CN114635137A - Organic-inorganic hybrid composite corrosion inhibitor and preparation method and application thereof - Google Patents
Organic-inorganic hybrid composite corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- CN114635137A CN114635137A CN202011484607.3A CN202011484607A CN114635137A CN 114635137 A CN114635137 A CN 114635137A CN 202011484607 A CN202011484607 A CN 202011484607A CN 114635137 A CN114635137 A CN 114635137A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 85
- 230000007797 corrosion Effects 0.000 title claims abstract description 83
- 239000003112 inhibitor Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 56
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 pyridine aldehyde compound Chemical class 0.000 claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YYLBDBOSXXSZQQ-UHFFFAOYSA-N 5-chloropyridine-2-carbaldehyde Chemical compound ClC1=CC=C(C=O)N=C1 YYLBDBOSXXSZQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- YOVIXSRXKCZJRN-UHFFFAOYSA-N 5-methoxypyridine-3-carbaldehyde Chemical compound COC1=CN=CC(C=O)=C1 YOVIXSRXKCZJRN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 11
- 230000010287 polarization Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an organic-inorganic hybrid composite corrosion inhibitor and a preparation method and application thereof. The composite corrosion inhibitor is prepared from a component A and a component B in a weight ratio of 1: 0.3-1.5, wherein the component A is pyridine aldehyde compound modified chitosan obtained by reacting 2-8 parts by weight of pyridine aldehyde compound with 4-16 parts by weight of chitosan, and the component B is nano zinc oxide. The composite corrosion inhibitor has excellent corrosion inhibition effect, can play a role under an acidic condition, and has the advantages of simple preparation method, mild condition and easy control of the process.
Description
Technical Field
The invention belongs to the field of metal corrosion and protection, and particularly relates to an organic-inorganic hybrid composite corrosion inhibitor, and a preparation method and application thereof.
Background
Metals play an irreplaceable important role in modern industry and are widely applied to the fields of construction, mechanical manufacturing, catalysis and the like. However, in the practical application process of metals, serious corrosion phenomena exist, the corrosion of metals can not only cause the leakage of harmful substances and the pollution to the environment, but also cause serious even serious disastrous accidents, and bring great loss to the social economy, and the corrosion of steel is the most common.
Although the corrosion phenomenon of the metal is difficult to eliminate, the metal can be inhibited from corroding by adopting a proper method, and the service life of the metal is prolonged. At present, the protection method for metal comprises the steps of adding corrosion-resistant metal to form alloy, using an anti-corrosion coating, adding a corrosion inhibitor and the like. The corrosion inhibitor has the advantages of low cost, effectiveness, flexibility, simple operation and the like, and is an important means for metal corrosion prevention. Various inorganic or organic corrosion inhibitors have been developed, which can form an oxide layer or a precipitate layer on the metal surface, such as chromate, molybdate and other inorganic corrosion inhibitors, which can form a relatively dense film on the metal surface to inhibit corrosion; the organic corrosion inhibitor can form an adsorption layer on the metal surface, so that corrosive substances such as carboxylate, benzotriazole and other organic corrosion inhibitors are difficult to contact the metal surface. However, the common corrosion inhibitor needs a large amount of corrosion inhibitor, which is likely to cause serious environmental pollution, or the metal protection in the practical application process is not good enough to reach the ideal expectation, so that the search for a high-efficiency environment-friendly corrosion inhibitor has become a research hotspot of corrosion science.
In the previous research and exploration process, a research team invents an environment-friendly glycol cooling liquid which has the functions of sterilization and algae removal, has good heat-conducting property and corrosion resistance, is environment-friendly, has long service cycle and is convenient to recover. On the basis of the research, the environment-friendly organic-inorganic hybrid composite corrosion inhibitor is obtained through Schiff base reaction and nano zinc oxide compounding, and the corrosion prevention efficiency is further improved.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention mainly aims to provide an organic-inorganic hybrid composite corrosion inhibitor.
The invention also aims to provide a preparation method of the organic-inorganic hybrid composite corrosion inhibitor.
The invention also aims to provide application of the organic-inorganic hybrid composite corrosion inhibitor.
The purpose of the invention is realized by the following technical scheme:
an organic-inorganic hybrid composite corrosion inhibitor is prepared from a component A and a component B in a weight ratio of 1: 0.3-1.5, wherein the component A is pyridine aldehyde compound modified chitosan obtained by reacting 2-8 parts by weight of pyridine aldehyde compound with 4-16 parts by weight of chitosan, and the component B is nano zinc oxide.
Preferably, the weight ratio of the chitosan to the pyridine aldehyde compound is 2-4: 1, more preferably 2 to 3.2: 1.
preferably, the molecular weight of the chitosan is 3000-.
Preferably, the pyridine aldehyde compound is at least one of pyridine-4-carbaldehyde, 5-chloro-2-pyridinecarbaldehyde, pyridine-2-carbaldehyde, 2, 6-pyridinedicarboxaldehyde, pyridine-3-carbaldehyde, and 5-methoxy-3-pyridinecarbaldehyde.
Preferably, the weight ratio of the component A to the component B is 1: 0.3-1.3.
The method for preparing the organic-inorganic hybrid composite corrosion inhibitor comprises the following steps:
(1) reacting chitosan with pyridine aldehyde compounds at 30-60 ℃ for 4-6h by taking a solvent as a reaction medium, filtering, washing and drying to obtain pyridine aldehyde compound modified chitosan;
(2) adding pyridine aldehyde compound modified chitosan into nano zinc oxide aqueous solution, stirring and reacting for 2-4h at room temperature, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Preferably, the solvent in step (1) is at least one of acetic acid, ethanol and water.
Preferably, the pyridine aldehyde compound modified chitosan in the step (1) is prepared by the following method: uniformly mixing the aqueous solution of chitosan acetic acid and the aqueous solution of pyridine aldehyde compound ethanol, then reacting for 4-6h at 30-60 ℃, filtering, washing and drying to obtain the pyridine aldehyde compound modified chitosan.
More preferably, the chitosan acetic acid aqueous solution is obtained by dissolving chitosan in acetic acid aqueous solution, wherein the concentration of chitosan in the solution is 12-24mg/mL, and the concentration of acetic acid in the acetic acid aqueous solution is 0.1-0.3 mol/L.
More preferably, the aqueous ethanol solution of the pyridine aldehyde compound is obtained by dissolving the pyridine aldehyde compound in an aqueous ethanol solution, wherein the concentration of the pyridine aldehyde compound in the aqueous ethanol solution is 40-60mg/mL, and the concentration of ethanol in the aqueous ethanol solution is 0.2-0.3 mol/L.
Preferably, the concentration of the nano zinc oxide water dispersion liquid in the step (2) is 1-4 mg/mL; more preferably, the nano zinc oxide aqueous solution is obtained by adding 0.1-0.4g of nano zinc oxide into 100mL of water and performing ultrasonic treatment for 0.5-1.5 h.
The reaction equation of the chitosan and pyridine aldehyde compound in the step (1) of the invention is as follows:
the application of the organic-inorganic hybrid composite corrosion inhibitor is provided.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the pyridine aldehyde compound modified chitosan obtained by Schiff base reaction solves the defect of poor water solubility of chitosan, and greatly improves the anti-corrosion effect on metal due to the pyridine heterocycle; on the other hand, the modified chitosan can provide lone-pair electrons and pi electrons in a conjugated structure can form coordinate bonds with a metal empty-d orbit so as to wrap the nano zinc oxide, and the modified chitosan is protonated under an acidic condition and adsorbed on the metal surface, so that the corrosion inhibition effect is greatly improved. The organic-inorganic hybrid composite corrosion inhibitor obtained by the invention has excellent corrosion inhibition effect under lower concentration, has small harm to the environment, and is an environment-friendly green corrosion inhibitor. The preparation method is simple, has moderate conditions, is easy to operate, and has larger application market and research value.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Fully dissolving 0.5g of chitosan with the molecular weight of 3000 in 30mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) adding 5mL of 0.3mol/L ethanol aqueous solution containing 0.25g of pyridine-3-formaldehyde into the chitosan solution in the step (1), heating to 50 ℃, reacting for 5h, filtering, washing and drying to obtain pyridine-3-formaldehyde modified chitosan;
(3) adding 0.3g of nano zinc oxide into 100mL of deionized solution, performing ultrasonic treatment for 1h, adding 0.3g of pyridine-3-formaldehyde modified chitosan into the nano zinc oxide aqueous solution after ultrasonic treatment, stirring at room temperature for reaction for 2h, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Example 2
(1) Fully dissolving 0.6g of chitosan with the molecular weight of 10000 in 40mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) adding 5mL of 0.3mol/L ethanol water solution containing 0.25g of 5-chloro-2-pyridinecarbaldehyde into the chitosan solution in the step (1), heating to 60 ℃, reacting for 4h, filtering, washing and drying to obtain 5-chloro-2-pyridinecarbaldehyde modified chitosan;
(3) adding 0.2g of nano zinc oxide into 100mL of deionized solution, performing ultrasonic treatment for 1h, then adding 0.3g of 5-chloro-2-pyridylaldehyde modified chitosan into the nano zinc oxide aqueous solution after ultrasonic treatment, stirring at room temperature for reaction for 2h, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Example 3
(1) Fully dissolving 0.7g of chitosan with the molecular weight of 50000 in 50mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) adding 5mL of 0.3mol/L ethanol aqueous solution containing 0.25g of pyridine-2-formaldehyde into the chitosan solution in the step (1), heating to 60 ℃, reacting for 4h, filtering, washing and drying to obtain pyridine-2-formaldehyde modified chitosan;
(3) adding 0.2g of nano zinc oxide into 100mL of deionized solution, performing ultrasonic treatment for 1h, then adding 0.3g of pyridine-2-formaldehyde modified chitosan into the nano zinc oxide aqueous solution after ultrasonic treatment, stirring at room temperature for reaction for 2h, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Example 4
(1) Fully dissolving 0.7g of chitosan with the molecular weight of 100000 in 30mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) adding 5mL of 0.3mol/L ethanol water solution containing 0.25g of 5-methoxy-3-pyridylaldehyde into the chitosan solution in the step (1), heating to 40 ℃, reacting for 6h, filtering, washing and drying to obtain 5-methoxy-3-pyridylaldehyde modified chitosan;
(3) adding 0.1g of nano zinc oxide into 100mL of deionized solution, performing ultrasonic treatment for 1h, then adding 0.3g of 5-methoxy-3-pyridylaldehyde modified chitosan into the nano zinc oxide aqueous solution after ultrasonic treatment, stirring at room temperature for reaction for 2h, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Example 5
(1) Fully dissolving 0.8g of chitosan with the molecular weight of 200000 in 40mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) adding 5mL of 0.3mol/L ethanol aqueous solution containing 0.25g of pyridine-4-formaldehyde into the chitosan solution in the step (1), heating to 50 ℃, reacting for 4h, filtering, washing and drying to obtain pyridine-4-formaldehyde modified chitosan;
(3) adding 0.4g of nano zinc oxide into 100mL of deionized solution, performing ultrasonic treatment for 1h, then adding 0.3g of pyridine-4-formaldehyde modified chitosan into the nano zinc oxide aqueous solution after ultrasonic treatment, stirring at room temperature for reaction for 3h, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
Comparative example 1
(1) Fully dissolving 0.5g of chitosan with the molecular weight of 3000 in 30mL of 0.3mol/L acetic acid aqueous solution at room temperature;
(2) and (2) adding 5mL of 0.3mol/L ethanol water solution containing 0.25g of pyridine-3-formaldehyde into the chitosan solution in the step (1), heating to 50 ℃, reacting for 5 hours, filtering, washing and drying to obtain pyridine-3-formaldehyde modified chitosan, namely the corrosion inhibitor.
And (3) testing the corrosion inhibition performance of the organic-inorganic hybrid composite corrosion inhibitor:
the corrosion inhibitors were prepared according to the preparation methods of examples 1 to 5 and comparative example 1, the corrosion inhibition performance of the corrosion inhibitor was studied electrochemically, and the prepared corrosion inhibitors were analyzed and verified.
The electrochemical test adopts CHI660E electrochemical workstation (Shanghai Chenghua), which comprises Q235 steel sample (working electrode), platinum sheet (auxiliary electrode) and saturated calomel electrode (reference electrode), the potentiodynamic polarization scanning range is: -0.25V, the scanning rate is 0.5mV/s, and the frequency variation range of the electrochemical AC impedance spectrum is as follows: 0.1 Hz-100 kHz, the disturbance amplitude is as follows: 5 mV;
the electrochemical test of example 1 was divided into four groups, all soaked for 72 h. The corrosion medium of the first group is 1mol/L hydrochloric acid solution (100mL) without adding a corrosion inhibitor; the corrosion medium of the second group is 1mol/L hydrochloric acid solution (100mL), and 50ppm (0.0055g) of corrosion inhibitor is added; the corrosion medium of the third group is 1mol/L hydrochloric acid solution (100mL), and 100ppm (0.0103g) of corrosion inhibitor is added; the etching medium of the fourth group was 1mol/L hydrochloric acid solution (100mL) to which 200ppm (0.0204g) of corrosion inhibitor was added.
Example 1 polarization curve data obtained by potentiodynamic polarization curve testing is shown in table 1:
TABLE 1 potentiodynamic polarization curve test results for example 1
Example 1 ac impedance spectroscopy data obtained by electrochemical ac impedance testing are shown in table 2:
table 2 ac impedance spectroscopy test results for example 1
The electrochemical test of comparative example 1 was divided into four groups, all soaked for 72 h. The corrosion medium of the first group is 1mol/L hydrochloric acid solution (100mL) without adding a corrosion inhibitor; the corrosion medium of the second group is 1mol/L hydrochloric acid solution (100mL), and 50ppm (0.0055g) of corrosion inhibitor is added; the corrosion medium of the third group is 1mol/L hydrochloric acid solution (100mL), and 100ppm (0.0103g) of corrosion inhibitor is added; the etching medium of the fourth group was 1mol/L hydrochloric acid solution (100mL) to which 200ppm (0.0204g) of corrosion inhibitor was added.
Comparative example 1 polarization curve data obtained by potentiodynamic polarization curve testing is shown in table 3:
table 3 potentiodynamic polarization curve test results for comparative example 1
Comparative example 1 ac impedance spectroscopy data obtained by electrochemical ac impedance testing are shown in table 4:
table 4 ac impedance spectroscopy test results for comparative example 1
Examples 1-5 and comparative example 1 were subjected to electrochemical testing at a corrosion inhibitor concentration of 100ppm (0.0103g) and immersed for 72 hours.
Examples 1-5 and comparative example 1 polarization curve data obtained by potentiodynamic polarization curve testing are shown in table 5:
TABLE 5 potentiodynamic polarization curve test results for examples 1-5 and comparative example 1
The AC impedance spectra data obtained by the electrochemical AC impedance test of examples 1-5 and comparative example 1 are shown in Table 6:
TABLE 6 results of AC impedance Spectroscopy testing of examples 1-5 and comparative example 1
As can be seen from the table, the corrosion inhibitors of examples 1 to 5 exhibited excellent corrosion inhibition effects at low concentrations, and each of them exhibited the best corrosion inhibition effect at a corrosion inhibitor concentration of 100 ppm. And compared with the corrosion inhibition effect of the comparative example 1, the corrosion inhibition effects of the examples 1 to 5 are obviously improved.
Therefore, in the field of metal corrosion and protection, the organic-inorganic hybrid composite corrosion inhibitor has good application prospect, and has no relation to the application in other fields such as biology, medicine and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An organic-inorganic hybrid composite corrosion inhibitor is characterized by comprising a component A and a component B in a weight ratio of 1: 0.3-1.5, wherein the component A is pyridine aldehyde compound modified chitosan obtained by reacting 2-8 parts by weight of pyridine aldehyde compound with 4-16 parts by weight of chitosan, and the component B is nano zinc oxide.
2. The organic-inorganic hybrid composite corrosion inhibitor as claimed in claim 1, wherein the weight ratio of the chitosan to the pyridine aldehyde compound is 2-4: 1; the weight ratio of the component A to the component B is 1: 0.3-1.3.
3. The organic-inorganic hybrid composite corrosion inhibitor as claimed in claim 1, wherein the molecular weight of the chitosan is 3000-200000.
4. The organic-inorganic hybrid composite corrosion inhibitor as claimed in claim 1, wherein the pyridine aldehyde compound is at least one of pyridine-4-formaldehyde, 5-chloro-2-pyridinecarboxaldehyde, pyridine-2-carboxaldehyde, 2, 6-pyridinedicarboxaldehyde, pyridine-3-carboxaldehyde and 5-methoxy-3-pyridinecarboxaldehyde.
5. The preparation method of the organic-inorganic hybrid composite corrosion inhibitor as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) reacting chitosan with pyridine aldehyde compounds at 30-60 ℃ for 4-6h by taking a solvent as a reaction medium, filtering, washing and drying to obtain pyridine aldehyde compound modified chitosan;
(2) adding pyridine aldehyde compound modified chitosan into nano zinc oxide aqueous solution, stirring and reacting for 2-4h at room temperature, collecting precipitate, washing, and drying to obtain the organic-inorganic hybrid composite corrosion inhibitor.
6. The preparation method of the organic-inorganic hybrid composite corrosion inhibitor as claimed in claim 5, wherein the concentration of the nano zinc oxide aqueous dispersion in step (2) is 1-4 mg/mL.
7. The preparation method of the organic-inorganic hybrid composite corrosion inhibitor according to claim 5, wherein the pyridine aldehyde compound modified chitosan in the step (1) is prepared by the following method: uniformly mixing the aqueous solution of chitosan acetic acid and the aqueous solution of pyridine aldehyde compound ethanol, then reacting for 4-6h at 30-60 ℃, filtering, washing and drying to obtain the pyridine aldehyde compound modified chitosan.
8. The preparation method of the organic-inorganic hybrid composite corrosion inhibitor according to claim 7, wherein the chitosan acetic acid aqueous solution is prepared by dissolving chitosan in acetic acid aqueous solution, wherein the concentration of chitosan in the solution is 12-24mg/mL, and the concentration of acetic acid in the acetic acid aqueous solution is 0.1-0.3 mol/L;
the pyridine aldehyde compound ethanol aqueous solution is obtained by dissolving a pyridine aldehyde compound in an ethanol aqueous solution, wherein the concentration of the pyridine aldehyde compound in the ethanol aqueous solution is 40-60mg/mL, and the concentration of ethanol in the ethanol aqueous solution is 0.2-0.3 mol/L.
9. The preparation method of the organic-inorganic hybrid composite corrosion inhibitor according to claim 5, wherein the solvent in the step (1) is at least one of acetic acid, ethanol and water.
10. Use of an organic-inorganic hybrid composite corrosion inhibitor as claimed in any one of claims 1 to 4.
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| CN (1) | CN114635137A (en) |
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| US20160208165A1 (en) * | 2015-01-21 | 2016-07-21 | University Of Science And Technology Beijing | Preparation method of low-ph controlled-release intelligent corrosion inhibitor |
| CN106117391A (en) * | 2016-06-28 | 2016-11-16 | 田东县浙缘农业科技有限公司 | A kind of preparation method of chitosan aroma type Schiff |
| CN108866560A (en) * | 2018-08-27 | 2018-11-23 | 合肥绿洁环保科技有限公司 | A kind of environment-friendly antirust metal cleaner |
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| US20160208165A1 (en) * | 2015-01-21 | 2016-07-21 | University Of Science And Technology Beijing | Preparation method of low-ph controlled-release intelligent corrosion inhibitor |
| CN106117391A (en) * | 2016-06-28 | 2016-11-16 | 田东县浙缘农业科技有限公司 | A kind of preparation method of chitosan aroma type Schiff |
| CN108866560A (en) * | 2018-08-27 | 2018-11-23 | 合肥绿洁环保科技有限公司 | A kind of environment-friendly antirust metal cleaner |
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| RAMANATHAN MENAKA ET AL.: ""Chitosan Schiff base as effective corrosion inhibitor for mild steel in acid medium"", 《POLYMER INTERNATIONAL》 * |
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Application publication date: 20220617 |