CN113214309B - Mannich base, Mannich base quaternary ammonium salt, and preparation method and application thereof - Google Patents
Mannich base, Mannich base quaternary ammonium salt, and preparation method and application thereof Download PDFInfo
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 51
- 230000007797 corrosion Effects 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002798 polar solvent Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 aldehyde compound Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- 239000000022 bacteriostatic agent Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000008398 formation water Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WHMCHAMRUSRTNP-UHFFFAOYSA-N azane;butyl acetate Chemical compound N.CCCCOC(C)=O WHMCHAMRUSRTNP-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- KCFKHWSNVPJBEP-UHFFFAOYSA-N butylazanium;sulfate Chemical compound CCCCN.CCCCN.OS(O)(=O)=O KCFKHWSNVPJBEP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000008282 halocarbons Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000854 inhibitional effect Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WYNGSXIYPSAWFZ-UHFFFAOYSA-N CO[Si](CCCNCCC(C1=CC=CC=C1)=O)(OC)OC Chemical compound CO[Si](CCCNCCC(C1=CC=CC=C1)=O)(OC)OC WYNGSXIYPSAWFZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C23F11/141—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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Abstract
The application belongs to the technical field of corrosion inhibitors, and particularly relates to a Mannich base, a Mannich base quaternary ammonium salt, and a preparation method and application thereof. In a first aspect, the application provides a mannich base having a structure represented by formula i; formula I; wherein R is-CH 3 、‑C 2 H 5 、‑C 3 H 8 or-Ph; the R is 1 is-CH 3 Or C 2 H 5 (ii) a The R is 2 is-OCH 3 or-CH 3 . In a second aspect, the present application provides a process for the preparation of the mannich base, comprising: using hydrogen chloride as a catalyst, mixing aminosilane, an aldehyde compound, an anhydrous polar solvent and a compound containing active hydrogen for reaction, and then removing the anhydrous polar solvent to prepare the Mannich base with the structure shown in the formula I. The application provides a Mannich base, a Mannich base quaternary ammonium salt, and a preparation method and application thereof, which can effectively solve the technical problem that the conventional Mannich base corrosion inhibitor generally has weak adsorption capacity.
Description
Technical Field
The application belongs to the technical field of corrosion inhibitors, and particularly relates to a Mannich base, a Mannich base quaternary ammonium salt, and a preparation method and application thereof.
Background
A corrosion inhibitor is a chemical substance or a mixture of chemical substances that, when present in the environment (medium) in an appropriate concentration and form, prevents or slows down corrosion. In general, corrosion inhibitors are those substances which are used to protect metal surfaces, and the addition of small amounts or traces of such chemical substances can significantly reduce the corrosion rate of the metal material in the medium to zero. Meanwhile, the original physical and mechanical properties of the metal material can be kept unchanged. The reasonable use of corrosion inhibitors is an effective way to prevent metals and their alloys from corroding in the environment medium. The corrosion inhibitor technology has become one of the most widely applied methods in the corrosion prevention technology due to good effect and higher economic benefit. In particular, corrosion inhibition technology has become one of the main anti-corrosion means in the production and processing, chemical cleaning, atmospheric environment, industrial water, machine and instrument manufacturing and petrochemical production processes of petroleum products.
The Mannich base has polar genes and can be adsorbed by the surface charges of metal to form a monomolecular film on the whole anode and cathode areas, so that the corresponding electrochemical reaction is prevented or slowed down, and the metal surface is protected from corrosion, therefore, the Mannich base can be used for an adsorption type corrosion inhibitor. However, the conventional Mannich base corrosion inhibitor generally has the problem of weak adsorption capacity.
Disclosure of Invention
In view of the above, the application provides a mannich base, a mannich base quaternary ammonium salt, and a preparation method and application thereof, and can effectively solve the technical problem that the conventional mannich base corrosion inhibitor generally has weak adsorption capacity.
In a first aspect, the application provides a mannich base having a structure represented by formula i;
wherein R is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph;
the R is 1 is-CH 3 Or C 2 H 5 ；
The R is 2 is-OCH 3 or-CH 3 。
In a second aspect, the present application provides a process for the preparation of the mannich base, comprising:
the Mannich base with the structure shown in the formula I is prepared by taking hydrogen chloride as a catalyst, mixing and reacting aminosilane, an aldehyde compound, an anhydrous polar solvent and a compound containing active hydrogen, and then removing the anhydrous polar solvent.
In another embodiment, the molar ratio of the aminosilane, the aldehyde compound, and the anhydrous polar solvent is 1: (1-1.2): (10-20); the amount of the active hydrogen-containing compound added is 1 to 1.2 times equivalent.
In another embodiment, the reaction temperature is 50-80 ℃; the reaction time is 3-7 h.
In another embodiment, the reaction temperature is 60-80 ℃; the reaction time is 4 hours.
In another embodiment, the aminosilane is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethylsilane and gamma-aminopropylmethyldiethoxysilane.
In another embodiment, the aminosilane is gamma-aminopropyltriethoxysilane.
In another embodiment, the aldehyde compound is selected from one or more of paraformaldehyde, acetaldehyde, and benzaldehyde.
In another embodiment, the aldehyde compound is paraformaldehyde.
In another embodiment, the anhydrous polar solvent is selected from one or more of anhydrous n-butanol, anhydrous n-propanol, anhydrous ethanol, and anhydrous dimethyl sulfoxide.
In another embodiment, the anhydrous polar solvent is anhydrous n-butanol.
In another embodiment, the active hydrogen-containing compound is selected from one or more of acetone, acetophenone, methyl ethyl ketone, methyl acetone, and acetonitrile.
In another embodiment, the active hydrogen-containing compound is acetone or/and acetophenone.
Specifically, the anhydrous polar solvent is removed by distillation under reduced pressure.
Specifically, the preparation method of the Mannich base comprises the following steps: under the protection of protective gas, adding aminosilane, aldehyde compound, anhydrous polar solvent and active hydrogen-containing solvent into a reactor, wherein the molar ratio of the aminosilane to the aldehyde compound to the anhydrous polar solvent is 1: (1-1.2): (10-20), reacting at 50-80 ℃ for 1-2 h with the addition of active hydrogen as the addition of the conventional catalyst, adding 1-1.2 times of equivalent of an active hydrogen-containing compound, continuing to react at 50-70 ℃ for 3-5 h, and removing the solvent by reduced pressure evaporation to obtain the Mannich base, wherein the active hydrogen-containing compound is one or more of acetone, acetophenone, methyl ethyl ketone, methyl acetone and acetonitrile.
Specifically, the mannich base of the present application has the following synthetic route: r is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph; r 1 is-CH 3 Or C 2 H 5 ；R 2 is-OCH 3 or-CH 3 ；
In a third aspect, the application provides a Mannich base quaternary ammonium salt having a structure represented by formula II;
wherein R is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph;
the R is 1 is-CH 3 Or C 2 H 5 ；
The R is 2 is-OCH 3 or-CH 3 ；
A is-CH 3 、-C 2 H 5 、-C 3 H 8 、-C 4 H 10 、-C 5 H 12 、-C 6 H 14 、-C 7 H 16 or-Bn.
In a third aspect, the present application provides a method of preparing a mannich base quaternary ammonium salt, comprising: mixing the Mannich base, a reaction reagent and absolute ethyl alcohol for reaction, and removing small molecular substances to obtain a Mannich base quaternary ammonium salt shown in a formula II; wherein the reactant is selected from halogenated hydrocarbon or/and dimethyl sulfate.
In another embodiment, the halogenated hydrocarbon is a brominated hydrocarbon or a chlorinated hydrocarbon.
In another embodiment, the molar ratio of the mannich base to the reactants is 1: (1.8-2.2).
In another embodiment, the reaction temperature is 50-80 ℃, and the reaction time is 4-7 h.
In another embodiment, the reaction temperature is 65-75 ℃, and the reaction time is 4 h.
Specifically, under the protection of gas, adding Mannich base, bromohydrocarbon (or dimethyl sulfate) and absolute ethyl alcohol into a reactor, wherein the molar ratio of the Mannich base to the bromohydrocarbon is 1: 1.8-1: 2.2, heating to 65-75 ℃, reacting for 4-6h, and evaporating under reduced pressure to remove small molecular substances to obtain the organosilicon Mannich base quaternary ammonium salt corrosion inhibitor.
Specifically, the protective gas is nitrogen.
Specifically, the mannich base quaternary ammonium salt has the following synthetic route: r is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph; r 1 is-CH 3 Or C 2 H 5 (ii) a The R is 2 is-OCH 3 or-CH 3 (ii) a A is-CH 3 、-C 2 H 5 、-C 3 H 8 、-C 4 H 10 、-C 5 H 12 、-C 6 H 14 、-C 7 H 16 or-Bn;
in a fourth aspect, the application discloses the Mannich base, the Mannich base prepared by the preparation method, the Mannich base quaternary ammonium salt, or the Mannich base quaternary ammonium salt prepared by the preparation method in corrosion inhibition and bacteriostasis.
The application aims to solve the problem that the conventional Mannich base corrosion inhibitor is poor in adsorption capacity. The Mannich base of the formula I and the Mannich base quaternary ammonium salt of the formula II contain silicon methoxyl which can change the hydrophilic and hydrophobic structure of the surface of metal and can be hydrolyzed to form silanol and methanol, wherein the silanol can form strong coordination with the metal through a coordination bond, so that the Mannich base and the quaternary ammonium salt thereof are tightly combined with the metal to form a firm film. The Mannich base quaternary ammonium salt has the excellent surface activity of organosilicon and the performance of quaternary ammonium salt, and can meet the corrosion inhibition requirement of acidizing and fracturing. Therefore, the defect of insufficient adsorption capacity of the conventional Mannich base is overcome, the types of corrosion inhibitors can be increased, and the requirements on acidification and corrosion inhibition under different conditions are met. Meanwhile, the Mannich base and the Mannich base quaternary ammonium salt are relatively simple in synthesis method, mild in reaction condition, easy to separate and high in yield. The Mannich base and the Mannich base quaternary ammonium salt can be used in the fields of industrial cooling water, acid cleaning, oil-gas well acidification, metal product storage and transportation and the like, and can also be used in the industries of textile, daily chemical industry and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a nuclear magnetic diagram of Mannich base A provided in the examples herein;
FIG. 2 is an infrared spectrum of Mannich base A provided in the examples herein;
FIG. 3 is a nuclear magnetic map of Mannich base Quaternary ammonium salt B provided in the examples herein;
FIG. 4 is an infrared spectrum of a Mannich base quaternary ammonium salt B provided in an example herein;
FIG. 5 is a nuclear magnetic diagram of Mannich base C provided in an example herein;
FIG. 6 is a chart of an infrared spectrum of Mannich base C provided in examples herein;
FIG. 7 is a nuclear magnetic diagram of a Mannich base quaternary ammonium salt D provided in an example herein;
FIG. 8 is an infrared spectrum of a Mannich base quaternary ammonium salt D provided in examples herein;
FIG. 9 is a graph of the corrosion rates of Mannich base Quaternary ammonium salt D provided in the examples herein;
FIG. 10 is a graph of the effect of Mannich base Quaternary ammonium salt D on bacteriostasis provided in the examples herein;
FIG. 11 is a chemical structure of a Mannich base provided in an example herein;
FIG. 12 is a chemical structural formula of a Mannich base quaternary ammonium salt provided in an embodiment herein;
FIG. 13 is a scheme of a Mannich base provided in an embodiment of the present application;
FIG. 14 is a synthetic route for a Mannich base quaternary ammonium salt provided in an embodiment of the present application.
Detailed Description
The application provides a Mannich base, a Mannich base quaternary ammonium salt, and a preparation method and application thereof, which are used for solving the technical defect that the Mannich base corrosion inhibitor in the prior art generally has weak adsorption capacity.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, 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 application.
The reagents or raw materials used in the following examples are commercially available or self-made.
The mannich bases of the following examples were prepared by a process comprising: under the protection of nitrogen, adding aminosilane, paraformaldehyde, an anhydrous polar solvent and hydrogen chloride into a reactor, wherein the molar ratio of gamma-aminopropyltriethoxysilane to paraformaldehyde to the anhydrous polar solvent is 1:1:10 to 1:1.2:20, the hydrogen chloride is used as a catalyst amount, reacting for about 1-2 h at 50-80 ℃, adding 1-1.2 times of equivalent of an active hydrogen-containing compound, continuing to react for 3-5 h at 50-70 ℃, and evaporating the solvent under reduced pressure to obtain the Mannich base, wherein the active hydrogen-containing compound is acetone, acetophenone, methyl ethyl ketone, methyl acetone, acetonitrile and the like.
The preparation method of the Mannich base quaternary ammonium salt of the following embodiment comprises the following steps: adding Mannich base, bromohydrocarbon (or dimethyl sulfate) and absolute ethyl alcohol into a reactor under the protection of nitrogen, wherein the molar ratio of the Mannich base to the bromohydrocarbon is 1: 1.8-1: 2.2, heating to 65-75 ℃, reacting for 4-6h, and removing small molecular substances through reduced pressure evaporation to obtain the organosilicon Mannich base quaternary ammonium salt corrosion inhibitor, wherein R is-CH 3 、-C 2 H 5 、-C 3 H 8 -Ph, A is-CH 3 、-C 2 H 5 、-C 3 H 8 、-C 4 H 10 、-C 5 H 12 、-C 6 H 14 、-C 7 H 16 and-Bn.
The mannich bases and mannich base quaternary ammonium salts of the following examples are prepared without water and all reagents used are anhydrous.
Example 1
The embodiment of the application provides a Mannich base which is 4- ((3- (trimethoxysilyl) propyl) amino) butane-2-ketone, and the specific preparation method comprises the following steps:
in a 500mL three-neck flask with a condenser tube, under the protection of nitrogen, 35.8g (0.2mol) of gamma-aminopropyl triethoxy siloxane, 6.1g (0.2mol) of paraformaldehyde and 250mL of n-butanol are added to react for 1 hour at 60 ℃, then 12.2g (0.21mol) of acetone is added dropwise to react for 3 hours at 60 ℃, and the solvent is evaporated under reduced pressure to prepare 42.5g of a product named as Mannich base A, wherein the yield of the Mannich base A is 85.2%.
The results of measuring the nuclear magnetic pattern and the infrared spectrum of Mannich base A are shown in FIGS. 1 and 5.
Example 2
The embodiment of the application provides Mannich base quaternary ammonium salt which is N, N-dimethyl-3-oxo-N- (3- (trimethoxy silicon) propyl) ammonium butylacetate, and the specific preparation method comprises the following steps:
under the protection of nitrogen, 30g (0.12mol) of Mannich base A prepared in example 1, 60.54(0.24mol) of dimethyl sulfate and 400mL of absolute ethyl alcohol are added into a reactor, stirred for 3 hours at room temperature, then heated to 65 ℃, continuously reacted for 4 hours, cooled to room temperature, reduced pressure evaporated to remove small molecular substances, and absolute ethyl alcohol is recrystallized to obtain 33.6g of Mannich base quaternary ammonium salt B which is named as N, N-dimethyl-3-oxo-N- (3- (trimethoxy silicon) propyl) butyl ammonium sulfate and has the yield of the Mannich base quaternary ammonium salt B of 78.3%.
The results of measuring the nuclear magnetic pattern and the infrared spectrogram of the Mannich base quaternary ammonium salt B are shown in FIGS. 2 and 6.
Example 3
The embodiment of the application provides a Mannich base which is 1-phenyl-3- ((3- (trimethoxysilyl) propyl) amino) propane-1-ketone, and the specific preparation method comprises the following steps:
in a 500mL three-neck flask with a condenser tube, under the protection of nitrogen, 35.8g (0.2mol) of gamma-aminopropyl triethoxy siloxane, 6.1g (0.2mol) of paraformaldehyde and 250mL of n-butanol are added for reaction at 80 ℃ for 1 hour, 25.3g (0.21mol) of acetophenone is added dropwise for reaction at 80 ℃ for 3 hours, and the solvent is evaporated under reduced pressure to prepare 51.1g of a product, namely Mannich base C, wherein the yield of the Mannich base C is 82.1%.
The results of measuring the nuclear magnetic pattern and the infrared spectrum of Mannich base C are shown in FIGS. 3 and 7.
Example 4
The embodiment of the application provides Mannich base quaternary ammonium salt which is N, N-dimethyl-3-oxo-N- (3- (trimethoxy silicon) propyl) ammonium butylacetate, and the specific preparation method comprises the following steps:
under the protection of nitrogen, 35g (0.112mol) of the Mannich base C prepared in example 3, 28.3(0.224mol) of dimethyl sulfate and 300mL of absolute ethyl alcohol are added into a reactor, stirred for 3h at room temperature, heated to 75 ℃, continuously reacted for 4h, cooled to room temperature, reduced pressure evaporated to remove small molecular substances, and absolute ethyl alcohol is recrystallized to obtain 41.9g of Mannich base quaternary ammonium salt D which is named as N, N-dibenzyl-3-oxo-3-phenyl-N- (3- (trimethoxysilyl) propyl) ammonium butyl sulfate and has the yield of the Mannich base quaternary ammonium salt D of 72.4%.
The results of measuring the nuclear magnetic pattern and the infrared spectrogram of the Mannich base quaternary ammonium salt D are shown in FIGS. 4 and 8.
Example 5
In the embodiment of the application, the corrosion inhibition performance test of the products prepared in the embodiments 1 to 4 comprises the following specific steps:
in the embodiment, simulated formation water is used as a corrosion medium, and products prepared in the embodiments 1 to 4 are used as corrosion inhibitors. The corrosion rate of the N80 steel test piece is measured by a static hanging piece weight loss method when the addition of the corrosion inhibitor is 200ppm, the corrosion temperature is 80 ℃, and the corrosion time is 96 h. The corrosion rate is measured according to the oil and gas industry standard SY5405-1996, Corrosion inhibitor Performance test method for acidification and evaluation index for the people's republic of China.
The simulated formation water composition is shown in table 1, and the corrosion rates of the mannich bases and the quaternary ammonium salts thereof obtained in examples 1-4 are shown in table 2. As can be seen from the table 2, the Mannich bases and the quaternary ammonium salts thereof prepared in the embodiments 1 to 4 have excellent corrosion resistance, wherein the corrosion rate of the Mannich base quaternary ammonium salt D is lower than 0.076mm/a, and the corrosion protection requirements of the oil and gas field ground official networks can be met.
TABLE 1 ion content of simulated formation water
Table 2 examples 1-4 mannich bases and their quaternary ammonium salts have corrosion inhibiting effect under simulated formation water conditions
Example 6
The embodiment of the application provides a performance test of the corrosion inhibitor for acidification on the Mannich base quaternary ammonium salt D prepared in the embodiment 4, which specifically comprises the following steps:
the acidification operation of oil and gas wells is a common measure in the development process of oil and gas fields, but the acidic components in the process can cause serious corrosion to oil pipes, casings and the like. In order to inhibit and slow down the corrosion of acid liquor to oil pipes, casings and other equipment, the most common and effective method in the operation process is to add a corrosion inhibitor into the acid liquor. The corrosion medium is 10% HCl water, and the addition amount (mass fraction) of the Mannich base quaternary ammonium salt D of the N80 steel test piece is 1.0% by adopting a static hanging piece weight loss method, the corrosion time is 4h, and the corrosion rate is 40-90 ℃. The corrosion rate is measured according to the oil and gas industry standard SY5405-1996, Corrosion inhibitor Performance test method for acidification and evaluation index for the people's republic of China. The corrosion rates of the mannich base quaternary ammonium salt D are shown in fig. 9.
Example 7
The embodiment of the application provides a Mannich base quaternary ammonium salt D prepared in the embodiment 4 for a bacteriostasis rate test, which specifically comprises the following steps:
the antibacterial effect is measured according to the textile industry standard FZ/T-73023 and 2006 antibacterial knitwear. And (3) carrying out quantitative determination on the antibacterial effect of the antibacterial finished fabric by adopting an oscillation method according to national textile industry standard FZ/T-73023-2006, selecting 0.75g of the antibacterial fabric, soaking the antibacterial fabric in a buffer solution containing staphylococcus aureus, placing the antibacterial fabric in an oscillation culture box for oscillation culture for 18h, and determining the reproduction condition of the staphylococcus aureus in the solution to obtain the antibacterial effect of the fabric. The effect of mannich base quaternary ammonium salt D on the bacteriostatic ratio is shown in fig. 10.
Comparative example 1
Comparative example of the present application provides a control sample prepared by referring to example 3 except that water (amount of dissolved solute) was further added to the reaction system and the remaining steps were identical to example 3 to obtain a control product 1, however, the reaction failed due to the presence of water in the reaction system, the obtained control product 1 was not 1-phenyl-3- ((3- (trimethoxysilyl) propyl) amino) propan-1-one, and the control product 1 had no corrosion inhibition and antibacterial effects.
Comparative example 2
Comparative example of the present application provides a control sample, which was prepared by referring to example 4 except that water (the amount of dissolved solute) was further added to the reaction system and the remaining steps were identical to example 4, to obtain a control product 2, however, the reaction failed due to the presence of water in the reaction system, the obtained control product 2 was not N, N-dimethyl-3-oxo-N- (3- (trimethoxy silicon) propyl) butyl ammonium sulfate, and the control product 2 had no corrosion inhibition and antibacterial effects.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (9)
1. A Mannich base is characterized by having a structure shown as a formula I;
wherein R is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph;
the R is 1 is-CH 3 Or C 2 H 5 ；
The R is 2 is-OCH 3 or-CH 3 。
2. A process for the preparation of the mannich base according to claim 1, which comprises:
taking hydrogen chloride as a catalyst, mixing aminosilane, an aldehyde compound, an anhydrous polar solvent and a compound containing active hydrogen for reaction, and then removing the anhydrous polar solvent to prepare a Mannich base with a structure shown in a formula I;
the aminosilane is selected from gamma-aminopropyltrimethoxysilane or gamma-aminopropylmethyldiethoxysilane;
the aldehyde compound is paraformaldehyde;
the active hydrogen-containing compound is selected from one or more of acetone, acetophenone, methyl ethyl ketone and methyl acetone.
3. The preparation method according to claim 2, wherein the reaction temperature is 50-80 ℃; the reaction time is 3-7 h.
4. The production method according to claim 2,
the anhydrous polar solvent is one or more selected from anhydrous n-butanol, anhydrous n-propanol, anhydrous ethanol and anhydrous dimethyl sulfoxide.
5. A Mannich base quaternary ammonium salt is characterized by having a structure shown in a formula II;
wherein R is-CH 3 、-C 2 H 5 、-C 3 H 8 or-Ph;
the R is 1 is-CH 3 Or C 2 H 5 ；
The R is 2 is-OCH 3 or-CH 3 ；
A is-CH 3 、-C 2 H 5 、-C 3 H 7 、-C 4 H 9 、-C 5 H 11 、-C 6 H 13 、-C 7 H 15 or-Bn.
6. A method of preparing a Mannich base quaternary ammonium salt according to claim 5, comprising: mixing the Mannich base, the reaction reagent and absolute ethyl alcohol according to claim 1 for reaction, and removing small molecular substances to obtain Mannich base quaternary ammonium salt; wherein the reactive agent is selected from brominated hydrocarbons.
7. The method of claim 6, wherein the molar ratio of the Mannich base to the reactants is from 1: (1.8-2.2).
8. The preparation method according to claim 6, wherein the reaction temperature is 50-80 ℃ and the reaction time is 4-7 hours.
9. Use of a mannich base as claimed in claim 1, or of a mannich base obtainable by a process as claimed in any one of claims 2 to 4, or of a mannich base quaternary ammonium salt as claimed in claim 5, or of a mannich base quaternary ammonium salt obtainable by a process as claimed in any one of claims 6 to 8 for the preparation of corrosion-inhibiting and bacteriostatic agents.
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| CN102746840A (en) * | 2012-07-18 | 2012-10-24 | 天津大港油田科远石油工程有限责任公司 | Mannich base acidifying corrosion inhibitor and preparation method thereof |
| CN103881696A (en) * | 2014-03-11 | 2014-06-25 | 山东聚鑫化工有限公司 | High-water-solubility and high-temperature-resistant Mannich base corrosion inhibitor intermediate and preparation method thereof |
| WO2021077119A1 (en) * | 2019-10-18 | 2021-04-22 | Topikos Pharmaceuticals, Inc. | Antimicrobial organosilanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102746840A (en) * | 2012-07-18 | 2012-10-24 | 天津大港油田科远石油工程有限责任公司 | Mannich base acidifying corrosion inhibitor and preparation method thereof |
| CN103881696A (en) * | 2014-03-11 | 2014-06-25 | 山东聚鑫化工有限公司 | High-water-solubility and high-temperature-resistant Mannich base corrosion inhibitor intermediate and preparation method thereof |
| WO2021077119A1 (en) * | 2019-10-18 | 2021-04-22 | Topikos Pharmaceuticals, Inc. | Antimicrobial organosilanes |
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