CN108165995B - Schiff base corrosion inhibitor for iron cultural relics and preparation and application thereof - Google Patents
Schiff base corrosion inhibitor for iron cultural relics and preparation and application thereof Download PDFInfo
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- CN108165995B CN108165995B CN201711205450.4A CN201711205450A CN108165995B CN 108165995 B CN108165995 B CN 108165995B CN 201711205450 A CN201711205450 A CN 201711205450A CN 108165995 B CN108165995 B CN 108165995B
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- 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
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Abstract
The invention relates to a Schiff base corrosion inhibitor for iron cultural relics, and a preparation method and an application thereof. The compounded corrosion inhibitor has the advantages of small using amount, excellent corrosion inhibition effect, low toxicity and no harm. The corrosion inhibitor is used for protecting the cultural relics, and can avoid the problems of the coloring of the cultural relics and the like.
Description
Technical Field
The invention relates to the field of corrosion inhibitors, in particular to preparation and application of a Schiff base corrosion inhibitor for protecting iron cultural relics.
Background
China is one of the countries which are created at the earliest and develop the manufacturing technology of cast iron gradually in the world, but the iron is extremely easy to be corroded by the external environment due to the active property. Therefore, corrosion and protection mechanisms of ironware are continuously researched, and the ironware is protected by using a certain method, so that the method has important significance on cultural relic protection work in China.
At present, a plurality of corrosion inhibitors are widely applied to the protection of cultural relics, but all have the defects that Benzotriazole (BTA) has high toxicity, and the BTA can cause the surfaces of the cultural relics to yellow in practical application; the imidazoline corrosion inhibitor has low yield and is easy to color; the molybdate corrosion inhibitor has high cost and the like.
The yaohua (CN104342707A) discloses a carbon steel corrosion inhibitor which comprises 26-32 parts of sodium silicate, 28-38 parts of hexamethylenetetramine, 17-21 parts of morpholine malate, 13-15 parts of oxalic acid, 23-28 parts of carboxylic acid, 19-25 parts of propanol, 27-35 parts of benzotriazole, 7-9 parts of dehydroabietylamine o-vanillin Schiff base and 13-15 parts of PVA emulsion. The corrosion inhibitor is difficult to avoid the problem of yellowing of the surface of the cultural relics, and benzotriazole and hexamethylenetetramine have toxicity.
Yongchang et al (corrosion inhibition, corrosion and protection of cinnamaldehyde methylamine Schiff base in sulfamic acid, 2016 (8) months, volume 37, 106-. The corrosion inhibitor in the document has good corrosion inhibition efficiency only at high temperature, but the cultural relic protection is mostly carried out at normal temperature, so the corrosion inhibitor is not suitable for the cultural relic protection.
Therefore, the research on the corrosion inhibitor with low toxicity, high efficiency and low cost is of great significance for protecting the iron cultural relics.
Disclosure of Invention
The technical problems existing in the prior art are that the prior corrosion inhibitor has the defects of high toxicity, low yield, easy coloring, high cost and the like, and is difficult to be applied to cultural relic protection.
The Schiff base is compounded with the sodium silicate, the zinc dihydrogen phosphate and the triethanolamine, and the components in the compound corrosion inhibitor show good synergistic effect and have good corrosion inhibition performance.
Specifically, the invention provides the following technical scheme:
the invention provides a corrosion inhibitor, which contains Schiff base, silicate, phosphate and alcamines compounds.
Preferably, the corrosion inhibitor is prepared from the Schiff base, the silicate, the phosphate and the alcohol amine compound in a mass ratio of 3-14.5: 1.4-7.2: 0.2-1.5: 64-320.
Preferably, the mass ratio of the schiff base, the silicate, the phosphate and the alcohol amine compound is 3.3-10: 1.67-5: 0.33-1: 75-225.
Preferably, the corrosion inhibitor is one wherein the schiff base is selected from amino acid schiff bases.
Preferably, in the corrosion inhibitor, the amino acid schiff base is selected from glycine schiff base, glutamic acid schiff base, methionine schiff base, tyrosine schiff base, arginine schiff base, methionine schiff base, and cysteine schiff base.
Preferably, the corrosion inhibitor is one in which the schiff base has a benzene ring in its structure.
Preferably, the schiff base is selected from the group consisting of cinnamaldehyde schiff base, benzaldehyde schiff base, and salicylaldehyde schiff base.
Preferably, the corrosion inhibitor is one wherein the silicate is selected from sodium silicate and/or potassium silicate.
Preferably, the corrosion inhibitor is one wherein the phosphate is selected from zinc phosphate, zinc dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and/or potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate; preferably, the phosphate is zinc dihydrogen phosphate.
Preferably, the corrosion inhibitor is one wherein the alcohol amine compound is selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine; preferably, the alkanolamine compound is triethanolamine.
Preferably, the corrosion inhibitor comprises cinnamaldehyde-glycine schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine.
Preferably, the corrosion inhibitor comprises an organic solvent.
Preferably, the corrosion inhibitor is one wherein the organic solvent is selected from ethanol, ethyl acetate, methanol and/or acetone; preferably, the organic solvent is a mixture of ethanol and ethyl acetate; more preferably, the organic solvent is a mixture of ethanol and ethyl acetate in a mass ratio of 0.8-1.2.
Preferably, the ratio of the total mass of the schiff base, the silicate, the phosphate and the alcohol amine compound to the volume of the organic solvent is 0.048-0.15 g/ml.
In another aspect, the invention provides the use of the corrosion inhibitor in the field of corrosion protection, preferably in corrosion inhibition of cultural relics, more preferably in corrosion inhibition of iron cultural relics.
The beneficial effects of the invention include:
the Schiff base compound corrosion inhibitor has low toxicity, safety and environmental protection.
The components in the compound corrosion inhibitor show good synergistic effect, the effect of the compound corrosion inhibitor is obviously improved after compounding, and the compound corrosion inhibitor shows good effect on corrosion inhibition of cast iron.
Aiming at the problems existing in the prior iron cultural relic corrosion inhibitor, the low-toxicity environment-friendly corrosion inhibitor avoids the coloring problem.
The corrosion inhibitor can be used at normal temperature, and damage to cultural relics caused by high temperature is avoided.
The invention and its advantageous technical effects are explained in detail below with reference to the accompanying drawings and various embodiments, in which:
drawings
FIGS. 1a and 1b are Tafel graphs of a blank sample coated with the compounded corrosion inhibitor prepared in examples 1-5 and comparative examples 1-4 of the present invention, the pure Schiff base corrosion inhibitor prepared in example 1, and at normal temperature, wherein lgI is current density; and E is the electrode potential.
FIG. 2 is a Nyquist plot of the pure Schiff base corrosion inhibitor prepared in example 1 and coated with the compound corrosion inhibitors prepared in examples 1 to 5 and comparative examples 1 to 4 of the present invention at normal temperature, wherein Z' is the real part of impedance; -Z "is the imaginary impedance, where the impedance is, in order of magnitude: schiff base compounding 11, Schiff base compounding 10, Schiff base compounding 9, Schiff base compounding 12, pure Schiff base, Schiff base compounding 3, Schiff base compounding 2, Schiff base compounding 4, Schiff base compounding 5 and Schiff base compounding 1.
FIG. 3 is a graph showing the corrosion status of a galvanized iron sheet coated with the compounded corrosion inhibitor prepared in examples 1 to 5 and comparative examples 1 to 4 of the present invention and the Schiff base corrosion inhibitor prepared in example 1 after a salt spray test (standing for one month under 10% NaCl).
Detailed Description
As described above, the present invention aims to: aiming at the defects of the existing corrosion inhibitor, the preparation method of the Schiff base compound corrosion inhibitor is provided, and the prepared corrosion inhibitor has low toxicity and good effect.
The preferable Schiff base compound corrosion inhibitor comprises the following components in percentage by mass: sodium silicate: zinc dihydrogen phosphate: triethanolamine is 10:5:1:225, and the balance is organic mixed solvent.
In the Schiff base compound corrosion inhibitor, the organic mixed solvent is ethanol: ethyl acetate 1: 1.
The preparation method of the preferable Schiff base compound corrosion inhibitor comprises the following steps:
step one, thermally dissolving glycine and potassium hydroxide in a round-bottom flask at 50 ℃, stirring for reaction for 2 hours, cooling, and then carrying out vacuum filtration; preferably, the thermosol is absolute ethanol. Preferably, the molar ratio of glycine to potassium hydroxide is 1: 1.
transferring the obtained solution into a three-mouth bottle, introducing nitrogen for protection, dropwise adding cinnamaldehyde at room temperature, heating to 60 ℃, refluxing and condensing for 1 h; preferably, the molar numbers of the cinnamaldehyde and the glycine and the sodium hydroxide are the same; preferably, reflux condensation is carried out in a serpentine condenser tube.
Standing at room temperature for reaction for 30min, separating out a white solid, keeping the temperature for reaction for 2h, filtering, washing the solid with acetone to white, and drying in vacuum to obtain cinnamaldehyde amino acid Schiff base; preferably, the vacuum drying temperature is 60 ℃; the vacuum drying time is preferably 10 h.
And step four, dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a mixed solvent of ethanol and ethyl acetate in sequence according to a proportion.
The nitrogen atom with high electronegativity contained in the carbon-nitrogen double bond in the Schiff base molecule provides lone pair electrons and a double bond structure capable of providing pi bond and empty orbit, and the double bond structure and the metal surface generate adsorption reaction to form a protective film layer. The preferable Schiff base contains a benzene ring structure, has good adsorption performance, is superior to a common corrosion inhibitor with a long-chain structure, and has good corrosion inhibition performance. However, the inventor finds that when the Schiff base corrosion inhibitor is used alone for corrosion prevention, the corrosion inhibitor is easy to absorb water, easy to color, easy to deteriorate and the like in the using process. Therefore, the Schiff base corrosion inhibitor needs to be compounded, and the efficiency of the corrosion inhibitor and the stability of the solution are improved through compounding.
In the preferable formula of the compound corrosion inhibitor, Schiff base is used as a main agent, and sodium silicate, zinc dihydrogen phosphate and triethanolamine are added for synergistic corrosion inhibition. The Schiff base and sodium silicate can generate a synergistic effect to form a high-efficiency corrosion inhibitor in a solution containing chloride ions; the ferrous iron ions in the iron cultural relics react with phosphate radicals to generate insoluble gamma-Fe2O3,Fe3O4And FePO4A passivation film; divalent zinc ions can precipitate to form Zn (OH)2Forming multiple protective films; triethanolamine and phosphate radical ions can form triethanolamine phosphate, can form five-membered chelate with iron ions, can also carry out certain repair when the film layer is damaged, and meanwhile, the triethanolamine can stabilize the system and avoid precipitation.
The inventor also finds that the corrosion inhibitor has the highest solubility in a mixed solvent of ethanol and ethyl acetate, and the corrosion inhibitor is not easy to deteriorate. The ratio of ethanol to ethyl acetate is different, the solubility of Schiff base in the mixed solvent is different, the preferable ratio of ethanol to ethyl acetate is 0.8-1.2, and the Schiff base is insoluble when the ratio exceeds the range.
The schiff base corrosion inhibitor of the invention is illustrated by the following specific examples, and the corrosion inhibition performance of the corrosion inhibitor of the invention is tested.
The reagents and instrumentation used in the following examples were from the following sources:
TABLE 1 reagents and apparatus used in the examples
The instrumentation and the specific operating conditions not mentioned in the present invention are those which can be routinely determined by the person skilled in the art.
And (3) polishing the tinplate step by using 600-mesh, 800-mesh and 1200-mesh metallographic abrasive paper, washing with deionized water, dehydrating with ethanol and acetone to remove oil, and drying for later use.
Example 1
In a round-bottom flask, 5g of glycine and 3.5g of potassium hydroxide were dissolved in 250ml of absolute ethanol at 50 ℃ by heating, and the reaction was stirred for 2 hours until no more solid at the bottom of the flask decreased, and then the reaction was stopped, cooled, and filtered under reduced pressure. Transferring the obtained filtrate to a three-necked bottle, introducing nitrogen for protection, dropwise adding 7.8ml (7.5mol) of cinnamyl aldehyde at room temperature, heating to 60 ℃, refluxing for 1h, standing at room temperature for reaction for 30min to separate out white solid, then preserving heat for reaction for 2h, filtering, washing the solid with acetone to white, and performing vacuum drying to obtain the cinnamyl aldehyde amino acid Schiff base.
The above reaction process can be represented by the following reaction formula:
and 2, dissolving the Schiff base obtained in the step 1 in ethanol: and preparing a 0.7 wt% solution in a solvent of which the ratio of ethyl acetate is 1:1 to obtain the Schiff base corrosion inhibitor.
And 3, dissolving the Schiff base, the sodium silicate, the zinc dihydrogen phosphate and the triethanolamine obtained in the step 1 in ethanol according to the mass ratio of 10:5:1: 225: ethyl acetate 1:1 (14.46g of corrosion inhibitor is dissolved in 100ml of solvent) to obtain the Schiff base compound corrosion inhibitor 1.
Example 2
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a ratio of 3.3:5:1:225 in ethanol: ethyl acetate 1:1 solvent (14.06g of corrosion inhibitor is dissolved in 100ml of solvent) to obtain the Schiff base compound corrosion inhibitor 2.
Example 3
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a ratio of 10:1.67:1:225 in ethanol: ethyl acetate 1:1 solvent (14.26g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 3.
Example 4
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a ratio of 10:5:0.33:225 in ethanol: ethyl acetate 1:1 solvent (14.42g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 4.
Example 5
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a ratio of 10:5:1:75 in ethanol: ethyl acetate 1:1 solvent (11.81g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 5.
Example 6
The difference from the preparation of schiff base in example 1 is that: cysteine is used to replace glycine, and salicylaldehyde is used to replace cinnamaldehyde.
Dissolving Schiff base, potassium silicate, sodium dihydrogen phosphate and isopropanolamine in ethanol according to the ratio of 10:5:0.33: 225: ethyl acetate 1:1 solvent (14.26g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 6.
Example 7
The difference from the preparation of schiff base in example 1 is that: tyrosine is used for replacing glycine, and salicylaldehyde is used for replacing cinnamaldehyde.
Dissolving Schiff base, potassium silicate, potassium dihydrogen phosphate and 2- (methylamino) ethanol in a ratio of 3.3:5:1:225 in ethanol: ethyl acetate 1:1 solvent (14.42g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 7.
Example 8
The difference from the preparation of schiff base in example 1 is that: cysteine was used instead of glycine and benzaldehyde was used instead of cinnamaldehyde.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and n-propanolamine in ethanol according to the proportion of 10:5:1: 75: ethyl acetate 1:1 solvent (11.81g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 8.
Comparative example 1
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in ethanol according to the proportion of 10:0:1: 225: ethyl acetate 1:1 solvent (14.16g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 9.
Comparative example 2
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in a ratio of 10:5:0:225 in ethanol: ethyl acetate 1:1 solvent (14.4g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 10.
Comparative example 3
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in ethanol according to the proportion of 10:5:1: 0: ethyl acetate 1:1 solvent (0.96g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 11.
Comparative example 4
Schiff bases were prepared in the same manner as in example 1.
Dissolving Schiff base, sodium silicate, zinc dihydrogen phosphate and triethanolamine in ethanol according to the proportion of 5:5:1: 225: ethyl acetate 1:1 solvent (28.32g of corrosion inhibitor dissolved in 100ml of solvent) to obtain the compound corrosion inhibitor 12.
Alternating current impedance and polarization curve tests are carried out on the Schiff base corrosion inhibitor obtained in the example 1, the compound corrosion inhibitor prepared in the examples 1 to 5 and the comparative example coated tinplate and the tinplate (blank) which is not treated by the corrosion inhibitor, and the alternating current impedance curve of the tinplate cast iron subjected to corrosion inhibition treatment in 3.5% NaCl is measured by an autolab electrochemical workstation in the experiment, wherein the working electrode is a test piece, the auxiliary electrode is a platinum electrode, and the reference electrode is a saturated calomel electrode. The test results are shown in fig. 1a, fig. 1b, fig. 2 and table 2.
TABLE 2 comparison of different corrosion inhibitors
In the table, Icorr is corrosion current density, Ecorr is self-corrosion potential, Ba and Bc are Tafel slope, and IE is corrosion inhibition efficiency obtained by calculation, corrosion kinetic parameters of the corrosion inhibitor obtained by Tafel extrapolation, and a calculation formula of the corrosion inhibition efficiency IE is η ═ I (I is a calculation formula of corrosion inhibition efficiency IE)0-I)/I0X 100% where I0The corrosion current density of the blank sample is shown, and I is the corrosion current density of the sample after the corrosion inhibitor is added.
Through electrochemical tests, a polarization curve and an electrochemical impedance diagram are respectively obtained, and compared with the curves in attached figures 1a and 1b, the corrosion potential and the corrosion current density are changed, the self-corrosion potential is improved, the corrosion current density is reduced, and the corrosion inhibition efficiency is improved. As can be seen from fig. 1a, fig. 1b and table 2, the schiff base complex formulation 1 has the minimum corrosion current density, which proves that the corrosion current is significantly reduced by adding the corrosion inhibitor, and the corrosion inhibition efficiency is arranged from large to small: schiff base compounding 1, Schiff base compounding 4, Schiff base compounding 3, Schiff base compounding 5, Schiff base compounding 2, Schiff base compounding 9, Schiff base compounding 12, Schiff base compounding 10 and Schiff base compounding 11, and the self-corrosion potential of the Schiff base compounding 1 is high, so that the Schiff base is difficult to corrode. Meanwhile, the comparative example shows that when the consumption of the corrosion inhibitor is too much or the compound components are not enough, the corrosion inhibition efficiency is reduced to different degrees compared with the compound corrosion inhibitor of the invention.
FIG. 2 is a Nyquist plot of various corrosion inhibitors after addition, the Nyquist plot showing a semicircular arc of impedance, indicating that the corrosion inhibitors carry a number of complex groups that react readily with the cast iron matrix to form a protective film; the Schiff base contains C-N double bonds and contains-OH which is easy to form a stable complex with metal, so that the Schiff base can provide good protective adsorption effect on the metal surface, and the corrosion of the metal is prevented. The size of the impedance arc diameter directly reflects the size of the charge transfer resistance on the surface of the electrode, the larger the resistance is, the smaller the corrosion rate is, and as can be seen from the curve, the pure Schiff base corrosion inhibitor already shows good effect, while the Schiff base compound corrosion inhibitor 1 shows more excellent effect compared with other corrosion inhibitors, the impedance reaches twice of the original impedance, which shows that the corrosion inhibition effect is greatly enhanced after the compound.
The corrosion inhibitors prepared in examples 1 to 8 and comparative examples 1 to 4 were coated on a tinplate and then subjected to a salt spray test, and fig. 3 is a corrosion state diagram of the tinplate after the salt spray test (standing for one month under 10% NaCl) using different corrosion inhibitors, and the corrosion resistance of the corrosion inhibitor can be visually observed through the salt spray test, so that the performance of the compounded schiff base corrosion inhibitor is improved, and the corrosion area of the schiff base compounded corrosion inhibitor 1 is greatly reduced.
The test results of the polarization curve and the alternating current impedance both verify the excellent performance of the Schiff base compound corrosion inhibitor, but errors appear in the alternating current impedance and the polarization curve aiming at the Schiff base compound result of 2-5, which is mainly because the polarization curve method is a test carried out under a stronger electric field, corrosion potential and current are determined in a tangential extension mode of the polarization curve, the alternating current impedance is tested near an open circuit potential in a state close to equilibrium by a sine wave, and the alternating current impedance is very sensitive to tiny changes on the surface of an electrode, so when the concentration of the corrosion inhibitor is reduced or the corrosion inhibition effect is reduced, particularly when the adsorption film forming effect on the surface of the electrode is weak, the polarization curve is not easy to distinguish the differences, but the alternating current impedance can distinguish the differences.
No matter a polarization curve or an alternating current impedance test or a salt spray test shows that the Schiff base has a good corrosion inhibition effect, and compared with pure Schiff base, the stability of the compounded Schiff base corrosion inhibitor is greatly improved. Meanwhile, the compounded Schiff base can be used at normal temperature, and has no coloring trouble, so that the Schiff base can be used for protecting iron cultural relics.
Claims (37)
1. The corrosion inhibitor is characterized by comprising Schiff base, silicate, phosphate and alcohol amine compounds, wherein the mass ratio of the Schiff base to the silicate to the phosphate to the alcohol amine compounds is 3.3-10: 1.67-5: 0.33-1: 75-225; wherein the Schiff base is selected from amino acid Schiff bases; the corrosion inhibitor contains an organic solvent; the ratio of the total mass of the Schiff base, the silicate, the phosphate and the alcohol amine compound to the volume of the organic solvent is 0.048-0.15 g/ml.
2. The corrosion inhibitor of claim 1, wherein the amino acid type schiff base is selected from glycine schiff base, glutamic acid schiff base, methionine schiff base, tyrosine schiff base, arginine schiff base, methionine schiff base, cysteine schiff base.
3. The corrosion inhibitor according to claim 1 or 2, wherein the schiff base has a structure comprising a benzene ring.
4. The corrosion inhibitor of claim 3, wherein the Schiff base is selected from cinnamaldehyde Schiff base, benzaldehyde Schiff base, salicylaldehyde Schiff base.
5. The corrosion inhibitor according to claim 1 or 2, wherein the silicate is selected from sodium silicate and/or potassium silicate.
6. The corrosion inhibitor according to claim 3, wherein the silicate is selected from sodium silicate and/or potassium silicate.
7. The corrosion inhibitor according to claim 4, wherein the silicate is selected from sodium silicate and/or potassium silicate.
8. The corrosion inhibitor according to claim 1 or 2, wherein the phosphate is selected from zinc phosphate, zinc dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and/or potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
9. The corrosion inhibitor according to claim 3, wherein the phosphate is selected from zinc phosphate, zinc dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and/or potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
10. The corrosion inhibitor according to claim 4, wherein the phosphate is selected from zinc phosphate, zinc dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and/or potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
11. The corrosion inhibitor according to claim 5, wherein the phosphate is selected from zinc phosphate, zinc dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and/or potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
12. The corrosion inhibitor of claim 1 or 2, wherein the phosphate is zinc dihydrogen phosphate.
13. The corrosion inhibitor of claim 3 wherein the phosphate is zinc dihydrogen phosphate.
14. The corrosion inhibitor of claim 4 wherein the phosphate is zinc dihydrogen phosphate.
15. The corrosion inhibitor of claim 5 wherein the phosphate is zinc dihydrogen phosphate.
16. The corrosion inhibitor according to claim 1 or 2, wherein the alcamines are selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine.
17. The corrosion inhibitor according to claim 3, wherein the alcamines are selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine.
18. The corrosion inhibitor according to claim 4, wherein the alcamines are selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine.
19. The corrosion inhibitor according to claim 5, wherein the alcamines are selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine.
20. The corrosion inhibitor according to claim 8, wherein the alcamines are selected from monoethanolamine, diethanolamine, triethanolamine, 2- (methylamino) ethanol, 2-ethylamine ethanol, 2-diethylaminoethanol, n-propanolamine, isopropanolamine, diisopropanolamine, butanolamine and/or dibutanolamine.
21. The corrosion inhibitor according to claim 1 or 2, wherein the alcamines are triethanolamine.
22. The corrosion inhibitor of claim 3, wherein the alcamines are triethanolamine.
23. The corrosion inhibitor of claim 4, wherein the alcamines are triethanolamine.
24. The corrosion inhibitor of claim 5, wherein the alcamines are triethanolamine.
25. The corrosion inhibitor of claim 8, wherein the alcamines are triethanolamine.
26. The corrosion inhibitor of claim 1 or 2, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
27. The corrosion inhibitor of claim 3, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine Schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
28. The corrosion inhibitor of claim 4, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine Schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
29. The corrosion inhibitor of claim 5, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine Schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
30. The corrosion inhibitor of claim 8, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
31. The corrosion inhibitor of claim 16, wherein the corrosion inhibitor comprises cinnamaldehyde-glycine schiff base, sodium silicate, zinc dihydrogen phosphate, and triethanolamine.
32. The corrosion inhibitor according to claim 1, wherein the organic solvent is selected from ethanol, ethyl acetate, methanol and/or acetone.
33. The corrosion inhibitor of claim 1 wherein the organic solvent is a mixture of ethanol and ethyl acetate.
34. The corrosion inhibitor according to claim 1, wherein the organic solvent is a mixture of ethanol and ethyl acetate in a mass ratio of 0.8-1.2.
35. Use of a corrosion inhibitor according to any one of claims 1 to 34 in the field of corrosion protection.
36. Use of a corrosion inhibitor according to any one of claims 1 to 34 for the inhibition of corrosion of cultural relics.
37. Use of a corrosion inhibitor according to any one of claims 1 to 34 for the corrosion inhibition of iron material cultural relics.
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