CN117126063A - Metal corrosion inhibition component and preparation method and application thereof - Google Patents
Metal corrosion inhibition component and preparation method and application thereof Download PDFInfo
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- CN117126063A CN117126063A CN202210543892.4A CN202210543892A CN117126063A CN 117126063 A CN117126063 A CN 117126063A CN 202210543892 A CN202210543892 A CN 202210543892A CN 117126063 A CN117126063 A CN 117126063A
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- metal corrosion
- corrosion inhibition
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- 230000007797 corrosion Effects 0.000 title claims abstract description 174
- 238000005260 corrosion Methods 0.000 title claims abstract description 174
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 122
- 239000002184 metal Substances 0.000 title claims abstract description 122
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 239000003112 inhibitor Substances 0.000 claims description 23
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000002401 inhibitory effect Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical group [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims 3
- 239000002198 insoluble material Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000000007 visual effect Effects 0.000 abstract description 5
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 4
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
-
- 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
- C23F11/143—Salts of amines
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a metal corrosion inhibition component, a preparation method and application thereof, wherein the metal corrosion inhibition component is thiocyanate of primary amine containing tetraphenyl ethylene, and the metal corrosion inhibition component is excellent in metal corrosion inhibition performance and easy to detect the concentration in a corrosive medium. In addition, the compound can emit stronger fluorescence after being adsorbed on the metal surface, which is beneficial to visual detection.
Description
Technical Field
The invention relates to a metal corrosion inhibition component and a preparation method and application thereof, in particular to a metal corrosion inhibition component with a fluorescent effect and a preparation method and application thereof.
Background
Metal corrosion is a common problem in industrial production, and safety accidents and unplanned shutdown accidents caused by metal corrosion cause huge losses to enterprises. The metal corrosion prevention measures comprise material upgrading, process corrosion prevention, corrosion monitoring and the like, wherein the corrosion monitoring is used for realizing predictive maintenance and repair, and a process corrosion prevention foundation is made.
The upgrading of metal materials, which is more corrosion resistant, is one method of slowing down corrosion, but it is more economical to add metal corrosion inhibitors. Common metal corrosion inhibitors include organic amines, thiourea derivatives, imidazoline derivatives, alkynols, benzotriazole and the like, but these metal corrosion inhibitors have disadvantages such as unsatisfactory corrosion inhibition performance, poor water solubility and the like, and thus it is necessary to provide corrosion inhibitors which are more advantageous in performance. The existing metal corrosion inhibitor is difficult to detect the effective concentration, more targeted supplement measures are difficult to implement, the current mode is to periodically and quantitatively supplement the corrosion inhibitor, proper dosage of the chemical agent is difficult to ensure, waste is generated when the chemical agent concentration is too high, and the required corrosion inhibition effect cannot be achieved when the chemical agent concentration is too low. In particular, the existing metal corrosion inhibitor is more difficult to detect the adsorption degree of the metal corrosion inhibitor on the metal surface, and is difficult to realize predictability positioning maintenance.
CN107973732a discloses a method for preparing corrosion inhibition component, its product and application, and the maximum carbon number of hydrocarbon group in the organic ammonium salt disclosed in this document is 18. In general, larger hydrocarbon groups result in reduced solubility and dispersibility in water, affecting corrosion inhibition performance. In addition, this document does not disclose hydrocarbon groups containing a plurality of benzene rings, nor do the corrosion inhibiting components thereof have a fluorescent effect.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
The invention provides a metal corrosion inhibition component, a preparation method and application thereof, and the metal corrosion inhibition component not only has better metal corrosion inhibition performance, but also is easy to detect the concentration in a corrosive medium, so that corrosion protection can be more conveniently carried out. In addition, the metal corrosion inhibition component has a fluorescent effect when being adsorbed on the metal surface, so that corrosion hidden danger can be found in time, and the occurrence of metal corrosion can be prevented and reduced more effectively.
The main content of the invention is as follows:
1. the metal corrosion inhibition component is characterized by having a structure shown in a formula I:
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 、R 2 And R is 3 Each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
2. A metal corrosion inhibiting composition according to any one of the preceding claims, characterized in that R 1 、R 2 And R is 3 Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a hydrocarbon group, or the same substituent as that bonded to the benzene ring (4).
3. The metal corrosion inhibiting composition according to any one of the preceding claims, wherein the substituents on the benzene rings (labeled (1), (2), (3), (4)) are all para to the vinyl group.
4. The metal corrosion inhibition component according to any one of the preceding claims, wherein m and n are each 0, R 1 、R 2 And R is 3 One, two or all of the substituents on the benzene ring (4) are the same, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.
5. A method of preparing a metal corrosion inhibiting composition comprising:
(1) In a polar solvent, firstly, reacting a compound shown in a formula II with acid;
(2) Then adding thiocyanate to react to generate precipitate, and removing insoluble substances and polar solvents generated in the reaction system to obtain the metal corrosion inhibition component;
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
8. The process according to any one of the preceding processes, wherein R in the compound of formula II 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that bonded to the benzene ring (4).
9. The process according to any one of the preceding processes, wherein the substituents on the benzene rings (labeled (1), (2), (3), (4)) are all para to the vinyl group in the compound of formula II.
10. The preparation method according to any one of the above, characterized in that in the compound shown in the formula II, m and n are 0 and R 1 ’、R 2 ' and R 3 One, two or all of the substituents' are the same as the substituents on the benzene ring (4), and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.
11. The preparation method according to any one of the preceding methods, characterized in that the polar solvent consists of 35 to 0% by volume of water and 65 to 100% by volume of a water-miscible organic solvent.
12. The preparation method is characterized in that the organic solvent which can be mixed with water is one or more of methanol, ethanol, N-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 1, 4-dioxane and ethylene glycol.
13. The preparation method according to any one of the above methods is characterized in that the dosage ratio of the compound shown in the formula II, the acid and the thiocyanate is 1:1:1 based on the total molar amount of amino, acid dissociable hydrogen ions and thiocyanate ions in the compound shown in the formula II.
14. The preparation method according to any one of the above, wherein the thiocyanate is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.
15. The process according to any one of the preceding claims, characterized in that the acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.
16. The preparation method according to any one of the above methods is characterized in that in the step (1), the reaction temperature is 20-50 ℃ and the reaction time is 10 min-2 h.
17. The preparation method according to any one of the above methods is characterized in that in the step (2), the reaction temperature is 30-100 ℃ and the reaction time is 20 min-4 h.
18. The metal corrosion inhibition component is characterized in that after the reaction is finished, insoluble matters are removed by filtration, and then the solvent is removed or not removed, so that the metal corrosion inhibition component is obtained.
19. The metal corrosion inhibition component is applied to the field of metal hydrogen evolution corrosion protection.
20. A metal corrosion inhibitor, characterized by comprising any one of the foregoing metal corrosion inhibiting components.
21. A metal corrosion inhibition method is characterized in that the corrosion medium contains any metal corrosion inhibition component.
22. The metal corrosion inhibition method is characterized in that the corrosion medium contains any one of the metal corrosion inhibition components, and the concentration of the metal corrosion inhibition components in the corrosion medium is detected and controlled by an ultraviolet-visible absorption spectrometry; the concentration of the metal corrosion inhibition component in the corrosive medium is preferably controlled between 40mg/L and 160mg/L.
23. The copper corrosion protection method is characterized in that any one of the metal corrosion inhibition components is adsorbed on the copper surface, and corrosion inhibition treatment is carried out on areas of the copper surface, which are not fluorescent or have weaker fluorescence than other areas, through fluorescence of the copper surface under ultraviolet light irradiation.
The invention has the following beneficial technical effects:
1. although the metal corrosion inhibition component provided by the invention has larger tetrastyryl groups, the metal corrosion inhibition component is easy to adsorb on the metal surface, and further has good performance of protecting metal corrosion.
2. The metal corrosion inhibition component can emit stronger visible fluorescence even if adsorbed and accumulated on the metal surface, so that visual detection can be realized when the metal corrosion inhibition component is used as the metal corrosion inhibition component, and the positioned metal corrosion protection can be realized.
3. The metal corrosion inhibition component can detect the concentration in the corrosive medium, and can take the supplement measures more pertinently by detecting the concentration.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the product of example 1.
FIG. 2 is a mass spectrum of the product of example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the product of example 2.
Fig. 4 is a mass spectrum of the product of example 2.
Fig. 5 is an ultraviolet-visible absorption spectrum of the product of example 2.
FIG. 6 is a photograph of a brass coupon after the corrosion test has been completed, the coupon being exposed to ultraviolet light.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The following are definitions of partial terms:
hydrocarbon groups, groups in which one hydrogen atom is removed from the hydrocarbon.
Alkyl, hydrocarbon group formed by removing one hydrogen atom from saturated alkane molecule.
Aryl, hydrocarbon groups formed by removing one hydrogen atom from an aromatic ring carbon.
Primary amines, compounds in which one hydrogen atom in the ammonia molecule is substituted with a hydrocarbyl or substituted hydrocarbyl group.
Precipitation, reaction to form insoluble matter.
In the present invention, the corrosive medium refers to an aqueous or substantially aqueous acidic medium.
In the present invention, when referring to substituents on benzene rings in a tetraphenyl ethylene derivative, the substituents other than vinyl groups on four benzene rings of tetraphenyl ethylene are meant.
1. The metal corrosion inhibition component of the invention
The invention provides a metal corrosion inhibition component, which has a structure shown in a formula I:
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 、R 2 And R is 3 Each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
According to the metal corrosion inhibition component, the metal corrosion inhibition component is easy to adsorb on the surface of metal, has metal corrosion inhibition performance, and can easily detect the concentration of the metal corrosion inhibition component in corrosive media.
The metal corrosion inhibition component can emit stronger fluorescence under ultraviolet light excitation after being adsorbed on certain metal surfaces, such as copper surfaces. Fluorescent quenching may occur when a general fluorescent substance is adsorbed on a metal surface; some fluorescent substances have stronger fluorescence in dilute solutions, but the fluorescence is weakened or vanished at high concentrations or in an aggregated state. However, the compound of the invention can emit stronger visible fluorescence even if adsorbed and accumulated on the metal surface, so that the compound can realize visual detection when being used as a metal corrosion inhibition component. However, the metal corrosion inhibition component can emit stronger visible fluorescence even if adsorbed and accumulated on the metal surface, so that the metal corrosion inhibition component can realize visual detection when being used as the metal corrosion inhibition component. When the metal corrosion inhibitor is used as the metal corrosion inhibitor, if the metal surface emits uniform fluorescence everywhere, the metal corrosion inhibitor forms a uniform and complete protective film, and the corrosion inhibitor does not need to be added at the moment; if no fluorescence or weak fluorescence exists in a certain area of the metal surface, the area is not adsorbed with the corrosion inhibitor, the protective film is not formed or the corrosion inhibitor is desorbed, the protective film is incomplete, or the corrosion inhibitor is less adsorbed, and only the corrosion inhibitor is needed to be added and the protective film is repaired in a positioning way, so that the medicament is saved, the high-efficiency protection is realized, and the positioned corrosion protection can be realized.
According to the metal corrosion inhibition component of the invention, R 1 、R 2 And R is 3 Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a hydrocarbon group, or the same substituent as that bonded to the benzene ring (4). The hydrocarbyl group may be an alkyl group, may be an alkanyl group such as methyl, ethyl or propyl, may be cycloalkyl, and may be an aryl group such as phenyl.
According to the metal corrosion inhibition component of the invention, the substituent groups on the benzene rings (marked as (1), (2), (3) and (4)) can be positioned at any positions on the benzene rings, namely ortho-position, meta-position or para-position of vinyl; preferably, the substituent on the benzene ring (4) is located at the para position of the vinyl group; more preferably, all substituents on the phenyl ring are para to the vinyl group.
According to the metal corrosion inhibiting composition of the present invention, a preferred embodiment is: m and n are 0, R 1 、R 2 And R is 3 One, two or all of the substituents on the benzene ring (4) are the same, and the remaining substituents are each independently a hydrogen atom or a C1-C4 alkyl group.
2. Preparation method of metal corrosion inhibition component
The invention also provides a preparation method of the metal corrosion inhibition component, which comprises the following steps:
(1) In a polar solvent, firstly, reacting a compound shown in a formula II with acid;
(2) Then adding thiocyanate to react to generate precipitate, and removing insoluble substances and polar solvents generated in a reaction system to obtain the compound;
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
The preparation method according to the invention has the following reaction scheme:
according to the preparation method of the invention, R in the compound shown in the formula II 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that bonded to the benzene ring (4).
According to the preparation method of the present invention, the compound represented by formula II may be obtained either commercially or by any known method.
According to the preparation method of the invention, in the compound shown in the formula II, the substituent groups on the benzene rings (marked as (1), (2), (3) and (4)) can be positioned at any positions on the benzene rings, namely, can be positioned at the ortho position, the meta position or the para position of vinyl; preferably, the substituent on the benzene ring (4) is located at the para position of the vinyl group; more preferably, all substituents on the phenyl ring are para to the vinyl group.
According to the preparation method of the invention, in the compound shown in the formula II, m and n are both 0 and R 1 ’、R 2 ' and R 3 One of the' substituents is the same as the substituent on the benzene ring (4), and the remaining substituents are each independently a hydrogen atom or a C1-C4 hydrocarbon group; or R is 1 ’、R 2 ' and R 3 Two of the' are the same as the substituent on the benzene ring (4), and the other substituent is a hydrogen atom or a C1-C4 hydrocarbon group; or R is 1 ’、R 2 ' and R 3 ' all are identical to substituents on the benzene ring (4).
According to the preparation method of the invention, the polar solvent consists of 35-0 v% of water and 65-100 v% of water-miscible organic solvent, preferably 25-4 v% of water and 75-96 v% of water-miscible organic solvent.
According to the preparation method of the invention, the organic solvent which can be mixed with water is one or more of methanol, ethanol, N-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 1, 4-dioxane and ethylene glycol.
According to the preparation method of the invention, the amounts of acid and thiocyanate are determined relative to the amount of amino substance in the compound of formula II. The person skilled in the art can determine the ratio of the amounts of the suitable substances by simple experiments, depending on the requirements of the reaction. According to the preparation method of the invention, the dosage ratio of the compound shown in the formula II, the acid and the thiocyanate is about 1:1:1 based on the total molar quantity of amino, acid dissociable hydrogen ions and thiocyanate ions in the compound shown in the formula II.
According to the preparation method of the invention, the thiocyanate is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.
According to the preparation method of the invention, the acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.
According to the preparation method, in the step (1), the reaction temperature is 20-50 ℃ and the reaction time is 10 min-2 h.
According to the preparation method, in the step (2), the reaction temperature is 30-100 ℃ and the reaction time is 20 min-4 h.
In some embodiments, the compound of formula II is 4-aminotetrastyrene, di- (4-amino) -tetraphenyl ethylene (cis or trans), tri- (4-amino) -tetraphenyl ethylene, tetra- (4-amino) -tetraphenyl ethylene, or 4- (2-amino) ethoxytetraphenyl ethylene.
According to the preparation method of the present invention, any means of removing insoluble matter and solvent in the reaction system may be used, but it is convenient to remove insoluble matter by filtration and then remove polar solvent by evaporation.
The invention also provides a metal corrosion inhibition component: in the method, after the reaction is finished, insoluble matters are filtered and removed, and the solvent can be removed, partially removed or not removed, so that the metal corrosion inhibition component is obtained.
3. Application of metal corrosion inhibition component of the invention
The invention provides application of any metal corrosion inhibition component in the field of metal hydrogen evolution corrosion protection.
According to the application of the invention, the metal corrosion inhibition component is suitable for the environment with hydrogen evolution corrosion, and is particularly suitable for the environment with mainly or only hydrogen evolution corrosion.
According to the application of the invention, the metal corrosion inhibition component of any one of the foregoing is used in a strongly acidic environment. The strongly acidic environment may be an aqueous phase containing strong acids of different concentrations, such as an aqueous phase containing one or more of sulfuric acid, hydrochloric acid, earth acid, sulfamic acid, and the like. The strong acidity may be a pH < 3.
According to the application of the invention, the metal corrosion inhibition component is used in a weak acid environment. The weakly acidic environment can be aqueous phase containing weak acids with different concentrations, such as aqueous phase containing one or more of formic acid, acetic acid, citric acid, etc., or dissolved with CO 2 、H 2 S、SO 2 And the like. In the present invention, the weak acidity may be a pH of 3 to 7.
The invention provides a metal corrosion inhibitor which contains any one of the metal corrosion inhibition components.
The invention also provides a metal corrosion inhibition method, and the corrosion medium contains any metal corrosion inhibition component. The concentration of any of the foregoing metal corrosion inhibiting components in the corrosive medium may be controlled to be in the range of 40mg/L to 160mg/L, preferably in the range of 60mg/L to 140mg/L, and more preferably in the range of 70mg/L to 120mg/L.
The invention also provides another metal corrosion inhibition method, wherein the corrosion medium contains any metal corrosion inhibition component, and the total concentration of any metal corrosion inhibition component in the corrosion medium is detected and controlled by an ultraviolet-visible absorption spectrometry; preferably by ultraviolet-visible absorption spectroscopy, and controlling the total concentration of any of the foregoing metal corrosion inhibiting components in the corrosive medium to be between 40mg/L and 160mg/L.
The invention also provides a copper corrosion protection method, wherein the metal corrosion inhibition component is adsorbed on the copper surface, and the corrosion inhibition treatment is carried out on the areas of the copper surface which have no fluorescence or have weaker fluorescence than other areas through the fluorescence of the copper surface under the irradiation of ultraviolet light.
According to the copper corrosion protection method, the corrosion inhibition treatment is to supplement and adsorb any metal corrosion inhibition component.
According to the copper corrosion protection method, for the areas where the corrosion inhibitor is not adsorbed, the protective film is not formed or the corrosion inhibitor is desorbed and the protective film is damaged, only the corrosion inhibitor is required to be added and the protective film is required to be repaired in a positioning way, so that the medicament can be saved, the high-efficiency protection can be realized, and the positioning corrosion protection can be realized. This can be easily achieved on the metal surface plane, and even on the inner wall of the metal pipeline, the purposes of detection and directional dosing can be achieved by means of an endoscopic ultraviolet light source and dosing facilities.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way.
Instrument and test
In the examples, nuclear magnetic analysis (1H NMR) was performed using a Bruker Avance 400MHz nuclear magnetic resonance spectrometer; mass spectrometry (ESI-MS) was performed using a Bruker Solarix FT-ICR MS fourier transform ion cyclotron resonance mass spectrometer; the uv-vis absorption spectroscopy was performed using a Perkin Elmer Lambda uv spectrophotometer.
Example 1
The preparation method is shown in the following chart.
The method comprises the following specific steps: 10mL of methanol/acetone/water (v/v/v=45/45/10) and 0.695g of 4-aminotetrastyrene (0.002 mol) were added to a 50mL three-necked flask, and 0.2g of concentrated HCl (0.002 mol) was slowly dropped under stirring at 20℃to react under stirring for 20 minutes. 0.152g of ammonium thiocyanate (0.002 mol) was dissolved in 5mL of methanol/acetone/water (v/v/v=45/45/10) and added to a three-necked flask, a white precipitate was formed, and the temperature was raised to 40℃and reacted for 2 hours. After the reaction, cooling to room temperature, standing and layering, wherein the upper layer is yellow clear solution, and the lower layer is white precipitate. And filtering, and spin-drying the collected yellow clear solution to obtain 0.795g of yellow solid, namely the target product.
1H NMR(400MHz，DMSO)：δ7.30-6.85(19H，m)。
MS(ESI-MS)：[M-H + ]347.1684。
Example 2
The preparation method is shown in the following chart.
The method comprises the following specific steps: 10mL of ethanol/tetrahydrofuran/water (v/v/v=70/26/4), 0.725g of di- (4-amino) -tetraphenyl ethylene (0.002 mol) were added to a 50mL three-necked flask, and 0.2g of concentrated H was slowly dropped under stirring at 50 ℃ 2 SO 4 (0.002 mol) and stirred for 2h. 0.325g of sodium thiocyanate (0.004 mol) was dissolved in 5mL of ethanol/tetrahydrofuran/water (v/v/v=70/26/4) and added to a three-necked flask to give a white precipitate, which was warmed to 80℃and reacted for 20min. After the reaction, cooling to room temperature, standing and layering, wherein the upper layer is yellow clear solution, and the lower layer is white precipitate. And filtering, and spin-drying the collected yellow clear solution to obtain 0.945g yellow solid, namely the target product.
1H NMR(400MHz，DMSO)：δ7.20-7.11(6H，m),7.10-7.03(8H，m),7.01-6.95(4H，d)。
MS(ESI-MS)：[M-H + ]363.18574，[M-2H + +Na + ]385.16772。
Example 3
The preparation method is shown in the following chart.
The method comprises the following specific steps: 10mL of isopropanol/acetonitrile/water (v/v/v=20/50/30), 0.785g of tetra- (4-amino) -tetraphenyl ethylene (0.002 mol) were added to a 50mL three-necked flask, and 0.4g of concentrated H was slowly dropped with stirring at 30 ℃ 2 SO 4 (0.004 mol) and stirred for 1h. 0.777g potassium thiocyanate (0.008 mol) was dissolved in 10mL isopropanol/acetonitrile/water (v/v/v=20/50/30) and added to a three-necked flask to give a white precipitate, which was warmed to 60℃and reacted for 4 hours. After the reaction is finished, cooling to room temperature, standing and layering, wherein the upper layer is a brown yellow clear solution, and the lower layer isWhite precipitate. And filtering, and spin-drying the collected brown yellow clear solution to obtain 1.207g of brown yellow solid, namely the target product.
Example 4
The preparation method is shown in the following chart.
The method comprises the following specific steps: 10mL of N, N-dimethylformamide/water (v/v=80/20) and 0.783g of 4- (2-amino) ethoxytetraphenyl ethylene (0.002 mol) were added to a 50mL three-necked flask, and 0.2g of concentrated HCl (0.002 mol) was slowly dropped under stirring at 20℃to conduct a stirring reaction for 30 minutes. 0.162g sodium thiocyanate (0.002 mol) was dissolved in 5ml of N, N-dimethylformamide/water (v/v=80/20) and added to a three-necked flask to give a white precipitate, which was warmed to 100℃and reacted for 2 hours. After the reaction is finished, cooling to room temperature, standing and layering, wherein the upper layer is a brown yellow clear solution, and the lower layer is white sediment. And filtering, and spin-drying the collected brown yellow clear solution to obtain 0.857g of brown yellow solid, namely the target product.
Example 5
Corrosion test of rotating hanging piece
Preparing an etching solution: 208g of concentrated H 2 SO 4 Dissolving in 4L deionized water to obtain 0.5. 0.5M H 2 SO 4 A solution. 250mL of 0.5M H was then taken 2 SO 4 Solutions in different glass bottles, metal test pieces treated with ethanol and weighed were suspended in order in these glass bottles, and the test pieces were immersed in the solutions without touching the bottom and the wall of the bottle, one bottle was not added with any agent as a blank test (i.e., comparative example 0), and corrosion inhibition component products prepared in the foregoing examples (i.e., examples 1 to 4) were added in a certain concentration, respectively, and aminotetrastyrene raw materials in the foregoing examples (i.e., comparative examples 1 to 4) were added in a certain concentration, respectively. Placing a glass bottle filled with corrosive solution and test pieces into a rotary hanging piece instrument, setting the temperature of the rotary hanging piece instrument to be 60 ℃, the rotating speed to be 28r/min, the linear speed to be 1m/s, ending the test for a certain period of time, taking out the test pieces, weighing the test pieces after being treated by water, ethanol and the like, and calculating the quality of the test pieces before and after the testThe loss of the amount, and further the corrosion inhibition performance of the medicament is obtained.
The corrosion inhibition rate is calculated as follows:
η＝(Δm 0 -Δm 1 )/Δm 0 ×100
wherein: eta, corrosion inhibition rate%
Δm 0 Mass loss of test piece in blank test, g
Δm 1 -mass loss of test piece in dosing test, g
The rotary hanging piece corrosion tests are respectively carried out by using two metal test pieces of H62 brass and N80 carbon steel in the same method, wherein the test duration is different, and the brass is 72 hours and the carbon steel is 4 hours. The brass test pieces and carbon steel test pieces are shown in Table 1 and Table 2, respectively.
The results in table 1 show that for brass, the corrosion inhibition rate of the corrosion inhibition component of the present invention increases gradually with increasing concentration of the agent. When the concentration of the agent is 100mg/L, the corrosion inhibition rate of each of the examples 1 to 4 exceeds 75%, wherein the corrosion inhibition rate of the example 2 exceeds 99%, and the corrosion inhibition performance is good; the aminotetrastyrene raw materials used, comparative examples 1 to 4, however, have little corrosion inhibition properties and may even slightly exacerbate corrosion.
The results in Table 2 show that the corrosion inhibition rate of the corrosion inhibiting composition of the present invention increases progressively with increasing concentration of the agent for carbon steel. When the concentration of the agent is 100mg/L, the corrosion inhibition rate of each of the examples 1 to 4 exceeds 75%, wherein the corrosion inhibition rate of the example 2 exceeds 97%, and the corrosion inhibition performance is good; the aminotetrastyrene raw materials used, comparative examples 1 to 4, however, have little corrosion inhibition properties and may even slightly exacerbate corrosion.
TABLE 1
| Concentration of the agent | 40mg/L | 70mg/L | 100mg/L |
| Comparative example 0 | - | - | - |
| Example 1 | 56.3％ | 63.4％ | 77.0％ |
| Example 2 | 96.3％ | 98.1％ | 99.9％ |
| Example 3 | 87.8％ | 91.8％ | 95.6％ |
| Example 4 | 58.6％ | 68.1％ | 79.3％ |
| Comparative example 1: 4-aminotetrastyrene | 2.5％ | 7.7％ | 5.2％ |
| Comparative example 2: di- (4-amino) -tetraphenyl ethylene | 0.3％ | 17.8％ | 10.8％ |
| Comparative example 3: tetra- (4-amino) -tetraphenyl ethylene | 1.1％ | -2.1％ | 8.3％ |
| Comparative example 4:4- (2-amino) ethoxy tetraphenyl ethylene | -7.9％ | 4.6％ | 1.3％ |
TABLE 2
| Concentration of the agent | 40mg/L | 70mg/L | 100mg/L |
| Comparative example 0 | - | - | - |
| Example 1 | 32.2％ | 53.5％ | 76.3％ |
| Example 2 | 95.2％ | 96.8％ | 97.3％ |
| Example 3 | 95.6％ | 97.5％ | 97.8％ |
| Example 4 | 34.6％ | 56.8％ | 78.2％ |
| Comparative example 1: 4-aminotetrastyrene | 3.3％ | 6.8％ | 6.1％ |
| Comparative example 2: di- (4-amino) -tetraphenyl ethylene | 1.7％ | 11.2％ | 8.3％ |
| Comparative example 3: tetra- (4-amino) -tetraphenyl ethylene | -2.5％ | -0.9％ | 5.2％ |
| Comparative example 4:4- (2-amino) ethoxy tetraphenyl ethylene | -2.9％ | -8.3％ | 3.7％ |
Example 6
This example illustrates the determination of the concentration of the metal corrosion inhibiting component of the present invention in a corrosive medium. Taking the product of example 2 as an example, it is taken as 0.5. 0.5M H 2 SO 4 Solutions of different mass concentrations were formulated for solvents and subjected to uv-vis absorption spectrometry, see figure 5. It can be seen that the compound has an obvious ultraviolet absorption peak, and the absorbance Abs at 300nm of the peak is linearly fitted with the mass concentration c to obtain the relation abs= 0.03767c-0.00825. When the corrosion medium contains the compound with unknown concentration, the ultraviolet-visible absorption spectrum of the solution can be measured to obtain absorbance at 300nm, and the mass concentration of the compound in the corrosion medium can be measured by substituting the absorbance at 300nm into the relational expression. If the concentration is too high and the absorbance exceeds the measuring range, the concentration can be properly diluted and then measured.
Example 7
This example illustrates the fluorescence of the compounds of the invention adsorbed on copper surfaces.
After the corrosion test of the brass test piece in the embodiment 5 is finished, the test pieces in the embodiment 1 to the embodiment 4 are adsorbed with corrosion inhibition component products, and the test pieces show fluorescence with certain intensity under 365nm ultraviolet irradiation; the test piece of comparative example 0 without any agent is non-fluorescent under 365nm ultraviolet light; the test pieces of the aminotetrastyrene raw materials (comparative examples 1 to 4) having almost no corrosion inhibition property were non-fluorescent under 365nm ultraviolet light irradiation. In FIG. 6, photographs of the test pieces of comparative examples 0, 100mg/L comparative example 1, 100mg/L comparative example 2, 100mg/L comparative example 3, 100mg/L comparative example 4, 100mg/L example 1, 100mg/L example 2, 100mg/L example 3, and 100mg/L example 4 under 365nm ultraviolet light are shown from left to right, respectively. Therefore, the corrosion inhibition component provided by the invention has a visual detection effect.
Claims (18)
1. The metal corrosion inhibition component is characterized by having a structure shown in a formula I:
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 、R 2 And R is 3 Each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
2. The metal corrosion inhibiting composition according to claim 1, wherein R 1 、R 2 And R is 3 Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that bonded to the benzene ring (4).
3. The metal corrosion inhibiting composition according to claim 1, wherein the substituents on the benzene ring are all para to the vinyl group.
4. The metal corrosion inhibitor according to claim 1, wherein m and n are each 0, R 1 、R 2 And R is 3 One, two or all of the substituents on the benzene ring (4) are the same, and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.
5. A method of preparing a metal corrosion inhibiting composition comprising:
(1) In a polar solvent, firstly, reacting a compound shown in a formula II with acid;
(2) Then adding thiocyanate to react to generate precipitate, and removing insoluble substances and polar solvents generated in the reaction system to obtain the metal corrosion inhibition component;
wherein X is an oxygen atom, a sulfur atom or a nitrogen atom; r is R 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom or an optional substituent; m is 0 or 1, n is 0 or 2.
6. A process according to claim 5, wherein R is selected from the group consisting of compounds of formula II 1 ’、R 2 ' and R 3 ' each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a hydrocarbon group or the same substituent as that bonded to the benzene ring (4).
7. The process according to claim 5, wherein the substituents on the benzene ring are all para to the vinyl group in the compound of formula II.
8. A process according to claim 5, wherein m and n are each 0 and R in the compound of formula II 1 ’、R 2 ' and R 3 One, two or all of the substituents' are the same as the substituents on the benzene ring (4), and the remaining substituents are each independently a hydrogen atom or a hydrocarbon group.
9. The process according to claim 5, wherein the polar solvent comprises 35 to 0% by volume of water and 65 to 100% by volume of a water-miscible organic solvent.
10. The method according to claim 9, wherein the water-miscible organic solvent is one or more of methanol, ethanol, N-propanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 1, 4-dioxane and ethylene glycol.
11. The process according to claim 5, wherein the thiocyanate is ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate.
12. The process according to claim 5, wherein the acid is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, phosphorous acid or hypophosphorous acid.
13. A metal corrosion inhibiting composition according to any one of claims 5 to 12, wherein after the reaction, insoluble materials are removed by filtration, and the solvent is removed or not removed, thereby obtaining the metal corrosion inhibiting composition.
14. Use of a metal corrosion inhibiting composition according to any one of claims 1 to 4 and 13 in the field of protection against hydrogen evolution corrosion of metals.
15. A metal corrosion inhibitor comprising a metal corrosion inhibiting component according to any one of claims 1 to 4 and 13.
16. A method of corrosion inhibition of metals, characterized in that the corrosive medium contains a metal corrosion inhibiting component according to any one of claims 1 to 4 and 13.
17. A method of corrosion inhibition of metals, characterized in that the corrosion medium contains a metal corrosion inhibiting component according to any one of claims 1 to 4 and 13, and the concentration of said metal corrosion inhibiting component in the corrosion medium is detected and controlled by means of uv-vis absorption spectroscopy.
18. A copper corrosion protection method, characterized in that the copper surface is adsorbed with any one of the metal corrosion inhibition components of claims 1 to 4 and 13, and the corrosion inhibition treatment is carried out on the areas of the copper surface which have no fluorescence or have weaker fluorescence than other areas through the fluorescence of the copper surface under the irradiation of ultraviolet light.
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