CN110669019A - Melamine derivative corrosion inhibitor and preparation method and application thereof - Google Patents
Melamine derivative corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- CN110669019A CN110669019A CN201910962082.0A CN201910962082A CN110669019A CN 110669019 A CN110669019 A CN 110669019A CN 201910962082 A CN201910962082 A CN 201910962082A CN 110669019 A CN110669019 A CN 110669019A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 177
- 230000007797 corrosion Effects 0.000 title claims abstract description 176
- 239000003112 inhibitor Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000007974 melamines Chemical class 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 230000005764 inhibitory process Effects 0.000 claims abstract description 64
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 46
- 239000010962 carbon steel Substances 0.000 claims abstract description 46
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000012434 nucleophilic reagent Substances 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 290
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 22
- 238000004809 thin layer chromatography Methods 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000012544 monitoring process Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JDXOVLKPNKNLRW-UHFFFAOYSA-N octan-1-amine toluene Chemical compound C1(=CC=CC=C1)C.C(CCCCCCC)N JDXOVLKPNKNLRW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 10
- 239000000460 chlorine Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 230000000694 effects Effects 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 17
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 12
- 229920000877 Melamine resin Polymers 0.000 description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 11
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 10
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000012038 nucleophile Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229960003080 taurine Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- 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
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- 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 belongs to the technical field of synthesis and application of corrosion inhibitors for carbon steel in a strong acid environment, and particularly relates to a melamine derivative corrosion inhibitor and a preparation method and application thereof. The preparation method is designed according to the reaction characteristics of cyanuric chloride, and takes N-octylamine, N-dimethyl-1, 3-propane diamine and cyanuric chloride as raw materials; n-octylamine is used as a nucleophilic reagent to substitute two chlorine atoms (Cl) in cyanuric chloride step by step, and N, N-dimethyl-1, 3-propane diamine is also used as a nucleophilic reagent to substitute the remaining chlorine atom (Cl) of the cyanuric chloride to obtain the compound I. The corrosion inhibitor has the following advantages: 1. only hydrocarbon chains are introduced, so that the cost is further reduced, and the length of the carbon chain is optimized by taking the corrosion inhibition performance as an index. 2. Improve the solubility and enhance the adsorbability. 3. The use concentration of the corrosion inhibitor is reduced, the trace application concentration is achieved, the cost is reduced, and meanwhile, the pollution is favorably reduced.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of corrosion inhibitors for carbon steel in a strong acid environment, and particularly relates to a melamine derivative corrosion inhibitor and a preparation method and application thereof.
Background
Acid washing is one of important links of carbon steel application, and carbon steel is extremely easy to corrode in a strong acid environment, so that safety accidents are caused, and economic loss is caused. The addition of corrosion inhibitors is one of the most direct and effective methods with the lowest cost at present. The high-efficiency organic corrosion inhibitor generally contains heteroatoms such as phosphorus (P), oxygen (O), nitrogen (N), sulfur (S) and the like, and lone pair electrons on the heteroatoms are electron-rich centers and can be effectively combined with an electron-deficient metal surface to form a film. containing-NH2Conjugated double bond and triple bond with high electronegativity also have the bonding characteristics, and are potential corrosion inhibitor structure research objects. Cyanuric chloride is a nitrogen-rich compound, has unpaired N heteroatoms and abundant pi electrons, can play a corrosion inhibition role with a metal surface through the action of chemical adsorption (covalent bond) or physical adsorption (van der Waals force), but the application of melamine is limited because the melamine is difficult to dissolve in water, the melamine is modified to improve the solubility, and a plurality of schemes are used for designing and synthesizing melamine derivative corrosion inhibitors. Cyanuric chloride is a cheap and easily available chemical raw material, and a large number of functional compounds are synthesized and applied to various fields by utilizing the chemical reaction characteristic that cyanuric chloride can be gradually substituted. The patent ZL201610031658.8 utilizes the reaction characteristic of cyanuric chloride, introduces amphoteric groups and imidazole corrosion inhibition heterocycles onto triazine rings, and endows the triazine ring derivatives with good corrosion inhibition performance. However, if the nitrogen heteroatom and unsaturated bond of the triazine ring are ignored, corrosion inhibition can be carried out and utilized, but the solubility needs to be improved. The introduction of the heterocyclic ring with corrosion inhibition can increase the production cost of the corrosion inhibitor; the melamine has poor solubility and is difficult to be applied to corrosion inhibition; the prior corrosion inhibitor is concentratedThe corrosion inhibition effect under low concentration is not obvious; the compound corrosion inhibitor has large dosage and pollutes the environment.
In view of the above, there is a need to provide a solution to overcome or at least mitigate at least one of the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to solve the problems, the invention provides a melamine derivative corrosion inhibitor, a preparation method and application thereof, wherein the corrosion inhibitor has the following advantages: 1. only hydrocarbon chains are introduced, so that the cost is further reduced, and the length of the carbon chain is optimized by taking the corrosion inhibition performance as an index. 2. Improve the solubility and enhance the adsorbability. 3. The use concentration of the corrosion inhibitor is reduced, the trace application concentration is achieved, the cost is reduced, and meanwhile, the pollution is favorably reduced.
The invention is realized by the following technical scheme:
a melamine derivative corrosion inhibitor, which is a metal corrosion inhibitor for carbon steel in an acidic environment; the corrosion inhibitor is a compound I, and the chemical structural formula of the compound I is as follows:
the invention also provides a preparation method of the melamine derivative corrosion inhibitor, the preparation method is designed according to the reaction characteristics of cyanuric chloride, and the preparation method takes N-octylamine, N-dimethyl-1, 3-propane diamine and cyanuric chloride as raw materials; n-octylamine is used as a nucleophilic reagent to substitute two chlorine atoms (Cl) in cyanuric chloride step by step, and N, N-dimethyl-1, 3-propane diamine is also used as a nucleophilic reagent to substitute the remaining chlorine atom (Cl) of the cyanuric chloride to obtain the compound I.
Further, the preparation method specifically comprises the following steps:
step 1: n-octylamine is used as a nucleophilic reagent to replace the first chlorine atom in cyanuric chloride to obtain a mono-substituted intermediate compound II, and the reaction is shown as the following formula (I):
step 2: n-octylamine as a nucleophile to replace the second chlorine atom in cyanuric chloride, to give a disubstituted intermediate compound III, which is represented by the following formula (II):
and step 3: substituting a third chlorine atom in cyanuric chloride by N, N-dimethyl-1, 3-propanediamine as a nucleophile to obtain the compound I, wherein the reaction is shown as the following formula (III):
further, in the preparation method, the reaction sequence of step 1 to step 3 cannot be changed for the following reasons:
firstly, the requirements of three-step nucleophilic substitution reaction of cyanuric chloride on reaction conditions are gradually increased, namely, the substitution temperature of the second step (step 2) and the third step (step 3) is higher than that of the first step (step 1), and the reaction conditions are more severe; step three (step 3) replaces the situation that if the reaction activity of the raw materials is too low, the requirement on the reaction condition is high or the reaction cannot be carried out due to too low activity; therefore, the first step (step 1) substitution and the second step (step 2) substitution are carried out by using n-octylamine with lower substitution reaction activity, and the third step (step 3) substitution is carried out by using propylene diamine with higher nucleophilic substitution reaction activity;
secondly, the nucleophilic substitution reaction of the melamine is related to reaction raw materials and reaction conditions; the nucleophilic substitution activity of the propane diamine is stronger than that of n-hexylamine, and the n-hexylamine is selected as a primary substitution raw material of cyanuric chloride, so that the possibility of side reaction can be reduced.
Further, the specific content of the reaction in the step 1 is as follows:
slowly dripping a toluene solution of n-octylamine into a toluene solution of cyanuric chloride ice slurry while stirring at the temperature of 0-5 ℃ and under the condition that the pH value is 8.5-9.5; monitoring the reaction by thin layer chromatographyAt the end point, the cyanuric chloride completely reacts (because cyanuric chloride is easy to react in the solution, the amount of substances which react with the n-octylamine is lower than that of the n-octylamine), and insoluble substances are filtered off while the solution is hot; the filtrate is sequentially used with 1mol and L-1Hydrochloric acid solution, 1 mol. L-1Washing with NaOH solution, washing with distilled water for several times to obtain toluene layer, drying, and concentrating to obtain intermediate compound II.
Further, the solid-to-liquid ratio of n-octylamine to the toluene solvent in the toluene solution of n-octylamine is as follows: n-octylamine (g): toluene (ml) at a solid-to-liquid ratio of 1:8-15, optimally at a solid-to-liquid ratio of 1: 12; the amount of n-octylamine is related to the inability to completely replace one chlorine atom on cyanuric chloride.
Further, the cyanuric chloride raw material in the step 1 is rapidly and mechanically stirred into ice slurry by crushed ice with the mass of 5-6 times, the temperature of an ice water bath is maintained at 0-5 ℃, and the PH value is 8.5-9.5, so that excessive reaction of cyanuric chloride is avoided.
Further, the amount ratio of the substances of n-octylamine and cyanuric chloride in the step 1 is 1: 1.1-1.5; the optimal dosage is 1: 1.2; n-octylamine dissolved in toluene solvent, n-octylamine (g): the solid-to-liquid ratio of toluene (ml) was 1:8-15, and the optimal solid-liquid ratio is 1: 12.
further, the n-octylamine can also be dissolved in an acetone or dichloromethane solvent; however, the toluene after-treatment effect is optimal and the after-treatment is relatively simple in order to facilitate the reaction, and the content of the by-product can be reduced by using the toluene as an organic solvent; acetone is a solvent easy to prepare toxin, and post-treatment of a chlorine-containing solvent is troublesome; thus, the best solvent is also toluene.
Further, the n-octylamine toluene solution of step 1 is slowly added dropwise to an ice slurry containing cyanuric chloride for 1 to 2 hours per 100ml of the solution.
Further, the reaction of the step 1 is monitored by thin layer chromatography, the developing agent is toluene and methanol, and the volume ratio of toluene to methanol is 3-5: 1.
further, the drying agent used in the drying in the step 1 is anhydrous Na2SO4。
Further, when the concentration of the step 1 is carried out, the solvent toluene is removed by reduced pressure rotary evaporation.
Further, the compound II is a white solid.
Further, the specific content of the reaction in the step 2 is as follows:
under the conditions that the reaction temperature is 30-35 ℃ and the PH value is 8.0-9.0, the toluene solution of the n-octylamine is dropwise added into the toluene solution of the compound II, and a 500mL three-necked bottle is used as a reactor. And (3) monitoring the end point by thin-layer chromatography, finishing the reaction when the compound II is completely consumed, filtering to obtain a filter cake, washing the filter cake for multiple times by using toluene and distilled water in sequence, and drying to obtain the intermediate compound III.
Further, the amount ratio of the substances of n-octylamine and cyanuric chloride in the step 2 is 1: 1.1-1.5; the optimal dosage is 1: 1.2; n-octylamine dissolved in toluene solvent, n-octylamine (g): the solid-to-liquid ratio of toluene (ml) was 1:8-15, and the optimal solid-liquid ratio is 1: 12.
further, the compound II in step 2 is a raw material, toluene is a solvent, and the compound II: the solid-liquid ratio of toluene is 1: 6-10.
Further, the amount ratio of the n-octylamine to the compound II in the step 2 is 1: 1.0-1.5, and the optimal dosage is 1: 1.1.
further, the nucleophile n-octylamine used in step 2 is dissolved in toluene solvent, n-octylamine (g): toluene (ml) at a solid to liquid ratio of 1: 8-12. The optimal solid-liquid ratio is 1: 10.
furthermore, the toluene solution of n-octylamine in the step 2 needs to be slowly dropped at a rate of 1-3 drops per second.
Further, the reaction of the step 2 is carried out by tracking a reaction end point by using a thin layer chromatography, a developing agent system comprising toluene and methanol is adopted, the volume ratio of the toluene to the methanol is 6-4:1, and the reaction end point is obtained when the compound II is completely consumed.
Further, the obtained filter cake of the step 2 is washed by toluene and distilled water in sequence.
Further, the compound III is a white solid.
Further, the specific content of the reaction in the step 3 is as follows:
adding 0.10mol of the intermediate compound III into a three-necked bottle filled with 60mL of N, N-dimethyl-1, 3-propane diamine by 3 times, heating to 40-50 ℃, reacting and keeping for 1-1.5 h. Monitoring the reaction end point by thin-layer chromatography, and finishing the reaction when the compound III is completely reacted; dissolving the mixture after the reaction in 60mL of toluene, transferring the mixture into a separating funnel, and extracting the mixture for 3 times by using distilled water with the same volume until the toluene layer is neutral; the toluene layer was dried, and the toluene solvent was removed to obtain the objective compound I.
Further, in the step 3, the N, N-dimethyl-1, 3-propane diamine is used as a raw material and a solvent, and the reaction end point is that the intermediate compound III is completely reacted.
Further, the solid-to-liquid ratio of the compound III to the N, N-dimethyl-1, 3-propane diamine is 1: 1-1.5 (g/ml); preferably 1: 1.2.
Further, the compound I is a colorless oil.
The invention also aims to provide an application of the melamine derivative corrosion inhibitor in carbon steel corrosion inhibition in an acidic environment.
Further, the acidic environment is: carbon steel in 1M HCl solution.
Furthermore, the corrosion inhibitor is used at the temperature of between 25 and 50 ℃ and the use concentration of between 0.05 and 0.25 mmol.L-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibition efficiency of HCl acid medium to carbon steel reaches more than 90%, and the performance is excellent.
Furthermore, the corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.05 mmol.L-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 90.61%.
Furthermore, the corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.1 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 92.29%.
Furthermore, the corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.25 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 93.49 percent.
Further, the corrosion inhibitionThe agent is used at 25 ℃ and the concentration is 2.5 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 94.59%.
Furthermore, the corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.05 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 86.21 percent.
Furthermore, the corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.1 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 89.62%.
Furthermore, the corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.25 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 90.04%.
Furthermore, the corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 2.5 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 91.18 percent.
Furthermore, the corrosion inhibitor is used at the temperature of 50 ℃ and the use concentration of 0.05 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 62.24 percent.
Furthermore, the corrosion inhibitor is used at the temperature of 50 ℃ and the use concentration of 0.1 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 70.31 percent.
Furthermore, the corrosion inhibitor is used at the temperature of 50 ℃ and the use concentration of 0.25 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 76.28 percent.
Furthermore, the corrosion inhibitor is used at the temperature of 50 ℃ and the use concentration of 2.5 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 79.25 percent.
The invention has the following beneficial technical effects:
(1) the compound I is a melamine derivative only introduced with an aliphatic chain (the aliphatic chain is 6 or 8 carbon atoms, and a carbon chain containing nitrogen atoms is 3 carbon atoms), so that the cost is further reduced compared with the introduction of a heterocycle with corrosion inhibition performance.
(2) The compound I (melamine derivative) of the present invention has increased solubility in an acidic solution (hydrochloric acid) and enhanced adsorption as compared with the parent melamine.
(3) When the compound I is used, the dosage is small, and the compound I belongs to a micro-scale and is environment-friendly.
(4) The compound I of the invention has no special functional group and has simple structure.
(5) The compound I can be applied in strong acid medium, and the synthesis process is relatively simple and suitable for popularization.
Drawings
FIG. 1 is a high resolution mass spectrum of Compound I in the present example.
FIG. 2 preparation of Compound I in the example of the invention1H NMR chart.
FIG. 3 is a graph showing the corrosion inhibition efficiency of compound I in a static weight loss test according to an embodiment of the present invention.
FIG. 4 shows 1 mol. L in example of the present invention-1Potentiodynamic polarization curve of carbon steel corrosion in HCl solution.
FIG. 5 shows 1 mol. L in example of the present invention-1Electrochemical impedance spectrum of carbon steel corrosion in HCl solution.
FIG. 6 is a flow chart of a method for preparing a melamine derivative corrosion inhibitor in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The embodiment provides a melamine derivative corrosion inhibitor, which is a metal corrosion inhibitor for carbon steel in an acidic environment; the corrosion inhibitor is a compound I, and the chemical structural formula of the compound I is as follows:
the invention also provides a preparation method of the melamine derivative corrosion inhibitor, the preparation method is designed according to the reaction characteristics of cyanuric chloride, and the preparation method takes N-octylamine, N-dimethyl-1, 3-propane diamine and cyanuric chloride as raw materials; n-octylamine is used as a nucleophilic reagent to substitute two chlorine atoms (Cl) in cyanuric chloride step by step, and N, N-dimethyl-1, 3-propane diamine is also used as a nucleophilic reagent to substitute the remaining chlorine atom (Cl) of the cyanuric chloride to obtain the compound I.
The preparation method specifically comprises the following steps:
step 1: n-octylamine is used as a nucleophilic reagent to replace the first chlorine atom in cyanuric chloride to obtain a mono-substituted intermediate compound II, and the reaction is shown as the following formula (I):
step 2: n-octylamine as a nucleophile to replace the second chlorine atom in cyanuric chloride, to give a disubstituted intermediate compound III, which is represented by the following formula (II):
and step 3: substituting a third chlorine atom in cyanuric chloride by N, N-dimethyl-1, 3-propanediamine as a nucleophile to obtain the compound I, wherein the reaction is shown as the following formula (III):
in the preparation method, the reaction sequence of step 1 to step 3 cannot be changed for the following reasons:
firstly, the requirements of three-step nucleophilic substitution reaction of cyanuric chloride on reaction conditions are gradually increased, namely, the substitution temperature of the second step (step 2) and the third step (step 3) is higher than that of the first step (step 1), and the reaction conditions are more severe; step three (step 3) replaces the situation that if the reaction activity of the raw materials is too low, the requirement on the reaction condition is high or the reaction cannot be carried out due to too low activity; therefore, the first step (step 1) substitution and the second step (step 2) substitution are carried out by using n-octylamine with lower substitution reaction activity, and the third step (step 3) substitution is carried out by using propylene diamine with higher nucleophilic substitution reaction activity;
secondly, the nucleophilic substitution reaction of the melamine is related to reaction raw materials and reaction conditions; the nucleophilic substitution activity of the propane diamine is stronger than that of n-hexylamine, and the n-hexylamine is selected as a primary substitution raw material of cyanuric chloride, so that the possibility of side reaction can be reduced.
The reaction in the step 1 comprises the following specific contents:
slowly dripping a toluene solution of n-octylamine into a toluene solution of cyanuric chloride ice slurry while stirring at the temperature of 0-5 ℃ and under the condition that the pH value is 8.5-9.5; monitoring the end point of the reaction by thin-layer chromatography, finishing the complete reaction of the cyanuric chloride (because the cyanuric chloride is easy to react in the solution, the amount of substances reacted with the n-octylamine is less than that of the n-octylamine), and filtering insoluble substances while the solution is hot; the filtrate is sequentially used with 1mol and L-1Hydrochloric acid solutionLiquid, 1 mol. L-1Washing with NaOH solution, washing with distilled water for several times to obtain toluene layer, drying, and concentrating to obtain intermediate compound II.
The solid-liquid ratio of n-octylamine to a toluene solvent in the toluene solution of n-octylamine is as follows: n-octylamine (g): toluene (ml) at a solid-to-liquid ratio of 1:8-15, optimally at a solid-to-liquid ratio of 1: 12; the amount of n-octylamine is related to the inability to completely replace one chlorine atom on cyanuric chloride.
The cyanuric chloride raw material in the step 1 is rapidly and mechanically stirred into ice slurry by crushed ice with the mass of 5-6 times, the temperature of an ice water bath is maintained at 0-5 ℃, the PH value is 8.5-9.5, and the cyanuric chloride excessive reaction is avoided.
The mass ratio of n-octylamine to cyanuric chloride in step 1 is 1: 1.1-1.5; the optimal dosage is 1: 1.2; n-octylamine dissolved in toluene solvent, n-octylamine (g): the solid-to-liquid ratio of toluene (ml) was 1:8-15, and the optimal solid-liquid ratio is 1: 12.
the n-octylamine can also be dissolved in an acetone or dichloromethane solvent; however, the toluene after-treatment effect is optimal and the after-treatment is relatively simple in order to facilitate the reaction, and the content of the by-product can be reduced by using the toluene as an organic solvent; acetone is a solvent easy to prepare toxin, and post-treatment of a chlorine-containing solvent is troublesome; thus, the best solvent is also toluene.
The n-octylamine toluene solution obtained in the step 1 is slowly dripped into ice slurry containing cyanuric chloride, and each 100ml of the solution is used for 1-2 hours.
Monitoring the reaction end point of the reaction in the step 1 by using thin-layer chromatography, wherein the developing agent is toluene and methanol, and the volume ratio of the toluene to the methanol is 3-5: 1.
the drying agent used in the drying in the step 1 is anhydrous Na2SO4。
And (3) removing the solvent toluene by adopting reduced pressure rotary evaporation when the step 1 is concentrated.
The compound II is a white solid.
The reaction in the step 2 comprises the following specific contents:
under the conditions that the reaction temperature is 30-35 ℃ and the PH value is 8.0-9.0, the toluene solution of the n-octylamine is dropwise added into the toluene solution of the compound II, and a 500mL three-necked bottle is used as a reactor. And (3) monitoring the end point by thin-layer chromatography, finishing the reaction when the compound II is completely consumed, filtering to obtain a filter cake, washing the filter cake for multiple times by using toluene and distilled water in sequence, and drying to obtain the intermediate compound III.
The mass ratio of n-octylamine to cyanuric chloride in the step 2 is 1: 1.1-1.5; the optimal dosage is 1: 1.2; n-octylamine dissolved in toluene solvent, n-octylamine (g): the solid-to-liquid ratio of toluene (ml) was 1:8-15, and the optimal solid-liquid ratio is 1: 12.
the compound II in the step 2 is used as a raw material, toluene is used as a solvent, and the compound II: the solid-liquid ratio of toluene is 1: 6-10.
The quantity ratio of n-octylamine to compound II in the step 2 is 1: 1.0-1.5, and the optimal dosage is 1: 1.1.
dissolving the nucleophilic reagent n-octylamine used in the step 2 into a toluene solvent, wherein n-octylamine (g): toluene (ml) at a solid to liquid ratio of 1: 8-12. The optimal solid-liquid ratio is 1: 10.
and (3) slowly dripping the n-octylamine toluene solution in the step (2) at the speed of 1-3 drops per second.
And (3) tracking the reaction end point of the reaction in the step (2) by using thin-layer chromatography, wherein a developing agent system comprises toluene and methanol, the volume ratio of the toluene to the methanol is 6-4:1, and the reaction end point is obtained when the compound II is completely consumed.
And washing the obtained filter cake of the step 2 by toluene and distilled water sequentially.
The compound III is a white solid.
The reaction in the step 3 comprises the following specific contents:
adding 0.10mol of the intermediate compound III into a three-necked bottle filled with 60mL of N, N-dimethyl-1, 3-propane diamine by 3 times, heating to 40-50 ℃, reacting and keeping for 1-1.5 h. Monitoring the reaction end point by thin-layer chromatography, and finishing the reaction when the compound III is completely reacted; dissolving the mixture after the reaction in 60mL of toluene, transferring the mixture into a separating funnel, and extracting the mixture for 3 times by using distilled water with the same volume until the toluene layer is neutral; the toluene layer was dried, and the toluene solvent was removed to obtain the objective compound I.
In the step 3, N-dimethyl-1, 3-propane diamine is used as a raw material and a solvent, and the reaction end point is that the intermediate compound III is completely reacted.
The solid-to-liquid ratio of the compound III to the N, N-dimethyl-1, 3-propane diamine is 1: 1-1.5 (g/ml); preferably 1: 1.2.
The compound I was a colorless oil.
The invention also aims to provide an application of the melamine derivative corrosion inhibitor in carbon steel corrosion inhibition in an acidic environment.
The acid environment is as follows: carbon steel in 1M HCl solution.
The corrosion inhibitor has the use concentration of 0.05-0.25 mmol.L at the temperature of 25-50 DEG C-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibition efficiency of HCl acid medium to carbon steel reaches more than 90%, and the performance is excellent.
The corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.05 mmol.L-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 90.61%.
The corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.1 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 92.29%.
The corrosion inhibitor is used at the temperature of 25 ℃ and the use concentration of 0.25 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 93.49 percent.
The corrosion inhibitor has the use concentration of 2.5 mmol.L at the temperature of 25 DEG C-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 94.59%.
The corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.05 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 86.21 percent.
The corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.1 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 89.62%.
The corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 0.25 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 90.04 percent。
The corrosion inhibitor is used at the temperature of 35 ℃ and the use concentration of 2.5 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 91.18 percent.
The corrosion inhibitor is used at the temperature of 50 ℃ and the use concentration of 0.05 mmol.L-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 62.24 percent.
The corrosion inhibitor has the use concentration of 0.1 mmol.L at 50 DEG C-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 70.31 percent.
The corrosion inhibitor has the use concentration of 0.25 mmol.L at 50 DEG C-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 76.28 percent.
The corrosion inhibitor has the use concentration of 2.5 mmol.L at 50 DEG C-1When 1 mol. L-1The corrosion inhibition efficiency of the HCl solution on carbon steel is 79.25 percent.
The following experiments were carried out according to the above described melamine derivative corrosion inhibitors, their preparation and use:
experiment 1
The experiment used a straight chain aliphatic amine (C)nH2n+1NH2) Comparing the performances of the corrosion inhibitor prepared from the linear aliphatic amine of the linear aliphatic amine with the carbon atoms n of 2, 3, 4 and 5, the specific reaction process is as follows:
experimental results show that when n is less than or equal to 5, the number of carbon atoms of a carbon chain is small, the corrosion inhibition performance of the prepared compound is not obvious, and the application is influenced. The short fatty carbon chains are not sufficient to impart solubility and adsorptivity to the melamine derivative, which in turn affects the corrosion inhibition effect.
The corrosion inhibitor is prepared according to the preparation method of the melamine derivative corrosion inhibitor, except that n-hexylamine is adopted to replace n-octylamine in the step 2; the corrosion inhibition performance of the prepared corrosion inhibitor is verified, and the specific reaction process is as follows:
the specific process of the step 1 is as follows: adding 18.45g (0.1mol) of cyanuric chloride and 100g of crushed ice into a 500ml four-mouth bottle, rapidly stirring to form ice slurry, and maintaining the temperature of an ice water bath at 0-5 ℃. 14.22g (0.11mol) of n-octylamine were dissolved in 100ml of toluene, and the solution was slowly added dropwise to an ice slurry of cyanuric chloride in a constant pressure dropping funnel at 1 mol. L-1The potassium hydroxide water controls the pH and keeps it at 8.5-9.0.
The reaction was followed by thin layer chromatography, with toluene: the methanol was 5:1 to 3:1 as a developed system, the end point was monitored, and insoluble matter was filtered after the reaction was completed. The toluene filtrate is sequentially used for 1 mol.L in a separating funnel-1Hydrochloric acid solution, 1 mol. L-1And washing with NaOH solution and distilled water for many times. The final toluene layer on the upper layer is dried by anhydrous sodium sulfate overnight, and is distilled under reduced pressure to obtain white solid, namely the mono-substituted intermediate compound.
The specific process of the step 2 is as follows: dissolving 0.10mol of the intermediate compound II in a 500mL three-necked bottle filled with 150mL of toluene solvent, dissolving 0.11mol of n-hexylamine in 100mL of toluene, dropwise adding into a dropping funnel at a speed of 1-2 drops per second, controlling the reaction temperature at 30-35 ℃, and controlling the reaction temperature to be 1 mol.L-1The pH of the NaOH solution is controlled to be 8.5-9.0. Mixing the following raw materials in percentage by weight of toluene: methanol 5:1 as developing agent, and monitoring the end point of the reaction by thin layer chromatography. Filtering to obtain a filter cake after the reaction is finished, washing the filter cake with toluene and distilled water in sequence, and drying to obtain a white solid which is a disubstituted intermediate compound.
The specific process of the step 3 is as follows: 0.10mol of the disubstituted intermediate compound III was added to a three-necked flask containing 60mL of N, N-dimethyl-1, 3-propanediamine in 3 portions, and the temperature was raised to 45 to 50 ℃ and maintained for 1.5 hours. Thin layer chromatography with toluene: the end of the reaction was monitored by using a 2:1 methanol developing system, and after completion of the reaction, the mixture was dissolved in toluene 60mL, and transferred to a separatory funnel, and extracted with distilled water of the same volume for 2 times until the toluene layer became neutral. The toluene layer was dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain a colorless oil, which was the corrosion inhibitor prepared in this experiment.
When the corrosion inhibitor is prepared in the experiment, n-hexylamine is used for replacing n-octylamine in the step 2, the yield of the prepared disubstituted product is 89% (the yield of the disubstituted product before replacement is 97%), and the yield of the prepared corrosion inhibitor is 87% (the yield of the corrosion inhibitor before replacement is 97%). This example illustrates that the use of n-hexylamine substituted n-octylamine to prepare a corrosion inhibitor in step 2 results in a decrease in product yield in both step 2 and step 3.
In the experiment, the corrosion inhibitor is prepared according to the preparation method of the invention, and the specific reaction process of replacing n-octylamine with n-hexylamine is as follows:
the specific process of the step 1 is as follows: adding 18.45g (0.1mol) of cyanuric chloride and 100g of crushed ice into a 500ml four-mouth bottle, rapidly stirring to form ice slurry, and maintaining the temperature of an ice water bath at 0-5 ℃. 14.22g (0.11mol) of n-hexylamine are dissolved in 100ml of toluene, and the solution is slowly added dropwise to an ice slurry of cyanuric chloride in a constant pressure dropping funnel in an amount of 1 mol.L-1The potassium hydroxide water controls the pH and keeps it at 8.5-9.0.
The reaction was followed by thin layer chromatography, with toluene: the methanol was 5:1 to 3:1 as a developed system, the end point was monitored, and insoluble matter was filtered after the reaction was completed. The toluene filtrate is sequentially used for 1 mol.L in a separating funnel-1Hydrochloric acid solution, 1 mol. L-1And washing with NaOH solution and distilled water for many times. The final toluene layer on the upper layer is dried by anhydrous sodium sulfate overnight, and is distilled under reduced pressure to obtain white solid, namely the mono-substituted intermediate compound.
The specific process of the step 2 is as follows: dissolving 0.10mol of the intermediate compound II in a 500mL three-necked bottle filled with 150mL of toluene solvent, dissolving 0.11mol of n-hexylamine in 100mL of toluene, dropwise adding into a dropping funnel at a speed of 1-2 drops per second, controlling the reaction temperature at 30-35 ℃, and controlling the reaction temperature to be 1 mol.L-1The pH of the NaOH solution is controlled to be 8.5-9.0. Mixing the following raw materials in percentage by weight of toluene: methanol 5:1 as developing agent, and monitoring the end point of the reaction by thin layer chromatography. Filtering to obtain filter cake, and sequentially using AAnd washing the filter cake with benzene and distilled water, and drying to obtain a white solid which is a disubstituted intermediate compound.
The specific process of the step 3 is as follows: 0.10mol of the disubstituted intermediate compound III was added to a three-necked flask containing 60mL of N, N-dimethyl-1, 3-propanediamine in 3 portions, and the temperature was raised to 45 to 50 ℃ and maintained for 1.5 hours. Thin layer chromatography with toluene: the end of the reaction was monitored by using a 2:1 methanol developing system, and after completion of the reaction, the mixture was dissolved in toluene 60mL, and transferred to a separatory funnel, and extracted with distilled water of the same volume for 2 times until the toluene layer became neutral. The toluene layer was dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain a colorless oily substance, which was the corrosion inhibitor in this experiment.
In the embodiment, the yield of the corrosion inhibitor prepared by replacing n-octylamine with n-hexylamine is obviously reduced and can only reach 70.73%.
The corrosion inhibitor prepared in the embodiment has the use concentration of 0.5-1 mmol.L at the temperature of 25-40 DEG C-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibitor in HCl acid medium has a corrosion inhibition efficiency of only 85% to metal (or metal alloy).
Experiment 4
In the experiment, when n-octylamine is replaced by n-hexylamine in the step 1 and n-octylamine is replaced by aminobenzimidazole in the step 2, the performance of the prepared corrosion inhibitor is verified, and the synthetic route is as follows:
the prepared corrosion inhibitor is used for inhibiting corrosion of carbon steel in an acidic medium, and the using concentration is 0.5 mmol.L-1When the corrosion inhibition rate reaches 90 percent, the use concentration is lower than 0.5 mmol.L-1The corrosion inhibition effect of the compound I is lower than that of the compound I. The corrosion inhibition effect of the experimental corrosion inhibitor is mainly characterized by introducing micromolecular aminobenzimidazole with corrosion inhibition performance, and the aminobenzimidazole is the corrosion inhibitor. The purpose of the three-step nucleophilic substitution reaction is to improve the solubility of aminobenzimidazole by the reaction characteristics of triazine ring, and the introduction of heterocyclic ring (aminobenzimidazole) can increase the corrosion inhibitorAnd (5) the production cost. And the heterocycle is introduced, the reaction temperature required by the third step reaction is far higher than that of the application, and the high temperature has potential safety hazard and increases the production cost. The solvent dioxane belongs to a micro-toxic substance and has irritation to skin, eyes and a respiratory system, and the application improves the solvent dioxane, improves the safety and has more applicability.
In the experiment, on the basis of experiment 3, N-dimethyl-1, 3-propane diamine is replaced by taurine, the performance of the prepared corrosion inhibitor is verified, and the synthetic route is as follows:
the corrosion inhibitor prepared by the synthetic route is used for inhibiting corrosion of carbon steel in an acidic medium, and the use concentration is 0.9g L-1And the corrosion inhibition rate reaches 81%, and the corrosion inhibition effect is lower than that of the compound I. The corrosion inhibitor prepared by the experiment has the corrosion inhibition effect mainly due to the introduction of micromolecule aminobenzimidazole with corrosion inhibition performance, and the aminobenzimidazole is the corrosion inhibitor. The purpose of the three-step nucleophilic substitution reaction is to improve the solubility of aminobenzimidazole through the reaction characteristics of triazine ring, and the introduction of heterocyclic ring can increase the production cost of the corrosion inhibitor. The heterocycle is introduced, the reaction temperature required by the third step of reaction is far higher than that of the method, the cost of raw materials is high, the method is improved and has better applicability, and the corrosion inhibition effect of the product is further improved.
Compared with N, N-dimethyl-1, 3-propane diamine, the taurine raw material cost of the corrosion inhibitor prepared by the synthesis is higher, the reaction temperature is higher when the taurine is used for carrying out the trisubstitution reaction of the cyanuric chloride, the difficulty of the reaction condition is improved, the yield of the reactant only can reach 67.38 percent and is lower than that (78.48 percent) of the corrosion inhibitor prepared by the N, N-dimethyl-1, 3-propane diamine. The taurine-substituted corrosion inhibitor belongs to an anionic corrosion inhibitor, is a cationic corrosion inhibitor for a corrosion inhibitor synthesized based on N, N-dimethyl-1, 3-propane diamine, and has higher corrosion inhibition effect than the anionic corrosion inhibitor for a corrosion inhibitor of carbon steel in an HCl medium. In summary, corrosion inhibition effect of the corrosion inhibitor prepared by replacing N, N-dimethyl-1, 3-propane diamine with taurine is relatively poor.
In the experiment, the corrosion inhibitor is prepared according to the preparation method of the invention, and the specific reaction process is as follows:
the specific process of the step 1 is as follows: adding 18.45g (0.1mol) of cyanuric chloride and 100g of crushed ice into a 500ml four-mouth bottle, rapidly stirring to form ice slurry, and maintaining the temperature of an ice water bath at 0-5 ℃. 14.22g (0.11mol) of n-octylamine were dissolved in 100ml of toluene, and slowly added dropwise to 1 mol. L of cyanuric chloride in ice slurry using a constant pressure dropping funnel-1The pH value of the potassium hydroxide aqueous solution is controlled and kept between 8.5 and 9.0.
Thin layer chromatography followed the reaction, toluene: and (3) taking methanol as a development system, monitoring the end point, finishing the reaction and filtering insoluble substances. The toluene filtrate is sequentially used for 1 mol.L in a separating funnel-1Hydrochloric acid solution, 1 mol. L-1NaOH solution and distilled water. The upper toluene layer was dried over anhydrous sodium sulfate overnight, and toluene was removed by distillation under reduced pressure to give a white solid, i.e., a mono-substituted intermediate compound.
The specific process of the step 2 is as follows: dissolving 0.10mol of intermediate compound II in a 500mL three-necked flask filled with 150mL of toluene, dissolving 0.11mol of n-octylamine in 100mL of toluene, dropwise adding at a speed of 1-2 drops per second by using a dropping funnel, controlling the reaction temperature at 30-35 ℃, and controlling the reaction temperature to be 1 mol.L-1The pH of the NaOH solution is controlled to be 8.5-9. Mixing the following raw materials in percentage by weight of toluene: methanol 5:1 as developing agent, and monitoring the end point of the reaction by thin layer chromatography. Filtering to obtain a filter cake after the reaction is finished, washing the filter cake with toluene and distilled water in sequence, and drying to obtain a white solid which is a disubstituted intermediate compound.
The specific process of the step 3 is as follows: 0.10mol of the disubstituted intermediate compound III was added to a three-necked flask containing 60mL of N, N-dimethyl-1, 3-propanediamine in 3 portions, and the temperature was raised to 45 to 50 ℃ and maintained for 1.5 hours. Thin layer chromatography with toluene: the end of the reaction was monitored by using a 2:1 methanol developing system, and after completion of the reaction, the mixture was dissolved in toluene 60mL, and transferred to a separatory funnel, and extracted with distilled water of the same volume for 2 times until the toluene layer became neutral. The toluene layer is dried by anhydrous sodium sulfate, and is distilled under reduced pressure to obtain colorless oily substance, namely the corrosion inhibitor (namely the compound I, the same below); the yield was 87.48%.
As shown in FIG. 1, the molecular weight of the prepared corrosion inhibitor is measured by a high-resolution mass spectrometer, and [ M + H ] of a target compound S can be obtained by mass spectrometry (ESI-MS Positive) analysis]+The peak was 436.4120, so the molecular weight of Compound I was judged to be 435.
As shown in FIG. 2, a Bruker-600 type nuclear magnetic resonance spectrometer was used as DH3OH is used as solvent, hydrogen spectrogram of the corrosion inhibitor is determined, and chemical shift values and splitting conditions of all hydrogen atoms in the spectrogram are consistent with chemical structures of the hydrogen atoms.
As shown in FIGS. 3 to 5, the corrosion inhibitors (compound I) with different concentrations and dosages at 25 ℃ are added to 1 mol.L-1Corrosion inhibition efficiency curve of carbon steel in hydrochloric acid medium. As can be seen from the figure, the corrosion inhibitor (containing the compound I) has good inhibition on the corrosion of carbon steel, and the concentration of the corrosion inhibitor (containing the compound I) is 0.05 mmol.L-1The corrosion inhibition efficiency can reach 90.61 percent, and the corrosion inhibition efficiency is 1.0 mmol.L-1The corrosion inhibition efficiency can reach 94.59% under the concentration. That is, the corrosion inhibitor (comprising compound I) is used in a concentration of 0.05 to 0.25 mmol.L-1(concentration of corrosion inhibitor directly dissolved in HCl solution, the same applies below), 1 mol. L-1The corrosion inhibition efficiency of HCl acid medium to carbon steel reaches more than 90%, and the performance is excellent.
In the experiment, the corrosion inhibitor (compound I) prepared by the preparation method is compared with the parent melamine in corrosion inhibition performance, and the comparison result is shown in the following table 1-2:
TABLE 1 potentiodynamic polarization experimental data sheet for compound I corrosion inhibition performance research
TABLE 2 electrochemical impedance experimental data sheet for compound I corrosion inhibition performance research
As is clear from tables 1 and 2 above, compound I (melamine derivative) has higher solubility in an acidic solution (hydrochloric acid) and enhanced adsorption than the parent melamine.
Claims (10)
1. A melamine derivative corrosion inhibitor, which is a metal corrosion inhibitor for carbon steel in an acidic environment; the corrosion inhibitor is a compound I;
the chemical structural formula of the compound I is as follows:
2. a process for the preparation of the melamine derivative corrosion inhibitor according to claim 1, characterized in that N-octylamine, N-dimethyl-1, 3-propanediamine and cyanuric chloride are used as starting materials; n-octylamine is used as a nucleophilic reagent to substitute two chlorine atoms in cyanuric chloride step by step, and N, N-dimethyl-1, 3-propane diamine is also used as a nucleophilic reagent to substitute the remaining chlorine atom in the cyanuric chloride to obtain the compound I.
3. The preparation method according to claim 2, characterized in that the preparation method comprises the following steps:
step 1: n-octylamine is used as a nucleophilic reagent to replace the first chlorine atom in cyanuric chloride to obtain a mono-substituted intermediate compound II;
step 2: n-octylamine is used as a nucleophilic reagent to replace a second chlorine atom in cyanuric chloride to obtain a disubstituted intermediate compound III;
and step 3: and (3) substituting the third chlorine atom in cyanuric chloride by using N, N-dimethyl-1, 3-propane diamine as a nucleophilic reagent to obtain the compound I.
4. The method according to claim 3, wherein the ratio of the amounts of n-octylamine and cyanuric chloride in step 1 is 1: 1.1-1.5.
5. The preparation method according to claim 3, wherein the reaction in the step 1 is specifically as follows:
slowly dripping a toluene solution of n-octylamine into a toluene solution of cyanuric chloride ice slurry while stirring at the temperature of 0-5 ℃ and under the condition that the pH value is 8.5-9.5; monitoring the reaction end point by thin-layer chromatography, finishing the complete reaction of the cyanuric chloride, and filtering insoluble substances while the solution is hot; the filtrate is sequentially used with 1mol and L-1Hydrochloric acid solution, 1 mol. L-1Washing with NaOH solution, washing with distilled water for several times to obtain toluene layer, drying, and concentrating to obtain intermediate compound II.
6. The method according to claim 3, wherein the ratio of the amounts of n-octylamine and the compound II substance in the step 2 is 1: 1.0-1.5.
7. The preparation method according to claim 3, wherein the step 2 reaction specifically comprises the following steps:
dropwise adding the n-octylamine toluene solution into the toluene solution of the compound II under the conditions that the reaction temperature is 30-35 ℃ and the pH value is 8.0-9.0, and using a 500mL three-necked bottle as a reactor; and (3) monitoring the end point by thin-layer chromatography, finishing the reaction when the compound II is completely consumed, filtering to obtain a filter cake, washing the filter cake for multiple times by using toluene and distilled water in sequence, and drying to obtain the intermediate compound III.
8. The method according to claim 3, wherein the solid-to-liquid ratio of the compound III to N, N-dimethyl-1, 3-propanediamine is 1: 1-1.5 (g/ml).
9. The preparation method according to claim 3, wherein the step 3 reaction specifically comprises:
adding 0.10mol of the intermediate compound III into a three-necked bottle filled with 60mL of N, N-dimethyl-1, 3-propane diamine by 3 times, heating to 40-50 ℃, reacting and keeping for 1-1.5 hours; monitoring the reaction end point by thin-layer chromatography, and finishing the reaction when the compound III is completely reacted; dissolving the mixture after the reaction in 60mL of toluene, transferring the mixture into a separating funnel, and extracting the mixture for 3 times by using distilled water with the same volume until the toluene layer is neutral; the toluene layer was dried, and the toluene solvent was removed to obtain the objective compound I.
10. Use of a melamine derivative corrosion inhibitor according to claim 1 for carbon steel corrosion inhibition in an acidic environment.
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| WO2021170034A1 (en) * | 2020-02-28 | 2021-09-02 | 深圳深信生物科技有限公司 | Amino lipid compound, preparation method therefor, and application thereof |
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| CN113637014A (en) * | 2021-08-19 | 2021-11-12 | 中北大学 | Quaternary ammonium salt containing heterocyclic triazine group and preparation and application thereof |
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