CN117384090A - Preparation method and application of 3-aminopyridine benzaldehyde corrosion inhibitor - Google Patents
Preparation method and application of 3-aminopyridine benzaldehyde corrosion inhibitor Download PDFInfo
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- CN117384090A CN117384090A CN202311150267.4A CN202311150267A CN117384090A CN 117384090 A CN117384090 A CN 117384090A CN 202311150267 A CN202311150267 A CN 202311150267A CN 117384090 A CN117384090 A CN 117384090A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 95
- 230000007797 corrosion Effects 0.000 title claims abstract description 95
- 239000003112 inhibitor Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 12
- WIMFFCQRZJFPID-UHFFFAOYSA-N benzaldehyde pyridin-3-amine Chemical compound C(C1=CC=CC=C1)=O.N1=CC(=CC=C1)N WIMFFCQRZJFPID-UHFFFAOYSA-N 0.000 title description 3
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims abstract description 122
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 26
- 239000002262 Schiff base Substances 0.000 claims abstract description 25
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 14
- 239000010962 carbon steel Substances 0.000 claims description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 11
- 230000002195 synergetic effect Effects 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000002633 protecting effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- -1 3-aminopyridine benzaldehyde compound Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XLOBHUFFBWEBQY-UHFFFAOYSA-N benzaldehyde;ethanol Chemical compound CCO.O=CC1=CC=CC=C1 XLOBHUFFBWEBQY-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940057004 coal tar extract Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a preparation method and application of a 3-aminopyridine formal corrosion inhibitor, and belongs to the technical field of organic synthesis. The structural formula of the 3-aminopyridine benzaldehyde compound provided by the invention is shown as the following formula (I): the invention provides a 3-aminopyridine formal compound, which is obtained by Schiff base reaction of 3-aminopyridine and benzaldehyde, and has the advantages of low metal corrosion rate, high slow release rate, less mass loss and good metal corrosion protection effect when the compound is used for carrying out corrosion protection on metal; the synthesis process is simple, the reaction condition is mild, the raw materials are cheap and easy to obtain, and the method is suitable for large-scale production and is used for goldBelongs to corrosion protection and has wide application.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method and application of a 3-aminopyridine formal corrosion inhibitor.
Background
In many industrial processes, corrosion of carbon steel causes serious damage to transportation and production equipment. Although corrosion problems are unavoidable, the necessary protection methods are indispensable. Taking petroleum exploitation as an example, due to the very complex exploitation and transportation environment, common acidic medium CO 2 、H 2 S further exacerbates metal corrosion. The corrosion inhibitor exists in a certain environment medium in a proper concentration and form, and in order to slow down the corrosion of the acid liquor to the pipeline equipment, the addition of the corrosion inhibitor is the most important protection measure.
The initial development of the acidizing corrosion inhibitor can be traced to the thirties of the last century, and a 'sulfonated anthracene oil' is prepared by a soviet union scientist and is widely applied. In the past fifty years, japanese researchers discovered that the coal tar extract "benzotriazole" was used as a copper-based corrosion inhibitor and exhibited excellent properties. The research of the acidizing corrosion inhibitor is later, and the new corrosion inhibitor product independently developed in China is a new step along with the further development of petrochemical industry, wherein the imidazoline corrosion inhibitor product is mainly used, and the slow release effect under different working conditions is achieved by introducing synergistic corrosion inhibitors such as antimony salt, potassium iodide, urotropine, thiourea and the like. In recent years, numerous corrosion inhibitor researchers have placed their focus on substrate synthesis and later compounding schemes for corrosion inhibitors, with green, low-toxicity, environmental-friendly corrosion inhibitors becoming increasingly interesting. For example, the introduction of small molecular compounds, degradable high molecular polymers and low-toxicity quaternary ammonium salts is favored by researchers.
After the 21 st century, schiff base corrosion inhibitors gradually enter the field of view as common high-temperature acidification corrosion inhibitors, and a series of corrosion inhibitor molecules with different characteristics are synthesized by aldehyde, ketone, acid compounds and amine compounds. The Schiff base structure contains N atoms with higher electronegativity, the lone pair electrons of the N atoms have strong coordination capability, are easy to adsorb on the surface of metal, and can form a stable p-pi conjugated system with-C=C-. Because of the good adaptability of the reaction substrate, the Schiff base corrosion inhibitor is far more excellent in variety and applicability than other corrosion inhibitors. The application research of Schiff base corrosion inhibitors is relatively few in China, and the Schiff base corrosion inhibitors mainly stay in basic theoretical research.
Disclosure of Invention
In order to overcome the problems of the prior art, it is an object of the present invention to provide a 3-aminopyridine formal compound having a corrosion inhibiting effect and a good metal corrosion protecting effect.
The second object of the present invention is to provide a process for producing the above 3-aminopyridine formal compound.
It is a further object of the present invention to provide a 3-aminopyridine formal corrosion inhibitor comprising the above 3-aminopyridine formal compound.
The invention also provides an application of the 3-aminopyridine formal compound or the 3-aminopyridine formal corrosion inhibitor.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a 3-aminopyridine benzaldehyde compound with a structural formula shown in the following formula (I):
in a second aspect, the present invention provides a method for preparing a 3-aminopyridine formal compound according to the first aspect of the present invention, comprising the steps of: and (3) performing Schiff base reaction on the 3-aminopyridine and benzaldehyde to obtain the 3-aminopyridine formal compound.
Preferably, in the preparation method of the 3-aminopyridine formal compound, the molar ratio of 3-aminopyridine to benzaldehyde is 1: (0.5-2); further preferably 1: (0.6-1.5); still more preferably 1: (0.8-1.2).
Preferably, in the preparation method of the 3-aminopyridine formal compound, the schiff base reaction is performed in a solvent; further preferably, the solvent comprises at least one of methanol, ethanol, dichloromethane or dimethyl sulfoxide; still more preferably, the solvent is selected from methanol.
Preferably, in the preparation method of the 3-aminopyridine formal compound, the temperature of the Schiff base reaction is 20-100 ℃; further preferably 30 to 90 ℃; still more preferably 60 to 80 ℃.
Preferably, in the preparation method of the 3-aminopyridine formal compound, the Schiff base reaction time is 2-15 h; further preferably 4 to 10 hours; more preferably 5 to 7 hours.
In a third aspect the present invention provides a 3-aminopyridine formal corrosion inhibitor comprising a 3-aminopyridine formal compound according to the first aspect of the invention.
The 3-aminopyridine benzaldehyde corrosion inhibitor is a Schiff base corrosion inhibitor.
Preferably, the mass percentage of the 3-aminopyridine formal compound in the corrosion inhibitor is 0.01-0.2 wt%; further preferably 0.02 to 0.15wt%; still more preferably 0.06 to 0.1wt%.
Preferably, the corrosion inhibitor further comprises a synergistic corrosion inhibitor, wherein the synergistic corrosion inhibitor comprises at least one of potassium iodide (KI), thiourea, benzotriazole or sodium molybdate; further preferably, the synergistic corrosion inhibitor comprises at least one of thiourea, benzotriazole or sodium molybdate; still more preferably, the synergistic corrosion inhibitor is selected from thiourea.
Preferably, in the corrosion inhibitor, the mass ratio of the 3-aminopyridine formal compound to the synergistic corrosion inhibitor is 10: (0.5-3); further preferably 10: (0.7-2); still more preferably 10: (0.8-1.2).
In a fourth aspect, the present invention provides the use of a 3-aminopyridine formal compound according to the first aspect of the invention, or a 3-aminopyridine formal corrosion inhibitor according to the third aspect of the invention, for protecting metals against corrosion.
Preferably, the metal is selected from carbon steel.
Preferably, the carbon content in the carbon steel is 1-3 wt%; further preferably 1.5 to 2.5wt%.
Preferably, the alloying elements of the carbon steel further comprise at least one of manganese, phosphorus or sulfur.
Preferably, the carbon steel comprises the following alloy elements in percentage by mass: 1 to 3 weight percent of carbon, 1 to 3 weight percent of manganese, 1 to 3 weight percent of phosphorus and 2 to 4 weight percent of sulfur; further preferably, the carbon steel comprises the following alloy elements in mass percent: 1.5 to 2.5 weight percent of carbon, 1.5 to 2.5 weight percent of manganese, 1.5 to 2.5 weight percent of phosphorus and 2.5 to 3.5 weight percent of sulfur.
In a specific embodiment of the invention, the carbon steel is selected from X65 carbon steel.
The beneficial effects of the invention are as follows: the invention provides a 3-aminopyridine formal compound, which is obtained by Schiff base reaction of 3-aminopyridine and benzaldehyde, and has the advantages of low metal corrosion rate, high slow release rate, less mass loss and good metal corrosion protection effect when the compound is used for carrying out corrosion protection on metal; the synthesis process is simple, the reaction condition is mild, the raw materials are cheap and easy to obtain, the method is suitable for large-scale production, and the method has wide application in metal corrosion protection.
Specifically, compared with the prior art, the invention has the following advantages:
1. the preparation method of the 3-aminopyridine formal compound provided by the invention has the advantages of simple process, mild reaction conditions, good synthesis efficiency and high yield.
2. The invention adopts the synergistic corrosion inhibitor to compound the prepared 3-aminopyridine formal compound, and the obtained Schiff base corrosion inhibitor has better corrosion inhibition efficiency and good slow release effect.
3. The 3-aminopyridine formal compound has good corrosion protection effect on metals, especially carbon steel, and has wide application in the field of metal corrosion protection, especially carbon steel corrosion protection.
Drawings
FIG. 1 shows the nuclear magnetic resonance spectrum of the product obtained in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the product obtained in example 1.
FIG. 3 is an infrared spectrum of the product obtained in example 1.
FIG. 4 is a graph showing the mass loss of steel sheet as a function of the concentration of 3-aminopyridine formal compound in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
Wherein, in a specific embodiment of the invention, the carbon steel is selected from X65 carbon steel, and the X65 carbon steel comprises the following alloy elements in percentage by mass: 2wt% carbon, 2wt% manganese, 2wt% phosphorus, 3wt% sulfur.
Example 1
The example provides a 3-aminopyridine formal compound with a structural formula shown as the following formula (I):
the preparation method of the 3-aminopyridine formal compound comprises the following steps:
(1) Weighing 0.53g of benzaldehyde, placing the benzaldehyde into a round bottom flask containing 15mL of absolute ethyl alcohol, and magnetically stirring the benzaldehyde uniformly;
(2) Weighing 3-aminopyridine of corresponding mass according to the mole ratio of 3-aminopyridine to benzaldehyde in table 1, adding the 3-aminopyridine into 30mL absolute ethyl alcohol, and slightly heating until the 3-aminopyridine is completely dissolved;
(3) Heating the benzaldehyde ethanol solution in the step (1) to the temperature shown in the table 1, slowly mixing the solution obtained in the step (2) with the benzaldehyde ethanol solution, and carrying out reflux reaction through TLC detection in the reaction process, wherein the reaction time is the reaction time shown in the table 1;
(4) After the reaction was completed, the liquid was concentrated to 30mL by distillation under reduced pressure, the obtained product was cooled in an ice-water bath, and after the solid was precipitated, it was washed with ethanol, and V ethanol was used: v chloroform = 3:1, recrystallizing the mixed solution, and drying to obtain a product; or purifying the crude product by column chromatography (V petroleum ether: V ethyl acetate=5:1) to finally obtain a yellow product.
Table 1 3 preparation reaction conditions and products of aminopyridine formal compounds
In this example, four-factor four-level orthogonal experimental screening of the preparation conditions of 3-aminopyridine formal compounds was performed, and as can be seen from Table 1, the method provided in this example can be used to prepare 3-aminopyridine formal compounds with high yields. Wherein, the optimal reaction conditions obtained by the screening of the orthogonal test are as follows: the molar ratio of 3-aminopyridine to benzaldehyde is 1: 1. the reaction temperature is 70 ℃, the reaction time is 6 hours, and the solvent is C 2 H 5 OH, under the optimal reaction conditions, 3-aminopyridine formal compounds with yields as high as 91% can be obtained. The obtained product is subjected to structural characterization, a nuclear magnetic hydrogen spectrum is shown in a figure 1, a nuclear magnetic carbon spectrum is shown in a figure 2, and specific nuclear magnetic characterization data are as follows:
1 H NMR(600MHz,Chloroform-d)δ8.57-8.42(m,3H),7.92(dd,J＝8.0,1.7Hz,2H),7.64–7.44(m,4H),7.33(ddd,J＝8.0,4.7,0.8Hz,1H).
13 C NMR(151MHz,Chloroform-d)δ162.1,147.9,147.2,142.6,135.7,132.0,129.0,128.9,127.9,123.7.
the standard H spectrum and the carbon spectrum of the combined benzaldehyde pyridyl molecule can correspond to known molecules, and the synthetic product is a compound shown as a quasi-synthesized formula (I).
The infrared spectrum of the product is shown in FIG. 3, 2917cm -1 Is provided with a-C-H-bond telescopic vibration absorption peak at 1623cm -1 The strong absorption peak for-c=n-stretching vibration indicates that the most critical functional group-c=n-indicates that synthesis has been successful.
Example 2
The Schiff base corrosion inhibitor is prepared by dissolving the 3-aminopyridine benzaldehyde compound prepared in the embodiment 1 in acid, and the concentration of the 3-aminopyridine benzaldehyde compound is 0.02wt%, 0.04wt%, 0.06wt%, 0.08wt% and 0.1wt% respectively.
The Schiff base corrosion inhibitor obtained in the example is applied to corrosion protection of metals. Wherein the metal used is X65 metal steel sheet. The specific process comprises the following steps:
cleaning X65 metal steel sheet with ethanol and acetone respectively, air drying, weighing (denoted as m), suspending in blank (i.e. no Schiff base corrosion inhibitor) and 15wt% HCl solution containing Schiff base corrosion inhibitor, soaking for 6 hr, cleaning steel sheet with clear water, ethanol and acetone respectively, drying, and weighing (denoted as m) t ) The mass loss DeltaW and the uniform corrosion rate r are calculated according to the following formula corr And a sustained release rate eta 1 。
ΔW＝m-m t ；
Wherein m is the mass/g of the steel sheet before the experiment, and m t Is the steel sheet after the experimentMass/g, S 1 Is the total area of the steel sheet/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the ρ is the density of the steel sheet/g.cm -3 The method comprises the steps of carrying out a first treatment on the surface of the t is experimental time/h; delta m0 The mass loss per gram of the steel sheet is a blank group experiment; delta m1 The steel sheet mass loss per gram is tested for adding the Schiff base corrosion inhibitor. The calculated data are shown in Table 2, and the change curve of the mass loss of the steel sheet with the concentration of the 3-aminopyridine formal compound is shown in FIG. 4.
TABLE 2 Metal Corrosion protection Effect of Schiff base Corrosion inhibitors of example 2
As is apparent from table 2 and fig. 4, the slow release rate gradually increases with an increase in the concentration of the 3-aminopyridine formal compound, mainly because the adsorption and coverage of the 3-aminopyridine formal compound on the surface of the steel sheet increases with an increase in the concentration. When the concentration of the 3-aminopyridine formal compound is 0.06wt%, the corrosion rate of the metal is significantly reduced. When the concentration of the 3-aminopyridine formal compound is 0.1wt%, the corrosion rate is reduced to 4.99g/m 2 And/h, and the highest sustained release rate can reach 95.97 percent. Therefore, the Schiff base corrosion inhibitor provided by the embodiment has better metal corrosion protection effect when the addition concentration of the 3-aminopyridine benzaldehyde compound is 0.02-0.1 wt%, and particularly has better metal corrosion protection effect when the addition concentration is 0.06-0.1 wt%.
Example 3
The example provides a Schiff base corrosion inhibitor which is prepared from a 3-aminopyridine formal compound and a synergistic corrosion inhibitor prepared in the example 1, wherein the specific compositions of the 3-aminopyridine formal compound (marked as a compound) and the synergistic corrosion inhibitor are shown in a table 3. The Schiff base corrosion inhibitor obtained in the example is also applied to corrosion protection of metals, the characterization means of the test process and the corrosion protection effect of metals are the same as those of the example 2, and the results are shown in Table 3.
TABLE 3 Schiff base corrosion inhibitor composition and Metal Corrosion protection Effect of example 3
In the example, the compounding work of KI, thiourea, benzotriazole, sodium molybdate and 3-aminopyridine formal compound is further carried out, 80ppm of 3-aminopyridine formal compound is selected to carry out a compounding experiment, as can be seen from Table 3, wherein thiourea, sodium molybdate and triazole all have different degrees of improvement on corrosion inhibition efficiency, the thiourea has the most excellent expression effect, and when the mass ratio of the 3-aminopyridine formal compound to thiourea is 10: at 1, corrosion inhibition rate eta 1 Up to 99.04%, while the further increase of thiourea content does not improve the corrosion inhibition effect.
The invention provides a 3-aminopyridine formal compound, which is obtained by Schiff base reaction of 3-aminopyridine and benzaldehyde, and has the advantages of low metal corrosion rate, high slow release rate, less mass loss and good metal corrosion protection effect when the compound is used for carrying out corrosion protection on metal; the synthesis process is simple, the reaction condition is mild, the raw materials are cheap and easy to obtain, the method is suitable for large-scale production, and the method has wide application in metal corrosion protection.
Claims (10)
1. A 3-aminopyridine formal compound, which is characterized by the following structural formula (I):
2. the method for producing a 3-aminopyridine formal compound according to claim 1, comprising the steps of:
and (3) performing Schiff base reaction on the 3-aminopyridine and benzaldehyde to obtain the 3-aminopyridine formal compound.
3. The method according to claim 2, wherein the molar ratio of 3-aminopyridine to benzaldehyde is 1: (0.5-2).
4. The process according to claim 2, wherein the schiff base reaction is carried out in a solvent; the solvent comprises at least one of methanol, ethanol, methylene chloride or dimethyl sulfoxide.
5. A 3-aminopyridine formal corrosion inhibitor comprising the 3-aminopyridine formal compound of claim 1.
6. The corrosion inhibitor according to claim 5, wherein the mass percentage of the 3-aminopyridine formal compound in the corrosion inhibitor is 0.01 to 0.2wt%.
7. The corrosion inhibitor of claim 5, further comprising a synergistic corrosion inhibitor comprising at least one of potassium iodide, thiourea, benzotriazole, or sodium molybdate.
8. The corrosion inhibitor according to claim 7, wherein the mass ratio of the 3-aminopyridine formal compound to the synergistic corrosion inhibitor is 10: (0.5-3).
9. Use of a compound according to claim 1 or a corrosion inhibitor according to any one of claims 5 to 8 for protecting metals against corrosion.
10. Use according to claim 9, wherein the metal is selected from carbon steel.
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| CN102531957A (en) * | 2012-01-11 | 2012-07-04 | 温州大学 | Synthesis method for imine compounds |
| CN102924324A (en) * | 2012-11-19 | 2013-02-13 | 长沙理工大学 | Schiff base, as well as preparation and applications of Schiff base as pickling inhibitor for steel products |
| CN109134359A (en) * | 2018-09-06 | 2019-01-04 | 桂林理工大学 | A kind of preparation method of 2,6- diamino-pyridine acetal acid Bis-Schiff Bases corrosion inhibiter |
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| CN102531957A (en) * | 2012-01-11 | 2012-07-04 | 温州大学 | Synthesis method for imine compounds |
| CN102924324A (en) * | 2012-11-19 | 2013-02-13 | 长沙理工大学 | Schiff base, as well as preparation and applications of Schiff base as pickling inhibitor for steel products |
| CN109134359A (en) * | 2018-09-06 | 2019-01-04 | 桂林理工大学 | A kind of preparation method of 2,6- diamino-pyridine acetal acid Bis-Schiff Bases corrosion inhibiter |
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