CN113637014B - Heterocyclic triazinyl quaternary ammonium salt and preparation and application thereof - Google Patents
Heterocyclic triazinyl quaternary ammonium salt and preparation and application thereof Download PDFInfo
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
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- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- 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
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- 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
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a heterocyclic triazinyl-containing quaternary ammonium salt, which has a structure represented by the following general formula (I):wherein R is C 4‑10 An alkyl group; x is-NH-or-S-or a combination thereof; y is a nitrogen-containing and/or sulfur-containing aromatic heterocycle with a thioether or imino linking group. The invention has higher corrosion inhibition and sterilization efficiency when the use amount is smaller by the synergistic coupling effect of the heterocycle and the quaternary ammonium salt functional group in the same molecule, and can be used as a corrosion inhibitor, in particular to the corrosion inhibition and sterilization treatment of carbon steel in the presence of sulfate reducing bacteria.
Description
Technical Field
The invention belongs to the technical field of metal corrosion and protection, relates to a quaternary ammonium salt corrosion inhibition bactericide, and particularly relates to a heterocyclic triazinyl quaternary ammonium salt corrosion inhibition bactericide and application thereof in inhibiting sulfate reducing bacteria corrosion.
Background
Microbial corrosion (Microbiologically influenced corrosion, MIC) refers to the phenomenon in which the corrosion of metallic materials is accelerated directly by the self-life activities of microorganisms or indirectly by their metabolites. It has been counted that the economic losses due to metal corrosion account for about 3-5% of GDP per year, with the economic losses due to microbial corrosion accounting for about 20% of the total economic losses (Chinese corrosion and protection journal, 2021, 41 (1): 1-12.).
Microorganisms involved in MIC mainly include sulfate-reducing bacteria (Sulfate reducing bacteria, SRB), iron-oxidizing bacteria (Iron-oxidizing bacteria, IOB), iron-reducing bacteria (IRB), acid-producing bacteria (Acid-producing bacteria, APB), and the like. It was investigated that in the known MIC case, SRBs were present and involved in one half. Thus, SRB is the primary species responsible for microbial corrosion.
For a long time, the most common method for controlling microbial corrosion is to add a bactericide, which can kill microorganisms and inhibit microbial corrosion. However, after a period of use, bacteria can develop drug resistance, so that the dosage and use cost of the bactericide are increased continuously, and the economic and environmental burden is increased. On the other hand, bactericides are effective against planktonic microorganisms, but hardly kill microorganisms in biofilms. Therefore, it is necessary to design a highly effective corrosion inhibiting bactericide against SRB corrosion and reduce the amount of bactericide used.
The quaternary ammonium salt surfactant has antibacterial and bactericidal functions, low toxicity and wide application range, and has a long history of research on the quaternary ammonium salt surfactant as a bactericide. Meanwhile, the quaternary ammonium salt surfactant can form directional adsorption at the interface, so that a compact protective film can be formed, corrosion of metal is slowed down, and the quaternary ammonium salt surfactant can also be used as a metal corrosion inhibitor.
However, it was found (Corrosion Science, 2017, 117: 24-34.) that SRB could still be locally adsorbed on the surface of the material to form a biofilm with significant localized pits of corrosion in the area where the biofilm was formed, at a mass concentration of 40mg/L of dimethyl alkyl ammonium chloride (alkyl chain length of 10-16).
The heterocyclic compound generally contains hetero atoms (such as N, S, O) with larger electronegativity in the molecule, so that lone pair electrons can be provided to form coordination bonds with the metal surface, and corrosion reaction is prevented; secondly, the heterocyclic compound has pi bond, and can act with the metal surface through a front line molecular orbit to prevent further corrosion reaction; in addition, due to the polarity of the molecules, the metal surface can be covered by electrostatic attraction, so that the corrosion process of the metal can be inhibited. Thus, heterocyclic compounds are commonly used in industry as corrosion inhibitors, but their bactericidal properties against microorganisms are relatively poor.
Disclosure of Invention
The invention aims to provide a heterocyclic triazinyl-containing quaternary ammonium salt, which has higher corrosion inhibition and sterilization efficiency when the use amount is small through the synergistic coupling effect of the same intramolecular heterocycle and the quaternary ammonium salt functional group.
The heterocyclic triazinyl-containing quaternary ammonium salt has a structure represented by the general formula (I):
wherein:
r is C 4-10 An alkyl group; x is-NH-or-S-or a combination thereof; y is a nitrogen-containing and/or sulfur-containing aromatic heterocycle with a thioether or imino linking group.
The heterocyclic triazinyl-containing quaternary ammonium salt represented by the above general formula (I) of the present invention can be prepared by the following method.
Cyanuric chloride is used as raw material, and C is represented by general formula RXH 4-10 Fatty amines or alkylthio of alkyl groupsAlcohol reaction to obtain the compound represented by the general formula (II).
And then the compound shown in the general formula (II) reacts with the sulfhydryl or amino substituted nitrogenous and/or thiaromatic heterocyclic compound shown in the general formula YH to obtain the compound shown in the general formula (III).
And reacting the compound shown in the general formula (III) with N, N-dimethyl-1, 3-propylene diamine to obtain the compound shown in the general formula (IV).
Finally, the compound shown in the general formula (IV) reacts with bromoethane to prepare the heterocyclic triazinyl-containing quaternary ammonium salt shown in the general formula (I).
Further, the specific synthetic route of the preparation method of the heterocyclic triazinyl-containing quaternary ammonium salt represented by the above general formula (I) of the present invention is given below.
Wherein the mercapto or amino substituted nitrogen and/or sulfur containing aromatic heterocyclic compound represented by the general formula YH is preferably any one of 2-mercaptobenzothiazole, 2-aminobenzimidazole or 2-mercapto-5-methyl-1, 3, 4-thiadiazole.
Further, the invention provides a more detailed preparation method of the heterocyclic triazinyl-containing quaternary ammonium salt.
1) In a solvent toluene system in the presence of sodium hydroxide or sodium carbonate acid binding agent, cyanuric chloride is reacted with C represented by the general formula RXH 4-10 The fatty amine or alkyl mercaptan of alkyl is reacted under ice bath conditionAccordingly, a white solid of the compound represented by the general formula (II) is precipitated from the reaction solution.
2) Dissolving a compound shown in a general formula (II) in acetone, adding an acetone water mixed solution of a sulfhydryl or amino substituted nitrogen-containing and/or sulfur-containing aromatic heterocyclic compound shown in a general formula YH, and reacting at 45-50 ℃ to obtain a compound light yellow solid shown in a general formula (III).
3) Gradually adding the compound shown in the general formula (III) into N, N-dimethyl-1, 3-propylene diamine, heating to 30 ℃ for reaction, and separating out a light yellow or white solid of the compound shown in the general formula (IV) from the reaction liquid.
4) Acetonitrile is used as a solvent, a compound shown in a general formula (IV) and bromoethane are added for reaction at 50-60 ℃ to prepare a compound target product shown in the general formula (I).
The invention also provides application of the heterocyclic triazinyl quaternary ammonium salt as a corrosion inhibitor.
In particular, the invention provides application of the heterocyclic triazinyl quaternary ammonium salt as a corrosion inhibitor for inhibiting corrosion of sulfate reducing bacteria.
The invention also provides application of the heterocyclic triazinyl quaternary ammonium salt as a bactericide against sulfate reducing bacteria.
More specifically, the invention provides application of the heterocyclic triazinyl-containing quaternary ammonium salt as a slow-release bactericide of carbon steel in the presence of sulfate reducing bacteria.
The molecular structure of the heterocyclic triazinyl-containing quaternary ammonium salt comprises an alkane chain, a heterocycle and a quaternary ammonium salt structure. The quaternary ammonium salt can be selectively adsorbed on the surface of a biological film of the SRB and permeate into a cell membrane, so that the biological functions of electron transfer, selective substance transfer, isolation barrier and the like of the cell membrane are changed, the selective permeability and genetic system of the cell membrane are destroyed, and the activity of the SRB is inhibited or even dead; on the other hand, the triazine ring and the heterocycle in the molecular structure have rich heteroatoms (N, S) and share pi electrons, and can form coordination bonds with empty d orbitals of iron to carry out chemical adsorption, so that the quaternary ammonium salt surfactant and the heterocyclic compound are combined, and the corrosion inhibition and sterilization performances of the quaternary ammonium salt surfactant and the heterocyclic compound can be further improved through the synergistic effect of the quaternary ammonium salt surfactant and the heterocyclic compound.
At the same time, the alkyl chain contained in the compound structure can form a layer of hydrophobic barrier to prevent invasion of corrosive ions and protect carbon steel from corrosion.
Therefore, the heterocyclic triazinyl-containing quaternary ammonium salt based on the structure disclosed by the invention has higher corrosion inhibition and sterilization performances under a smaller use amount. Compared with the common quaternary ammonium salt bactericide 1227, the heterocyclic triazinyl quaternary ammonium salt has higher efficiency of inhibiting the activity of sulfate reducing bacteria.
Drawings
Fig. 1 is an infrared spectrum of the preparation of the heterocyclic triazinyl-containing quaternary ammonium salt BTOTB of example 1.
FIG. 2 is an ESI-MS spectrum of the preparation of heterocyclic triazinyl quaternary ammonium salt BTOTB of example 1.
FIG. 3 is an infrared spectrum of the preparation of the heterocyclic triazinyl-containing quaternary ammonium salt MTOTB of example 2.
FIG. 4 is an ESI-MS spectrum of the preparation of the heterocyclic triazinyl-containing quaternary ammonium salt MTOTB of example 2.
Fig. 5 is a graph of surface tension versus concentration for BTOTB and MTOTB.
Fig. 6 is a graph showing the effect of static weightlessness experiment.
FIG. 7 is a Nyquist plot of carbon steel immersed in SRB-containing simulated seawater without and with 0.1mM of different corrosion inhibitors, respectively, for different days; in the figure: (a), SRB, (b), BTOTB, (c), MTOTB, (d), 1227.
FIG. 8 is a surface SEM image of a carbon steel coupon after 21d immersion in a different corrosive medium; in the figure: (a), polished carbon steel, (b), SRB, (c), 0.1mM MTOTB, (d), 1227.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are intended only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The experimental methods, production processes, instruments and equipment involved in the embodiments of the present invention have names and abbreviations that are all conventional in the art, and are well-known and obvious in the relevant fields of use, and those skilled in the art can understand the conventional process steps according to the names and apply corresponding equipment, and implement the methods according to conventional conditions or conditions suggested by manufacturers.
The various materials or reagents used in the examples of the present invention are not particularly limited in source, and are conventional products commercially available. The preparation may also be carried out according to conventional methods known to the person skilled in the art.
Example 1: synthesis of heterocyclic triazinyl-containing quaternary ammonium salts (I).
Into a 250mL four-necked flask, 9.25g (0.05 mol) of cyanuric chloride and 100mL of toluene were added, stirring was started, and after all the materials were completely dissolved, 7.10g (0.055 mol) of n-octylamine was added under ice bath conditions to give a 1mol/L concentration of Na 2 CO 3 The pH value of the reaction solution is regulated to 8-9 for reaction.
Thin layer chromatography (silica gel GF) 254 Toluene: methanol=1:1, v/v) was monitored to end.
After the reaction is finished, pumping filtration is carried out, and the filtrate is sequentially treated with 1mol/L hydrochloric acid and 0.5mol/L NaHCO 3 After washing with distilled water to neutrality, the organic layer is collected, dried over anhydrous sodium sulfate, filtered by suction and concentrated under reduced pressure to obtain white solid OT.
2.80g (0.01 mol) of the white solid OT and 100mL of acetone are added into a 250mL four-necked flask, the temperature is raised to 45-50 ℃ under stirring, and after the white solid is completely dissolved, 1.85g (0.011 mol) of the mixed solution of acetone and water=2:1 (v/v) in which 2-mercaptobenzothiazole is dissolved is dripped into the four-necked flask, and the temperature is maintained at 45-50 ℃ under stirring for reaction.
Thin layer chromatography (silica gel GF) 254 Petroleum ether: acetone=3:1, v/v) was monitored to end.
After the reaction is finished, distilled water is added into the reaction liquid, a large amount of light yellow solid BTOT is separated out, and the reaction liquid is washed by hot acetone and then dried in vacuum.
30mL of N, N-dimethyl-1, 3-propanediamine was added to a 250mL three-necked flask equipped with a mechanical stirring device, 2.05g (0.005 mol) of BTOT was added in portions, and the reaction was carried out at 30℃while maintaining the reaction temperature.
Thin layer chromatography (silica gel GF) 254 Acetone: toluene: water=6:1:0.5, v/v/v) was monitored to end.
The reaction solution was dissolved in 100mL of toluene, transferred to a separating funnel, and washed with saturated NaCl multiple times to neutrality. The organic layer was collected, dried over anhydrous sodium sulfate, filtered with suction, concentrated under reduced pressure to give a pale yellow/colorless oil, which was then placed in a fume hood to precipitate BTOTN as a pale yellow or white solid.
0.50g (0.001 mol) of BTOTN,0.16g (0.0015 mol) of bromoethane, and 100mL of acetonitrile were weighed into a 250mL three-necked flask equipped with a condensation reflux apparatus, and the reaction was carried out while maintaining the reaction temperature under stirring at 60 ℃.
Thin layer chromatography (silica gel GF) 254 Acetone: toluene: water=6:1:1, v/v/v) was monitored to end.
Concentrating the reaction solution under reduced pressure to remove the solvent and unreacted raw materials to obtain a light yellow crude product, and recrystallizing with acetone to obtain the target product heterocyclic-quaternary ammonium salt surfactant BTOTB.
The structural characterization of the target product is carried out according to the infrared spectrogram of fig. 1 and the high-resolution mass spectrogram of fig. 2, which proves that the target product containing the heterocyclic triazinyl quaternary ammonium salt (I) with the structure in the embodiment is finally prepared.
Example 2: synthesis of heterocyclic triazinyl-containing quaternary ammonium salts (II).
Into a 250mL four-necked flask, 2.80g (0.01 mol) of the white solid OT of example 1, 100mL of acetone was added, the temperature was raised to 45-50℃with stirring, and after the white solid was completely dissolved, a mixed solution of 1.45g (0.011 mol) of 2-mercapto-5-methyl-1, 3, 4-thiadiazole in acetone: water=2:1 (v/v) was added dropwise to the four-necked flask while maintaining the temperature at 45-50℃and the reaction was carried out with stirring.
Thin layer chromatography (silica gel GF) 254 Petroleum ether: acetone=3:1, v/v) was monitored to end.
After the reaction, distilled water is added into the reaction liquid to precipitate a large amount of light yellow solid MTOT, and the mixture is washed by hot acetone and then dried in vacuum.
30mL of N, N-dimethyl-1, 3-propanediamine was added to a 250mL three-necked flask equipped with a mechanical stirring device, 1.90g (0.005 mol) of MTOT was added in portions, and the reaction was carried out at 30℃while maintaining the reaction temperature.
Thin layer chromatography (silica gel GF) 254 Acetone: toluene: water=6:1:0.5, v/v/v) was monitored to end.
The reaction solution was dissolved in 100mL of toluene, transferred to a separating funnel, and washed with saturated NaCl multiple times to neutrality. The organic layer was collected, dried over anhydrous sodium sulfate, filtered with suction, concentrated under reduced pressure to give a pale yellow/colorless oil, which was then placed in a fume hood to precipitate a pale yellow or white solid, MTOTN.
0.45g (0.001 mol) of MTOTN,0.16g (0.0015 mol) of bromoethane and 100mL of acetonitrile were weighed into a 250mL three-necked flask equipped with a condensing reflux device, and the reaction was carried out while maintaining the reaction temperature under stirring at 60 ℃.
Thin layer chromatography (silica gel GF) 254 Acetone: toluene: water=6:1:1, v/v/v) was monitored to end.
Concentrating the reaction solution under reduced pressure to remove the solvent and unreacted raw materials to obtain a light yellow crude product, and recrystallizing with acetone to obtain the target product, namely the heterocycle-quaternary ammonium salt surfactant MTOTB.
The structural characterization of the target product is performed according to the infrared spectrogram of fig. 3 and the high-resolution mass spectrogram of fig. 4, which proves that the target product containing the heterocyclic triazinyl quaternary ammonium salt (II) with the structure in the embodiment is finally prepared.
Example 3: and (3) measuring the surface activity of the heterocyclic triazinyl quaternary ammonium salt.
In this example, the surface activity of the heterocyclic triazinyl-containing quaternary ammonium salts prepared in example 1 and example 2 in simulated seawater was measured by the surface tension method.
SRB medium ingredients were added to a 3.5% NaCl aqueous solution to simulate a seawater environment. The SRB medium comprises the following components (g/L): k (K) 2 HPO 4 0.5,NH 4 Cl 1.0,Na 2 SO 4 1.0,CaCl 2 ·2H 2 O 0.1,MgSO 4 ·7H 2 O2.0, DL-sodium lactate 2.0, yeast extract 1.0.
A series of heterocyclic triazinyl quaternary ammonium salt-containing solutions with different concentrations are prepared by using the simulated seawater, and the equilibrium surface tension of the heterocyclic triazinyl quaternary ammonium salt-containing solution is measured by using a K100 automatic surface tension meter and adopting a platinum ring method.
FIG. 5 is a graph showing the relationship between the surface tension and the concentration of the heterocyclic triazinyl-containing quaternary ammonium salt obtained from the measurement results. CMC values of BTOTB and MTOTB in simulated seawater at 30deg.C are 0.035mM and 0.11mM, respectively, corresponding to surface tension gamma CMC 32.8 mN.m respectively -1 And 35.7 mN.m -1 。
Example 4: and (3) measuring the minimum inhibitory concentration of the heterocyclic triazinyl quaternary ammonium salt.
The minimum inhibitory concentration of the heterocyclic triazinyl quaternary ammonium salt was determined in this example using a standard 2-fold dilution method.
1) Diluting the activated SRB bacterial liquid with sterile culture medium to obtain bacterial load of 10 6 Bacterial liquid of the order of magnitude of individual/mL.
2) Preparing a certain amount of heterocyclic triazinyl quaternary ammonium salt mother liquor by using a sterile culture medium, adding the mother liquor into 10mL test tubes according to a standard 2-fold dilution method to obtain a series of concentration gradients, and adding 1mL of the bacterial liquid into each test tube (the final bacterial liquid is 3-7 multiplied by 10) 5 and/mL).
3) Three parallel test tubes were set for each concentration and incubated at 30℃for 14d.
4) The color change of the medium in the tube was recorded. When SRB grows in the culture medium, black FeS precipitation is generated, and otherwise, the SRB does not change color. When all three test tubes are not discolored, the corresponding concentration is the lowest antibacterial concentration of the bactericide.
The corresponding minimum inhibitory concentrations for the products of example 1 and example 2 are listed in table 1 with dodecyldimethylbenzyl ammonium chloride (1227) as a reference. It can be seen that BTOTB and MTOTB have significantly better bacteriostatic effect on SRB than 1227.
Example 5: static weightlessness method for testing corrosion inhibition rate of heterocyclic triazinyl-containing quaternary ammonium salt on carbon steel
The carbon steel sheet sample size is 35mm multiplied by 28mm multiplied by 2mm, and 120 are sequentially used before testing # ~5000 # Polishing the water phase sand paper to be bright, degreasing with acetone, dehydrating with absolute ethyl alcohol, and drying for standby.
The treated carbon steel sheet samples were immersed in sterile simulated seawater without corrosion inhibitor and at a concentration of 0.1mM, respectively, and the coupon 21d was closed at 30 ℃.
After the experiment is finished, the sample is taken out, the corrosion product on the surface is removed by a bristle brush, and then the sample is washed by distilled water and dehydrated by absolute ethyl alcohol. The hanging piece experiment result is shown in figure 6.
As is obvious from the graph, the surface of the carbon steel sheet sample added with BTOTB and MTOTB is smooth and bright, and the corrosion inhibition effect on carbon steel is superior to 1227.
Example 6: electrochemical Impedance Spectroscopy (EIS) is used for testing corrosion inhibition and sterilization performances of the heterocyclic triazinyl quaternary ammonium salt on carbon steel in the presence of SRB.
Will be 45 # The carbon steel electrode is welded with the copper wire, and only one 1.0cm is exposed 2 The square end face of (2) is used as a working face, and the rest is sealed by epoxy resin.
Using 120 the working surface # ~5000 # The water-phase sand paper is polished step by step to a mirror surface, is degreased by acetone, is dehydrated by absolute ethyl alcohol, and is dried by cold air, and then the preservative film is sealed for later use. Before electrochemical test, the processed electrode slice is placed in an ultra-clean workbench and sterilized by ultraviolet for 30min.
Placing the electrode plate into a sterile mold containing heterocyclic triazinyl quaternary ammonium salt with concentration of 0.1mMIn the seawater-simulated anaerobic bottles, 2mL SRB seed solution (bacterial concentration 10) is added into each bottle except for the sterile control 7 and/mL) so that the final solution volume of all bottles is 100mL.
Each anaerobic bottle is filled with 5min N before sealing 2 Sealing, and standing in a constant temperature incubator at 30+ -1deg.C.
And after soaking for different days, taking out the electrode plate from the anaerobic bottle, and assembling a three-electrode system (a platinum plate electrode is used as an auxiliary electrode and a saturated calomel electrode is used as a reference electrode) in an ultra-clean workbench for electrochemical EIS test.
Fig. 7 (a) is a Nyquist plot of carbon steel after various days of soaking in SRB simulated seawater without corrosion inhibiting bactericide, and fig. 7 (b), (c) and (d) show Nyquist plots of carbon steel after various days of soaking in simulated seawater with 0.1mM BTOTB, MTOTB and 1227 added, respectively. Fitting by using an equivalent circuit, and finally obtaining the corrosion inhibition rate result shown in Table 2.
As can be seen from Table 2, the corrosion inhibition and sterilization performance of the heterocyclic triazinyl quaternary ammonium salt on carbon steel is superior to 1227 in all experimental periods.
Example 7: and observing the surface morphology of the carbon steel sheet sample with and without the corrosion inhibitor in the presence of SRB by a scanning electron microscope.
The carbon steel sheet sample size is 35mm multiplied by 28mm multiplied by 2mm, and 120 are used in sequence before testing # ~5000 # Polishing the water phase sand paper to be bright, degreasing by acetone, dehydrating by absolute ethyl alcohol, and drying for standby.
Before the soaking experiment, the treated carbon steel sheet sample is placed in an ultra-clean workbench for ultraviolet sterilization for 30min.
The solution containing heterocyclic triazinyl quaternary ammonium salt with the concentration of 0.1mM, which is prepared by using sterile simulated seawater, is respectively filled into 300mL corrosion inhibition bottles, each bottle is inoculated with activated SRB bacterial liquid according to the inoculation amount of 2 percent, and after nitrogen is introduced for deoxidization, a carbon steel sheet sample is hung, the corrosion inhibition bottles are sealed, and the mixture is soaked in a constant-temperature water bath at 30+/-1 ℃ for 21 days.
All the above operations are completed in an ultra clean bench.
Taking out the carbon steel sheet sample after the test, referring to ASTM G1-03 standard method, removing loose corrosion product on the surface by bristle brush, ultrasonic cleaning with Clark' S solution at 25deg.C for 10min, sequentially cleaning the sample with distilled water and absolute ethanol, and treating with N 2 And (5) drying under flowing.
The surface morphology of the carbon steel sheet samples after soaking for 21d in the SRB solution with or without the heterocyclic triazinyl quaternary ammonium salt was observed using a scanning electron microscope and compared with the surface morphology of the carbon steel sheet samples soaked with the SRB solution with 1227, and the specific results are shown in fig. 8.
In fig. 8 (a) is a surface topography of a polished carbon steel sheet sample, it can be seen that the surface is smooth and flat, and the texture is clear.
In FIG. 8 (b) is shown the corrosion morphology of a carbon steel sheet specimen after soaking in SRB medium without corrosion inhibitor, covered with a layer of loosely porous corrosion product, and the presence of sessile SRB strain was readily observed.
In fig. 8, (c) is a surface topography of a sample of carbon steel sheet after soaking in the SRB solution with MTOTB added, no SRB strain was found in the graph, and the carbon steel surface adsorption film was intact.
In FIG. 8 (d) is a graph showing the surface morphology of a sample of carbon steel sheet after soaking in the SRB solution with 1227 added thereto, and the SRB strain was not found on the surface, but there were many corrosion products.
Thus, comparison shows that when MTOTB is present in the SRB solution, corrosion inhibition and sterilization performance on carbon steel is significantly better than 1227.
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (7)
2. The method for producing a heterocyclic triazinyl-containing quaternary ammonium salt according to claim 1, comprising:
cyanuric chloride is taken as a raw material and reacts with a compound represented by a general formula RXH to obtain a compound represented by a general formula (II);
then the compound shown in the general formula (II) reacts with the compound shown in the general formula YH to obtain the compound shown in the general formula (III);
reacting the compound shown in the general formula (III) with N, N-dimethyl-1, 3-propylene diamine to obtain a compound shown in the general formula (IV);
and finally, reacting the compound shown in the general formula (IV) with bromoethane to prepare the heterocyclic triazinyl-containing quaternary ammonium salt shown in the general formula (I).
3. The method for producing a heterocyclic triazinyl-containing quaternary ammonium salt according to claim 2, wherein the compound represented by the general formula YH is selected from 2-mercaptobenzothiazole or 2-mercapto-5-methyl-1, 3, 4-thiadiazole.
4. The method for preparing the heterocyclic triazinyl-containing quaternary ammonium salt according to claim 2, comprising the steps of:
1) In a solvent toluene system in the presence of sodium hydroxide or sodium carbonate acid binding agent, cyanuric chloride reacts with a compound represented by a general formula RXH under ice bath conditions, and a white compound solid represented by a general formula (II) is precipitated from a reaction solution;
2) Dissolving a compound shown in a general formula (II) by using acetone, adding an acetone-water mixed solution of the compound shown in a general formula YH, and reacting at 45-50 ℃ to obtain a compound light yellow solid shown in a general formula (III);
3) Gradually adding a compound shown in a general formula (III) into N, N-dimethyl-1, 3-propylene diamine, heating to 30 ℃ for reaction, and separating out a compound light yellow or white solid shown in a general formula (IV) from a reaction liquid;
4) Acetonitrile is used as a solvent, a compound shown in a general formula (IV) and bromoethane are added for reaction at 50-60 ℃ to prepare a compound target product shown in the general formula (I).
5. The use of the heterocyclic triazinyl quaternary ammonium salt according to claim 1 for the preparation of a corrosion inhibitor for inhibiting sulfate reducing bacteria corrosion.
6. The use of the heterocyclic triazinyl-containing quaternary ammonium salt according to claim 1 for the preparation of a sulfate reducing bacteria fungicide.
7. The use of the heterocyclic triazinyl-containing quaternary ammonium salt according to claim 1 for the preparation of a corrosion inhibiting bactericide for carbon steel in the presence of sulfate reducing bacteria.
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