe modification.
A kind of thiadiazole corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification
Using the corrosion inhibitor compound answering in concrete mild steel material and its reinforcing bar product are carried out corrosion protection, repaired
With.
The seawater corrosion inhibitor compound is under concrete alkaline environment or corresponding alkaline condition to concrete medium carbon steel
Material and its reinforcing bar product carry out the application in corrosion protection, reparation.
The concrete alkaline environment or corresponding alkaline condition refer to that pH value is 9.5-13.5 in seawater or sodium chloride medium.
Further, carbon steel material and its reinforcing bar product are immersed in the alkaline seawater solution for adding corrosion inhibitor compound
It is preferably 0.1g/L or in medium, bath temperature is 15-45 DEG C, and the wherein amount of corrosion inhibitor compound is 0.05-0.2g/L.
Chlorion probe in corrosion inhibitor compound of the present invention is 4-(Metylamino)-benzoic acid, first protonates it using HBr,
Then chelated with corrosion inhibitor [cinnamic acid [5- (p-methylphenyl) -1,3,4- thiadiazoles -2- sulfydryls]-acetyl hydrazone], when there is chlorine
During ion, 4-(Metylamino)-benzoic acid preferentially with chlorion reaction bonded, and by corrosion inhibitor dissociate discharge；Cause corrosion when having
Chlorion when corrosion inhibitor can just be released and come into force, corrosion inhibitor can be loaded and is protected in when no chlorion does not corrode
It to avoid degraded between neatly stone veneer.
The beneficial effects of the invention are as follows：
Gained corrosion inhibitor compound of the invention is multi-functional in integral new corrosion inhibitor from function, green, structure effect is obtained
Start with, use hydrotalcite (double-layered hydroxides) as carrier, the thiadiazole corrosion inhibitor molecule of chlorion probe modification is carried out
Intercalation loads, it is therefore intended that the multi-functional hydrotalcite for carrying out Targeting delivery by chlorion identification and ion exchange and repairing is inserted
The reinforcing steel bar corrosion inhibitor of layer thiadiazoles compound, to suppress under alkaline condition concrete medium carbon steel and its bar material product in sea
Corrosion in water or sodium chloride medium；Specifically：
1. cost is low.The active ingredient of corrosion inhibitor compound of the present invention is hydrotalcite and thiadiazoles compound, the compound
Synthesis material derives from a wealth of sources, is of low cost, and industrially a large amount of productions, and preparation method is simple, and yield is high, can carry out large quantities of
Amount production, therefore integrated application cost is cheap.
2. environment Small side effects.Between corrosion inhibitor is supported on hydrotalcite bilayer by the present invention, there is preferable Environmental compatibility,
On the one hand the loss and failure of corrosion inhibitor can be reduced, on the other hand, corrosion inhibitor active ingredient is exposed under strong light or in soil
With it is degradable in organism be innocuous substance, load will not be brought to environment, meet the trend of green corrosion inhibitor development.
3. strong applicability.Corrosion inhibitor compound of the present invention it is applied widely, higher salinity, higher temperature and compared with
Excellent anticorrosion performance is respectively provided with wide alkaline pH range.
4. high efficiency.This corrosion inhibitor compound yield is high, and dosage is few, can large area be added in concrete, and can have
Effect suppresses carbon steel material or its destruction of corresponding reinforcing bar product in corrosive medium.
5. Targeting delivery and self-repairability.Corrosion inhibitor compound of the present invention is applied in corrosive medium, can be to aggressivity
Ion chlorion carries out targets identification release, while carries out Corrosion Repair to Corrosion Reinforcement, prevents reinforcing bar from further corroding.
6. durability is good.Between corrosion inhibitor is supported on hydrotalcite bilayer by the present invention, have to erosion carbon dioxide (chlorine in environment
Ion) response release ability, erosion carbon dioxide in medium (chlorion) can also be captured while discharging corrosion inhibitor, when can be long
Between keep higher resistance to become rusty efficiency in alkaline environment.
Brief description of the drawings
Fig. 1 is the synthetic route of corrosion inhibitor compound provided in an embodiment of the present invention.
Embodiment
The present invention is further explained with reference to the accompanying drawings and examples.
Protective effect of the present invention based on LDH confinement spaces to object activity, laminate electric charge inhale the specificity of anion
Attached effect, Inter layer exchange respond the release behavior to guest molecule, are assembled by building MCI in the supermolecular intercalation of LDH interlayers
System (MCI/LDH), strengthens adaptability of the MCI to concrete body environment, while forms layer of the MCI releases to chlorion absorption
Between exchange response mechanism, environment adaptation is carried out with this, chlorion is administered, the integration of reinforcing bar safeguard function.
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 characterization 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 (weightless test, electrochemical impedance spectroscopy measuring resistance rust efficiency)【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.(dynamic potential polarization curve measuring resistance rust efficiency)
Embodiment
The preparation of the thiadiazoles corrosion inhibitor compound of hydrotalcite intercalation chlorion probe modification
The first step：Prepare the thiadiazoles precursor of chlorion probe modification.
4-(Metylamino)-benzoic acid is pressed into [N+- H ... O] hydrogen bond formed mole metering than add a cinnamic acid [5- is (to methylbenzene
Base) -1,3,4- thiadiazoles -2- sulfydryls] (2.4 × 10 in the polynary ether corrosion inhibitor aqueous solution of-acetyl hydrazone-3Mol/L), work as using 2.2
The HBr of amount carries out protonation titration, prepares the thiadiazole corrosion inhibitor intercalation of active group containing cinnamic acid of chlorion probe modification
Presoma.
Second step：Synthesis zinc-aluminum hydrotalcite reaction equation is that reaction is as follows：
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.165Na2CO3=[Zn0.67Al0.33(OH)2][(CO3)0.165·
mH2O]+0.33NaOH (3)
First, by 14.85g Zn (NO3)2·6H2O and 9.38g Al (NO3)3·9H2O is dissolved into 100mL distilled water,
Obtain mixing salt solution A；Again by 15.9g Na2CO3It is dissolved into 200mL distilled water, obtains solution B；It is afterwards that 8g NaOH is molten
Solution obtains aqueous slkali C into 100mL distilled water.
Then, solution A is slowly dropped in B solution, while aqueous slkali C is added dropwise, maintain B solution pH=10 ± 0.5, phase
Between strong agitating solution B.
Then, the suspension obtained after the completion of titration is put into 65 DEG C of water bath processing 24h, crystallized.
Finally, by product by centrifuging (4500rpm, 10min), and cleaned four times with distilled water, 70 DEG C of vacuum are dried
Dry (24h) is simultaneously ground, and obtains zinc-aluminum hydrotalcite.
3rd step：Synthesize the thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification.
The corrosion inhibitor intercalation of previously prepared chlorion probe modification is added in the zinc-aluminum hydrotalcite solution of above-mentioned preparation
Precursor, the condensing reflux after ultrasound peels off 50min, carries out back-mixing precipitation about 30min, product centrifugation recycling, cleaning, drying is simultaneously
Grinding, obtains the zinc-aluminum hydrotalcite compound (table 1) of the corrosion inhibitor of intercalation chlorion probe modification.
Table 1
| Corrosion inhibitor aqueous solution | Precursor：Hydrotalcite | |
| Embodiment 1 | 1mol/L | 6:1 |
| Embodiment 2 | 1.5mol/L | 6.5:1 |
| Embodiment 3 | 2mol/L | 7:1 |
| Embodiment 4 | 2.5mol/L | 7.5:1 |
| Embodiment 5 | 3mol/L | 8:1 |
Application examples 1
Corrosion inhibitor compound is obtained to above-described embodiment 1 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.05g, and temperature is 25 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 91.4%, electrification
Impedance spectrum 91.7% is learned, dynamic potential polarization curve 92.6%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 2
Corrosion inhibitor compound is obtained to above-described embodiment 2 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 25 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 94.1%, electrification
Impedance spectrum 95.2% is learned, dynamic potential polarization curve 96.0%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 3
Corrosion inhibitor compound is obtained to above-described embodiment 3 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.15g, and temperature is 25 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 94.3%, electrification
Impedance spectrum 95.1% is learned, dynamic potential polarization curve 96.2%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 4
Corrosion inhibitor compound is obtained to above-described embodiment 4 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.2g, and temperature is 25 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 94.7%, electrification
Impedance spectrum 95.6% is learned, dynamic potential polarization curve 96.8%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 5
Corrosion inhibitor compound is obtained to above-described embodiment 5 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 15 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 93.9%, electrification
Impedance spectrum 94.8% is learned, dynamic potential polarization curve 95.9%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 6
Corrosion inhibitor compound is obtained to above-described embodiment 5 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 35 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 94.2%, electrification
Impedance spectrum 94.9% is learned, dynamic potential polarization curve 96.1%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 7
Corrosion inhibitor compound is obtained to above-described embodiment 5 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 55 DEG C, pH=11.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 93.8%, electrification
Impedance spectrum 94.6% is learned, dynamic potential polarization curve 96.1%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 8
Corrosion inhibitor compound is obtained to above-described embodiment 3 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 25 DEG C, pH=9.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 92.8%, electrification
Impedance spectrum 93.7% is learned, dynamic potential polarization curve 94.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 9
Corrosion inhibitor compound is obtained to above-described embodiment 3 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 25 DEG C, pH=10.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 93.6%, electrification
Impedance spectrum 94.2% is learned, dynamic potential polarization curve 95.0%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 10
Corrosion inhibitor compound is obtained to above-described embodiment 3 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 25 DEG C, pH=12.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 94.5%, electrification
Impedance spectrum 96.1% is learned, dynamic potential polarization curve 97.2%, shows compound for low, the efficient corrosion inhibitor of dosage.
Application examples 11
Corrosion inhibitor compound is obtained to above-described embodiment 3 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 thiadiazoles corrosion inhibitor compound of zinc-aluminum hydrotalcite intercalation chlorion probe modification, medium is 3.5% sodium chloride solution, is used
1L is measured, the effective content for adding corrosion inhibitor compound is 0.1g, and temperature is 25 DEG C, pH=13.5, and Immersion time is 180 days.
Resistance rust efficiency is obtained by experiment test according to the above-mentioned mensuration mode provided, is respectively weightlessness 95.2%, electrification
Impedance spectrum 96.9% is learned, dynamic potential polarization curve 97.6%, shows compound for low, the efficient corrosion inhibitor of dosage.
Compound of the present invention is assembled by chlorion probe modification and intercalation, is contained zinc-aluminum hydrotalcite intercalation is controllable
The chlorion trigger switch of cinnamic acid active group thiadiazole corrosion inhibitor release, the compound of formation.Resistance using the present invention
Become rusty agent compound, can volume production, can accomplish to corrosive environment respond release and repair corrosion carbon steel, and there is long-term protection
Effect, effectively can carry out corrosion protection to carbon steel, have significant application value and vast market prospect.
Claims (9)
1. a kind of thiadiazole corrosion inhibitor compound of active group containing cinnamic acid of hydrotalcite intercalation chlorion probe modification, it is special
Sign is：Assembled by chlorion probe modification and intercalation, in the controllable active group containing cinnamic acid of zinc-aluminum hydrotalcite intercalation
The chlorion trigger switch of group's thiadiazole corrosion inhibitor release, the compound of formation.
2. the thiadiazole corrosion inhibitor compound of active group containing cinnamic acid of the chlorion probe modification as described in claim 1,
It is characterized in that：The thiadiazole corrosion inhibitor of active group containing cinnamic acid that chlorion probe modification is prepared by protonation techniques is inserted
Layer precursor, is then embedded into zinc-aluminum hydrotalcite interlayer；Wherein, the dosage molar ratio between precursor and zinc-aluminum hydrotalcite is 6-8:
1。
3. the thiadiazole of active group containing the cinnamic acid resistance rust of the hydrotalcite intercalation chlorion probe modification as described in claim 2
Agent compound, it is characterised in that：The precursor is that 4-(Metylamino)-benzoic acid is pressed [N+- H ... O] hydrogen bond formed mole metering ratio
Add (1-3 × 10 in the thiadiazoles corrosion inhibitor aqueous solution of active group containing cinnamic acid-3Mol/L), carried out using the HBr of 2.2 equivalents
Protonation titration, prepares the corrosion inhibitor intercalation presoma of chlorion probe modification.
A kind of 4. system of zinc-aluminum hydrotalcite intercalation chlorion probe modification corrosion inhibitor composite as described in claim 1
Preparation Method, it is characterised in that：Carried out by following reactions
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.165Na2CO3
=[Zn0.67Al0.33(OH)2][(CO3)0.165·mH2O]+0.33NaOH (3)
First, at room temperature by zinc nitrate and aluminum nitrate (mole ratio 2:1) mixing, obtains mixed solution A, by mixed solution A
It is slowly dropped in sodium carbonate liquor B that (sodium carbonate and zinc nitrate molar equivalent are than 1:1), and using NaOH maintain its pH 10 ±
0.5, then suspension is crystallized in 65-70 DEG C of heating water bath 24-32h, obtains zinc-aluminum hydrotalcite；
The corrosion inhibitor intercalation precursor of chlorion probe modification is added in the zinc-aluminum hydrotalcite solution of preparation, peeled off by ultrasound,
Condensing reflux, carries out back-mixing precipitation, obtains the zinc-aluminum hydrotalcite compound of the corrosion inhibitor of intercalation chlorion probe modification.
5. the thiadiazole of active group containing the cinnamic acid resistance rust of the hydrotalcite intercalation chlorion probe modification as described in claim 4
The preparation method of agent compound, it is characterised in that：The precursor is that 4-(Metylamino)-benzoic acid is pressed [N+- H ... O] hydrogen bond formation
Mole metering than add the thiadiazoles corrosion inhibitor aqueous solution of active group containing cinnamic acid in (1-3 × 10-3Mol/L), using 2.2 equivalents
HBr carry out protonation titration, prepare the corrosion inhibitor intercalation presoma of chlorion probe modification.
A kind of 6. thiadiazole of active group containing the cinnamic acid resistance of the hydrotalcite intercalation chlorion probe modification described in claim 1
The application of rust agent compound, it is characterised in that：The corrosion inhibitor compound is to concrete mild steel material and its reinforcing bar product
Carry out the application in corrosion protection, reparation.
7. the thiadiazole of active group containing the cinnamic acid resistance rust of the hydrotalcite intercalation chlorion probe modification as described in claim 6
The application of agent compound, it is characterised in that：The seawater corrosion inhibitor compound is in concrete alkaline environment or corresponding alkaline condition
Under application in corrosion protection is carried out to concrete mild steel material and its reinforcing bar product, repair.
8. the thiadiazole of active group containing the cinnamic acid resistance rust of the hydrotalcite intercalation chlorion probe modification as described in claim 7
The application of agent compound, it is characterised in that：The concrete alkaline environment or corresponding alkaline condition refer to that seawater or sodium chloride are situated between
PH value is 9.5-13.5 in matter.
9. the thiadiazole of active group containing the cinnamic acid resistance rust of the hydrotalcite intercalation chlorion probe modification as described in claim 8
The application of agent compound, it is characterised in that：Carbon steel material and its reinforcing bar product are immersed in the alkalescence for adding corrosion inhibitor compound
In sea water solution or medium, bath temperature is 15-45 DEG C, and the wherein amount of corrosion inhibitor compound is 0.05-0.2g/L.
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| CN115707749A (en) * | 2022-09-30 | 2023-02-21 | 马鞍山拓锐金属表面技术有限公司 | High-adhesion antirust agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115707749A (en) * | 2022-09-30 | 2023-02-21 | 马鞍山拓锐金属表面技术有限公司 | High-adhesion antirust agent and preparation method thereof |
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