CN102433564B - Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline - Google Patents
Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline Download PDFInfo
- Publication number
- CN102433564B CN102433564B CN201110287039.2A CN201110287039A CN102433564B CN 102433564 B CN102433564 B CN 102433564B CN 201110287039 A CN201110287039 A CN 201110287039A CN 102433564 B CN102433564 B CN 102433564B
- Authority
- CN
- China
- Prior art keywords
- oxy
- acetatebenzaldehyde
- substituted aniline
- schiff
- contracting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/146—Nitrogen-containing compounds containing a multiple nitrogen-to-carbon bond
Abstract
The invention discloses a preparation method of a Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline. The Schiff-base corrosion inhibitor is a solution formed by water and a product generated from condensation of o-oxy-acetate-benzaldehyde and substituted aniline. In terms of structure, the Schiff base contains an acid group, imino and two phenylrings. As the molecular system forms a large Pi-Pi conjugate, the Schiff base is stable and is not easy to decompose. As the structure is easy to accept exotic electrons, it has strong coordination ability, and compact and stable assembled monolayers can be formed on the surface of metal, thus effectively inhibiting corrosion to metal. Based on the characteristic, the Schiff-base corrosion inhibitor can be applied to prevent a steel material from being corroded. The corrosion inhibitor provided by the invention is simple to prepare, is convenient to use, contains low toxicity, is high efficient, generates no pollution to the environment, and has good corrosion inhibition of the No. 20 carbon steel.
Description
Technical field
The present invention relates to suppress the preparation method of the o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases inhibiter that carbon steel corrodes in oil-field water, belong to green corrosion inhibitor molecular designing field.
Background technology
Metallic substance in use all can have corrosion in various degree, and the metallic substance after the corrosion has just lost original use value, has become solid waste.The chemical property of carbon steel is more active, is easy to suffer environmental factors to bring out various local corrosions and uniform corrosion, causes heavy losses for industrial production and national economy, and is therefore rather urgent and important to the research of this metalloid corrosion prevention.Metallic corrosion is in economic loss, also caused the waste of resource and the energy, because equipment or the hardware quantity of scrapping are huge, and the process of again smelting these discarded metals of regeneration not only can expend a large amount of energy, simultaneously owing to containing other impurity (such as plastics etc.) in this part metal, also go out a large amount of poisonous and hazardous smelting exhausts to environmental emission, affected Air quality, destroyed ecotope.
The petroleum industry etching problem is to enliven the most and one of the most valued research field.The data drawn according to relevant department's statistical study, scrapping of 70% oil exploration equipment is relevant with corrosion.Along with oilfield exploitation enters high water-cut stage, the oil well etching problem is day by day serious, has become the major hidden danger that affects oilfield safety production and economical operation.
1949, the U.S. reported the anti-CO of the organic N of containing imidazoline and its derivative
2The corrosion inhibitor for oil field of corrosion, until the end of the seventies, the appearance of 7701 type composite corrosion inhibitors, China has just solved the acidifying corrosion inhibitor for oil well technical barrier.
The Molecular Structure Design of present organic inhibitor, also there are problems in synthetic route and technique, application performance, and the theoretical investigation progress far lags behind the practice needs.The synthetic low cost of design, low toxicity, high-recovery, high-dissolvability, efficient, eco-friendly green corrosion inhibitor, carrying capacity of environment and the economic benefit of comprehensive evaluation and the application and development of understanding inhibiter have been the new direction of inhibiter and technical development thereof.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of efficient, nontoxic, cheap o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases inhibiter, self-assembly is at the 20# steel surface under the assistance of distilled water, thereby reach the efficient corrosion inhibition that carbon steel corrodes in the simulated oil water in field, to replace the inhibiter of existing serious environment pollution.
Concrete steps are:
(1) aqueous solution that 50mL is dissolved with 20.0～21.5g sodium hydroxide joins and is dissolved with in the pure salicylic aldehyde of 25.5～26.5mL and the pure chloroacetic 65～70mL aqueous solution of 23.0～24.0g, stirs, and refluxes cooling in the oil bath 3～4 hours; Then with weight percent concentration be 37.5% hcl acidifying to pH be 1～2, remove unreacted salicylic aldehyde with wet distillation; Remove again the dark oil thing, cooling, crystallization, suction filtration is precipitated, recrystallization in the boiling water, drying gets white crystalline o-Oxy-acetatebenzaldehyde;
(2) 5～7mL being dissolved with the anhydrous methanol of 0.224～1.23gKOH or dehydrated alcohol or water and dehydrated alcohol mixed solution is added in the anhydrous methanol or ethanol solution that 10～30mL contains the pure o-Oxy-acetatebenzaldehyde that 0.36～1.81g step (1) makes, mix with anhydrous methanol or the dehydrated alcohol that 10～30mL contains 0.274～1.371g gavaculine or 0.274～1.371g p-aminophenyl first carboxylic or 0.346～1.732g Sulphanilic Acid again, refluxed 3～4 hours 68～80 ℃ of lower water-baths, place cooling, suction filtration, the gained solid is with anhydrous methanol or absolute ethanol washing 2～3 times, drying gets o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases;
(3) be that to join weight percent be that stirring and dissolving is mixed with the aqueous solution and is inhibiter of the present invention in 95～99.99% the distilled water for o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases that 0.01～5% step (2) makes with weight percent.
The structural formula of above-mentioned o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases is:
Wherein: R be between position benzene first carboxylic sylvite, contraposition benzene first carboxylic sylvite or contraposition Phenylsulfonic acid sylvite.
Inhibiter of the present invention can be containing of 75～95g/L of saturated CO in salinity
2Simulation oil field aqueous corrosion solution in, temperature is used in 35～80 ℃ of situations well, inhibition efficiency can be up to 95.36%.
The inhibiter of the present invention preparation has that preparation is simple, easy to use, low toxicity, the advantage such as efficient, free from environmental pollution, and the 20# carbon steel is had good corrosion inhibition.
Description of drawings
Accompanying drawing is preparation technology's schema of o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases inhibiter of the present invention.
Embodiment
Embodiment 1:
(1) joins under the aqueous solution that 50mL is dissolved with 20.0g sodium hydroxide stirs and be dissolved with in the pure salicylic aldehyde of 26mL and the pure chloroacetic 70mL aqueous solution of 23.7g, ebuillition of heated in the oil bath, refluxed 3.5 hours, naturally cooling, then with weight percent concentration be 37.5% hcl acidifying to pH be 2, remove unreacted salicylic aldehyde with wet distillation; Remove again the dark oil thing, cooling, crystallization, suction filtration is precipitated, recrystallization in the boiling water, drying gets the crystalline o-Oxy-acetatebenzaldehyde of 9.8g snowy white;
(2) 5mL being dissolved with the dehydrated alcohol of 0.28gKOH and distilled water mixed solution is added in the ethanol solution that 20mL is dissolved with the o-Oxy-acetatebenzaldehyde that 0.91g step (1) makes, mix with the dehydrated alcohol that 20mL contains the 0.69g gavaculine again, refluxed 3.5 hours 70 ℃ of lower water-baths, place cooling, suction filtration, white-yellowish solid with a small amount of absolute ethanol washing 2 times, dry must 1.64g o-Oxy-acetatebenzaldehyde contracting gavaculine sylvite schiff bases;
(3) be that to join weight percent be that stirring and dissolving is mixed with the aqueous solution and is inhibiter of the present invention in 98.1% the distilled water for o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases that 1.9% step (2) makes with weight percent.
The structural formula of above-mentioned o-Oxy-acetatebenzaldehyde contracting gavaculine sylvite schiff bases is:
Evaluation result to the corrosion inhibitor product of embodiment 1:
Method of polarization curve is adopted in the inhibition experiment, use three-electrode system, it is working electrode that self-assembly has schiff bases inhibiter functional membrane and unassembled blank carbon steel sample, and platinum wire electrode is reference electrode, saturated calomel electrode is supporting electrode, and used etchant solution is that salinity is containing of 80g/L of saturated CO
2The simulated oil water in field has the variation of schiff bases inhibiter functional membrane and unassembled blank carbon steel sample corrosion current to measure erosion rate and inhibition efficiency according to self-assembly.Experiment material is the 20# carbon steel, and specification is 50mm * 13mm * 1.5mm, and specimen surface is long-pending to be 240mm
2, specimen in use is placed in the loft drier that silica-gel drier is housed for subsequent use behind the 24h through polishing, deionized water rinsing, alcohol wash, cold air drying.
During experiment working electrode is dipped in the simulation oil field aqueous corrosion solution, begins to test polarization curve after open circuit potential is stablized, scanning speed is 0.01V/s, and scanning polarization scope is-1.0V-1.0V.Read corrosion current from polarization curve, and be calculated as follows inhibition efficiency:
η＝(J
0 corr-J
corr)/J
0 corr×100％
In the formula, J
0 CorrBe blank test piece corrosion current, can utilize polarization curve to try to achieve by extrapotation; J
CorrCorrosion current for the self-assembly corrosion inhibition film test piece.
To the schiff bases inhibiter self-assembly of embodiment 1 at steel surface at saturated CO
2The evaluation result of simulation oil field aqueous corrosion solution sees Table 1.
Estimate under the inhibiter normal temperature and pressure conditions of table 1 couple embodiment 1
Embodiment 2:
(1) identical with embodiment 1;
(2) 5mL being dissolved with the dehydrated alcohol of 0.28gKOH and distilled water mixed solution is added in the ethanol solution that 20mL is dissolved with the o-Oxy-acetatebenzaldehyde that 0.91g step (1) makes, then mix with the dehydrated alcohol that 20mL is dissolved with the 0.69g para-amino benzoic acid, refluxed 3.5 hours 70 ℃ of lower water-baths, place cooling, suction filtration, the gained white solid is with a small amount of absolute ethanol washing 2 times, dry 1.62g o-Oxy-acetatebenzaldehyde contracting potassium ρ-aminobenzoate salt schiff bases;
(3) be that to join weight percent be that stirring and dissolving is mixed with the aqueous solution and is inhibiter of the present invention in 98.1% the distilled water for o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases that 1.9% step (2) makes with weight percent.
The structural formula of above-mentioned o-Oxy-acetatebenzaldehyde contracting potassium ρ-aminobenzoate salt schiff bases is:
Evaluation result to the corrosion inhibitor product of embodiment 2:
Schiff bases corrosion inhibitor product self-assembly to embodiment 2 sees Table 2 at steel surface in the evaluation result of saturated CO2 simulation oil field aqueous corrosion solution.
Estimate under the inhibiter normal temperature and pressure conditions of table 2 couple embodiment 2
Embodiment 3:
(1) identical with embodiment 1;
(2) 5mL being dissolved with the dehydrated alcohol of 0.28gKOH and distilled water mixed solution is added in the ethanol solution that 20mL is dissolved with the o-Oxy-acetatebenzaldehyde that 0.91g step (1) makes, then mix with the distilled water mixed solution with the dehydrated alcohol that 20mL is dissolved with the 0.866g Sulphanilic Acid, refluxed 3.5 hours 70 ℃ of lower water-baths, place cooling, suction filtration, the gained light yellow solid is with a small amount of absolute ethanol washing 3 times, dry 1.23g o-Oxy-acetatebenzaldehyde contracting Sulphanilic Acid sylvite schiff bases;
(3) be that to join weight percent be that stirring and dissolving is mixed with the aqueous solution and is inhibiter of the present invention in 97.9% the distilled water for o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases that 2.1% step (2) makes with weight percent.
The structural formula of above-mentioned o-Oxy-acetatebenzaldehyde contracting Sulphanilic Acid sylvite schiff bases is:
Evaluation result to the corrosion inhibitor product of embodiment 3:
To the schiff bases corrosion inhibitor product self-assembly of embodiment 3 at steel surface at saturated CO
2The evaluation result of simulation oil field aqueous corrosion solution sees Table 3.
Estimate under the inhibiter normal temperature and pressure conditions of table 3 couple embodiment 3
Claims (1)
1. the preparation method of an o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases inhibiter is characterized in that concrete steps are:
(1) aqueous solution that 50mL is dissolved with 20.0～21.5g sodium hydroxide joins and is dissolved with in the pure salicylic aldehyde of 25.5～26.5mL and the pure chloroacetic 65～70mL aqueous solution of 23.0～24.0g, stirs, and refluxes cooling in the oil bath 3～4 hours; Then with weight percent concentration be 37.5% hcl acidifying to pH be 1～2, remove unreacted salicylic aldehyde with wet distillation; Remove again the dark oil thing, cooling, crystallization, suction filtration is precipitated, recrystallization in the boiling water, drying gets white crystalline o-Oxy-acetatebenzaldehyde;
(2) 5～7mL being dissolved with the anhydrous methanol of 0.224～1.23gKOH or dehydrated alcohol or water and dehydrated alcohol mixed solution is added in the anhydrous methanol or ethanol solution that 10～30mL contains the pure o-Oxy-acetatebenzaldehyde that 0.36～1.81g step (1) makes, mix with anhydrous methanol or the dehydrated alcohol that 10～30mL contains 0.274～1.371g gavaculine or 0.274～1.371g para-amino benzoic acid or 0.346～1.732g Sulphanilic Acid again, refluxed 3～4 hours 68～80 ℃ of lower water-baths, place cooling, suction filtration, the gained solid is with anhydrous methanol or absolute ethanol washing 2～3 times, drying gets o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases;
(3) be that to join weight percent be that stirring and dissolving is mixed with the aqueous solution and is o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases inhibiter in 95～99.99% the distilled water for o-Oxy-acetatebenzaldehyde contracting substituted aniline schiff bases that the step (2) of 0.01～5 % makes with weight percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110287039.2A CN102433564B (en) | 2011-09-23 | 2011-09-23 | Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110287039.2A CN102433564B (en) | 2011-09-23 | 2011-09-23 | Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102433564A CN102433564A (en) | 2012-05-02 |
| CN102433564B true CN102433564B (en) | 2013-09-18 |
Family
ID=45981906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110287039.2A Active CN102433564B (en) | 2011-09-23 | 2011-09-23 | Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102433564B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924324B (en) * | 2012-11-19 | 2014-11-12 | 长沙理工大学 | Schiff base, as well as preparation and applications of Schiff base as pickling inhibitor for steel products |
| US9120914B2 (en) * | 2013-09-23 | 2015-09-01 | Milliken & Company | Thermoplastic polymer composition |
| CN103497122B (en) * | 2013-09-27 | 2015-07-22 | 桂林理工大学 | 3,5-dibromosalicylaldehyde shrinkage para aminobenzoic acid Schiff base based polyethylene glycol monolaurate and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074204A (en) * | 2007-06-16 | 2007-11-21 | 西南科技大学 | Production of schiff base |
| CN101805906A (en) * | 2010-04-15 | 2010-08-18 | 桂林理工大学 | Composite corrosion inhibitor for restraining corrosion of carbon steel in seawater and preparation method thereof |
| CN101988202A (en) * | 2009-08-07 | 2011-03-23 | 中国科学院海洋研究所 | Carboxymethyl chitosan oligosaccharide schiff base organic carbon steel seawater corrosion inhibitor and application thereof |
-
2011
- 2011-09-23 CN CN201110287039.2A patent/CN102433564B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074204A (en) * | 2007-06-16 | 2007-11-21 | 西南科技大学 | Production of schiff base |
| CN101988202A (en) * | 2009-08-07 | 2011-03-23 | 中国科学院海洋研究所 | Carboxymethyl chitosan oligosaccharide schiff base organic carbon steel seawater corrosion inhibitor and application thereof |
| CN101805906A (en) * | 2010-04-15 | 2010-08-18 | 桂林理工大学 | Composite corrosion inhibitor for restraining corrosion of carbon steel in seawater and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102433564A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Magnolia grandiflora leaves extract as a novel environmentally friendly inhibitor for Q235 steel corrosion in 1 M HCl: Combining experimental and theoretical researches | |
| Hegazy et al. | Synthesis, surface properties and inhibition behavior of novel cationic gemini surfactant for corrosion of carbon steel tubes in acidic solution | |
| Hegazy et al. | Electrochemical studies on the inhibition behavior of copper corrosion in pickling acid using quaternary ammonium salts | |
| Tawfik et al. | Three gemini cationic surfactants as biodegradable corrosion inhibitors for carbon steel in HCl solution | |
| CN103555313B (en) | A kind of imidazolium ionic liquid acidification corrosion inhibitor and preparation method thereof and application | |
| Yadav et al. | Eco-friendly corrosion inhibitors for N80 steel in hydrochloric acid | |
| CN103046055B (en) | Imidazolyl lysine salt ionic liquid is as the application of iron and steel inhibiter | |
| WO2020093444A1 (en) | Method for preparing mannich base quaternary ammonium salt-based high temperature resistant acidizing corrosion inhibitor and use of same | |
| CN102433564B (en) | Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline | |
| CN102352501B (en) | Method for forming corrosion inhibiting film on steel and iron surface | |
| Thirumalairaj et al. | Corrosion protection of mild steel by a new binary inhibitor system in hydrochloric acid solution | |
| CN104762075A (en) | Corrosion inhibitor used for oil field water, preparation method and detection method | |
| CN108642500B (en) | Water-soluble bipyridyl gemini quaternary ammonium salt corrosion inhibitor and preparation method and application thereof | |
| CN108754510B (en) | Composite pickling corrosion inhibitor containing Schiff base and preparation method thereof | |
| CN107501325A (en) | A kind of amino organophosphor acids corrosion inhibiter synthetic method and purposes | |
| CN101818349A (en) | Application of 1-myristyl-3-methylimidazolium chloride ionic liquid serving as steel corrosion inhibitor | |
| CN110105390B (en) | Alkyl triphenyl phosphonium bis (trifluoromethane) sulfonyl imide ionic liquid, synthesis method and application as corrosion inhibitor of magnesium alloy material | |
| CN108689865A (en) | A kind of water soluble rust inhibitor and preparation method and application containing xenyl | |
| Subramania et al. | Aldimines—Effective corrosion inhibitors for mild steel in hydrochloric acid solution | |
| CN110565100B (en) | Cobaltocene cation-based corrosion inhibitor and preparation method and use method thereof | |
| CN105002505A (en) | Preparation method of indigo carmine/benzyltrimethyl ammonium bromide composite corrosion inhibitor used for 1045 carbon steel hydrochloric acid pickling solution | |
| CN104876835B (en) | Preparation method and application of Mannich double base | |
| CN108341809A (en) | A kind of steel corrosion inhibitor and its preparation method and application | |
| CN108707107A (en) | A kind of bipyridyl gemini quaternary ammonium salt corrosion inhibiter and preparation method and application | |
| CN114671814A (en) | Mercapto pyrimidine derivative quaternary ammonium salt corrosion inhibitor and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201028 Address after: 226300 Shigang Science and Technology Industrial Park, Tongzhou District, Nantong City, Jiangsu Province Patentee after: NANTONG BOQIANG MACHINERY PARTS MANUFACTURING Co.,Ltd. Address before: 541004 Guilin city of the Guangxi Zhuang Autonomous Region Road No. 12 building of Guilin University of Technology Patentee before: GUILIN University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |