CN114015048B - Corrosion inhibitor for water-based anti-corrosion coating and preparation method and application thereof - Google Patents
Corrosion inhibitor for water-based anti-corrosion coating and preparation method and application thereof Download PDFInfo
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- CN114015048B CN114015048B CN202111286474.3A CN202111286474A CN114015048B CN 114015048 B CN114015048 B CN 114015048B CN 202111286474 A CN202111286474 A CN 202111286474A CN 114015048 B CN114015048 B CN 114015048B
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- mercaptobenzothiazole
- corrosion
- corrosion inhibitor
- olefine acid
- reaction
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- 238000005260 corrosion Methods 0.000 title claims abstract description 108
- 230000007797 corrosion Effects 0.000 title claims abstract description 84
- 239000003112 inhibitor Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000002253 acid Substances 0.000 claims abstract description 72
- 229920001021 polysulfide Polymers 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000005077 polysulfide Substances 0.000 claims abstract description 56
- 150000008117 polysulfides Polymers 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 235000007586 terpenes Nutrition 0.000 claims description 19
- 150000003505 terpenes Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 11
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 11
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 11
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 11
- 229930006722 beta-pinene Natural products 0.000 claims description 11
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 10
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- QJFMCHRSDOLMHA-UHFFFAOYSA-N phenylmethanamine;hydrobromide Chemical compound Br.NCC1=CC=CC=C1 QJFMCHRSDOLMHA-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000005536 corrosion prevention Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 125000003396 thiol group Chemical group [H]S* 0.000 description 29
- 238000012018 process simulation test Methods 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000001035 drying Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LCOSXVIRVHTJKR-UHFFFAOYSA-N 1-butoxybutane;hydrate Chemical compound O.CCCCOCCCC LCOSXVIRVHTJKR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
- C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the field of metal surface corrosion prevention, and discloses a corrosion inhibitor for an aqueous corrosion-resistant coating, a preparation method and application thereof. The invention prepares the mercaptobenzothiazole-olefine acid compound by the reaction of olefine acid and mercaptobenzothiazole, and then prepares the mercaptobenzothiazole-olefine acid-polysulfide oligomer corrosion inhibitor by the reaction of the compound and PST. The preparation process of the corrosion inhibitor comprises a mercapto coupling reaction between mercaptobenzothiazole and polysulfide oligomer (PST) and a mercapto-alkene clicking reaction between PST and alkene acid. The olefine acid has good solubility, a hydrophilic chain segment is added to the molecular structure of the mercaptobenzothiazole to increase the water solubility of the olefine acid, and meanwhile, the introduction of the polysulfide Polymer (PST) increases the corrosion resistance of the olefine acid, so that the corrosion inhibitor has good corrosion resistance and excellent solubility, and the olefine acid has wide application in the field of metal surface corrosion resistance.
Description
Technical Field
The invention belongs to the field of metal surface corrosion prevention, and particularly relates to a corrosion inhibitor for an aqueous corrosion-resistant coating, a preparation method and application thereof.
Background
The preservation of the ware is of great significance to the daily life of the human beings. Composite materials made of metals and other substances are widely used in various environments in daily necessities. However, the use of organic corrosion inhibitors is highly desirable because the composite metal, even with excellent properties, is susceptible to electrochemical corrosion by the microcells formed from oxygen and water in humid air. The existing metal corrosion inhibitor mostly adopts Benzotriazole (BTA) and mercaptobenzothiazole, and because the benzotriazole and mercaptobenzothiazole can carry out complex reaction with metal, a bonding layer is formed on the surface of the metal, and the passivation layer can delay corrosion, so that the service life of the metal is prolonged.
Mercaptobenzothiazole (MBT) is an important five-membered aromatic thiazole ring, contains nitrogen and sulfur heteroatoms, has very rich pi-bond electrons, and has the special property of the thiazole ring, so that the thiazole ring is easy to form hydrogen bonds, can be complexed with metal ions, can form pi-pi electron accumulation and the like, and can interact with various non-covalent bonds. Because pi-bond electrons of mercaptobenzothiazole can generate adsorption effect with the metal surface to form a metal protection layer, the mercaptobenzothiazole becomes one of important materials for researching metal corrosion inhibitors at present, but the solubility of mercaptobenzothiazole in water is very limited, and the solubility of mercaptobenzothiazole is smaller than 0.1g/100ml at normal temperature, so that the application of mercaptobenzothiazole in water-based paint is limited.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a method for preparing a corrosion inhibitor for use in an aqueous corrosion-resistant coating
The invention also aims to provide the corrosion inhibitor prepared by the method.
It is a further object of the present invention to provide the use of the above corrosion inhibitors in the field of corrosion protection of metal surfaces.
The aim of the invention is achieved by the following scheme:
a preparation method of a corrosion inhibitor for an aqueous corrosion-resistant coating comprises the steps of firstly reacting mercaptobenzothiazole with olefine acid to prepare a water-soluble mercaptobenzothiazole-olefine acid compound, and then reacting the mercaptobenzothiazole-olefine acid compound with a polysulfide oligomer to prepare the mercaptobenzothiazole-olefine acid-polysulfide oligomer compound, namely the corrosion inhibitor for the aqueous corrosion-resistant coating. The method specifically comprises the following steps:
(1) Dispersing mercaptobenzothiazole in an alkaline aqueous solution, increasing the temperature, adding a catalyst and olefine acid for reaction, and obtaining a water-soluble mercaptobenzothiazole-olefine acid compound after the reaction is finished;
(2) And dissolving the polysulfide oligomer in a solvent, raising the temperature, adding a catalyst and a mercaptobenzothiazole-olefine acid compound for reaction, and obtaining the mercaptobenzothiazole-olefine acid-polysulfide oligomer compound after the reaction is finished, namely the corrosion inhibitor which can be used in the water-based anti-corrosion coating.
The amount of the olefinic acid used in step (1) is equal to the molar amount of the mercaptobenzothiazole.
The olefmic acid in the step (1) has the following molecular structure:
the alkaline aqueous solution in the step (1) comprises an alkaline aqueous solution formed by at least one of potassium hydroxide, magnesium hydroxide, alkaline aluminum hydroxide and triethylamine, and the pH is more than 8.
The catalyst in the step (1) comprises at least one of sodium ethoxide, benzyl ammonium bromide and sodium amide, and the mass of the catalyst is 3-5% of the total mass of mercaptobenzothiazole and olefine acid.
The reaction in the step (1) is preferably carried out at a temperature of 50-70 ℃ for 7-21h under the protection of nitrogen.
The step (1) comprises the following specific steps: adding mercaptobenzothiazole into an alkaline aqueous solution, mechanically stirring at a stirring speed of 200-500r/min, raising the temperature after mercaptobenzothiazole is uniformly dispersed, and introducing nitrogen for protection and condensed water after the temperature is constant; and (3) dropwise adding a certain amount of catalyst, dropwise adding olefine acid with the mole number equal to that of mercaptobenzothiazole, and washing and drying the compound for later use after complete reaction.
The polysulfide oligomer of step (2) is a copolymer of elemental sulfur and a terpene; the terpene comprises at least one of beta-pinene, alpha-pinene and limonene; the usage amount of the terpene accounts for 5-60% of the total mass of the terpene and the elemental sulfur.
The average molecular weight of the polysulfide oligomer in the step (2) is 1100, and the dosage is equal to the molar weight of the mercaptobenzothiazole in the step (1).
The catalyst in the step (2) comprises at least one of AIBN, n-butyllithium and hexamethylenetetramine, and the dosage of the catalyst is 3-5% of the total mass of the mercaptobenzothiazole-enoic acid and the polysulfide oligomer.
The solvent in the step (2) comprises at least one of toluene, benzene, acetone-water, ethanol dibutyl ether-water and water.
The reaction temperature in the step (2) is 80-110 ℃ and the reaction time is 10-24 hours.
The step (2) comprises the following specific steps: dissolving a polysulfide oligomer with the same mole number as that of mercaptobenzothiazole in a solvent, and transferring the mixture into a four-neck flask, wherein the average molecular weight of the polysulfide oligomer is 1100; raising the temperature, stirring at 160-280r/min, introducing nitrogen and condensed water, adding a catalyst and a mercaptobenzothiazole-olefine acid compound for reaction after the temperature is constant, washing and drying the product after the reaction is finished, and obtaining the corrosion inhibitor applicable to the water-based anti-corrosion coating.
The corrosion inhibitor which can be used in the water-based anti-corrosion coating and is prepared by compounding mercaptobenzothiazole, olefine acid and polysulfide oligomer. The olefmic acid has the following molecular structure:
the polysulfide oligomer (PST) is a polymer of elemental sulfur and terpene.
PST has rich disulfide bonds, and the chain segment end has sulfhydryl groups, so that the PST has very good solubility in solvents such as tetrahydrofuran, dichloromethane, methacrylic acid and the like. The polysulfide oligomer contains abundant sulfhydryl groups, and can be used as a curing agent of epoxy resin and a substrate for providing sulfhydryl groups in a sulfhydryl-alkene clicking reaction.
The corrosion inhibitor which can be used in the water-based anti-corrosion coating is applied to the field of metal surface anti-corrosion. The corrosion inhibitor prepared by the invention is added into acrylic resin to obtain modified acrylic resin containing the corrosion inhibitor. The modified acrylic resin is coated on the surface of a metal matrix, and the corrosion resistance of the metal surface can be obviously improved by the modified acrylic resin containing the corrosion inhibitor through the test of a salt water soaking experiment.
The mechanism of the invention is as follows:
the invention prepares the mercaptobenzothiazole-olefine acid compound by the reaction of olefine acid and mercaptobenzothiazole, and improves the solubility of mercaptobenzothiazole in water by utilizing the water solubility of olefine acid; and then the compound reacts with PST to prepare the mercaptobenzothiazole-enoic acid-polysulfide oligomer corrosion inhibitor. The preparation process of the corrosion inhibitor comprises a mercapto coupling reaction between mercaptobenzothiazole and polysulfide oligomer (PST) and a mercapto-alkene clicking reaction between PST and alkene acid. The corrosion inhibitor structure prepared by the invention contains sulfonic acid groups or carboxyl groups which are easy to dissolve in water, the good solubility of the olefine acid is that a hydrophilic chain segment is added into the molecular structure of mercaptobenzothiazole to increase the water solubility of the mercaptobenzothiazole, and the molecular chain segment of PST has certain affinity in water, so that the corrosion inhibitor prepared by the invention has water solubility and can be applied to water-based anticorrosive paint. The prepared corrosion inhibitor has certain solubility in water in the experimental process. Meanwhile, the introduction of polysulfide Polymer (PST) increases the corrosion resistance of mercaptobenzothiazole, so that the corrosion inhibitor has good corrosion resistance and excellent solubility.
Compared with the prior art, the invention has the following advantages:
1. the corrosion inhibitor for the water-based anti-corrosion coating, which is prepared by the invention, introduces the olefine acid and the polysulfide oligomer into the mercaptobenzothiazole, increases the water solubility of the mercaptobenzothiazole, and simultaneously has better corrosion inhibition performance due to the introduction of sulfur element in the polysulfide oligomer, thus being an excellent anti-corrosion filler.
2. The polysulfide oligomer in the corrosion inhibitor is prepared from elemental sulfur, so that the problem of sulfur stacking in the petroleum refining process is solved.
3. The corrosion inhibitor can be dissolved in aqueous solution, can be used as filler in coating emulsion, and can increase corrosion inhibition performance of the coating.
4. The corrosion inhibitor has the advantages of novel structure, abundant raw material sources, simple preparation method, convenience for large-scale production and easiness for realizing industrialization.
Drawings
FIG. 1 is a graph showing the change in absorbance during the reaction of example 1 olefmic acid and mercaptobenzothiazole with PST.
FIG. 2 is an infrared spectrum of example 1, a is an infrared spectrum of mercaptobenzothiazole, b is an infrared spectrum of PST, and c is an infrared spectrum of mercaptobenzothiazole-enoic acid-PST.
FIG. 3 is a graph showing the corrosion resistance of a metal substrate coated with a modified acrylic resin containing the corrosion inhibitor prepared in example 1 of the present invention, wherein the left side is a graph showing the corrosion resistance of the metal substrate coated with the modified acrylic resin without the corrosion inhibitor, and the right side is a graph showing the corrosion resistance of the metal substrate coated with the corrosion inhibitor.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The polysulfide oligomer used in the examples was prepared according to the method of example 1 of chinese patent publication CN201710617001.4, using polysulfide oligomer (PST) as the final product elemental sulfur/terpene copolymer. Wherein the PST is prepared from beta-pinene and elemental sulfur according to a mass ratio of 5% -60%. It is also clear from published article L.Sun, et al European Polymer Journal 123 (2020) 109440 that the PST molecular chain contains abundant thiol groups.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
(1) 0.5mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 200r/min and purged with nitrogen. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of sodium ethoxide accounting for 3% of the total mass of the mercaptobenzothiazole and the olefine acid after the temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with the mercaptobenzothiazole, reacting for 7 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) Polysulfide oligomer according to example 1 of patent application No. CN201710617001.4The desired compound was determined by measuring the infrared spectrum (i.e., b in fig. 2) against the infrared spectrum data in article l.sun, et al European Polymer Journal 123 (2020) 109440, which produced a polysulfide Polymer, β -pinene accounting for 40% of the total mass of elemental sulfur and terpene. Dissolving 0.5mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at 160r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, adding 3% of the total mass of the mercapto benzothiazole-olefine acid and PST, washing after the reaction is completed for 24 hours, and drying to obtain the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating. By comparing the infrared spectrum of the mercaptobenzothiazole-enoic acid-polysulfide oligomer (FIG. 2 c) with the infrared spectrum of mercaptobenzothiazole (FIG. 2 a) and PST (FIG. 2 b), 1732.08cm in FIG. 2 c -1 The absorption peak of the hydroxyl group in the carboxyl group appears at the position, and it can be deduced that the enoate and the PST form a covalent bond through the ene-mercapto group clicking reaction.
Example 2
(1) 1mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 200r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of sodium ethoxide serving as a catalyst accounting for 3.5% of the total mass of the mercaptobenzothiazole and the olefine acid after the reaction temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with the mercaptobenzothiazole, reacting for 11 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the method for preparing the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and the beta-pinene accounts for 5 percent of the total mass of elemental sulfur and terpene. Dissolving 1mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at a speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, adding 3% of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours to obtain the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 3
(1) 1.5mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 300r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 3% of the total mass of mercaptobenzothiazole and olefine acid after the reaction temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 13 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the method for preparing the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and the beta-pinene accounts for 10 percent of the total mass of elemental sulfur and terpene. Dissolving 1.5mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at the speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, wherein the addition amount is 3.5 percent of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours, and obtaining the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 4
(1) 1.2mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 300r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 4% of the total mass of mercaptobenzothiazole and olefine acid after the reaction temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 15 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the preparation method of the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and the beta-pinene accounts for 15 percent of the total mass of elemental sulfur and terpene. Dissolving 1.2mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at the speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, wherein the addition amount is 3.5 percent of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours, and obtaining the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 5
(1) 0.8mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at a speed of 350r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of sodium ethoxide serving as a catalyst accounting for 4.5% of the total mass of mercaptobenzothiazole and olefine acid after the reaction temperature is constant, dropwise adding vinylsulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 15 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the preparation method of the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and beta-pinene accounts for 20 percent of the total mass of elemental sulfur and terpene. Dissolving 0.8mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at 220r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, wherein the addition amount is 3.5% of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours, so as to obtain the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 6
(1) 1.8mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at a speed of 350r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 3% of the total mass of mercaptobenzothiazole and olefine acid after the reaction temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 17 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the method for preparing the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and the beta-pinene accounts for 25 percent of the total mass of elemental sulfur and terpene. Dissolving 1.8mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at 220r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, wherein the addition amount is 4% of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours, so as to obtain the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 7
(1) 2mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 400r/min and purged with nitrogen. Setting the reaction temperature to 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 3% of the total mass of mercaptobenzothiazole and olefine acid after the reaction temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 19 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the method for preparing the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and beta-pinene accounts for 30 percent of the total mass of elemental sulfur and terpene. Dissolving 2mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at the speed of 240r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, adding 3.5% of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours to obtain the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 8
(1) 1.5mol of mercaptobenzothiazole is dispersed in an alkaline aqueous solution (pH > 8), heated, stirred at 300r/min and purged with nitrogen. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 5% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinyl sulfonic acid which is equimolar with mercaptobenzothiazole, reacting for 21 hours, obtaining the mercaptobenzothiazole-olefine acid compound after complete reaction, washing, drying and standby.
(2) According to the method for preparing the polysulfide oligomer in the example 1 of the patent application No. CN201710617001.4, a polysulfide polymer is prepared, and the beta-pinene accounts for 35 percent of the total mass of elemental sulfur and terpene. Dissolving 1.5mol of polysulfide oligomer in toluene solvent, adding the mercapto benzothiazole-olefine acid compound prepared in the step (1), heating to 80 ℃ in an oil bath, stirring at the speed of 240r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate reaction after the temperature is constant, wherein the addition amount is 3.5 percent of the total mass of the mercapto benzothiazole-olefine acid and PST, washing and drying after the reaction is completed for 24 hours, and obtaining the product mercapto benzothiazole-olefine acid-polysulfide oligomer, namely the corrosion inhibitor for the water-based anti-corrosion coating.
Example 9
The corrosion inhibitor prepared in the embodiment 1 of the invention is added into the aqueous acrylic resin, and the addition amount is 3% of the mass of the aqueous acrylic resin, so that the modified acrylic resin containing the corrosion inhibitor is obtained. The modified acrylic resin is coated on the surface of a metal matrix, wherein the metal matrix is tin plate, and surface treatments such as zinc protection layer removal, dust removal and the like are performed in advance before coating. The acrylic resin is coated twice by using a wire rod with the diameter of 25mm, then the wire rod is dried for 12 hours at the constant temperature of 80 ℃ in an oven, the wire rod is taken out, the metal surface is cooled and then a brine experiment is started, namely, the metal material is soaked in a sodium chloride solution with the constant temperature of 40 ℃ and the concentration of 3.5wt.% for 96 hours, and the anti-corrosion effect of the metal material is tested. As shown in fig. 3, the control group on the left is an acrylic coating without corrosion inhibitor, and the experimental group on the right is an acrylic coating with corrosion inhibitor. The left control group started to develop rust after 12 hours of saline experiments, and continued to soak and corrode until the surface was completely rusted after 48 hours. The right test group starts to generate membrane micro-bubbling after soaking for 52 hours, and the metal substrate generates small rust points at the wrapping edge until soaking is finished, so that corrosion of the metal substrate is not obvious.
The aqueous acrylic resin used in this example was prepared by the following method:
first, emulsifying a nuclear monomer: a 250ml four-neck flask is added with a core monomer of methyl methacrylate, dodecyl methacrylate and styrene with a mass ratio of 1:1:3, the total mass of the core monomer is 30g, then an emulsifier span 80 and op-10 with a total mass of 1.5g and water with a mass ratio of 40g are added, and mechanical stirring is adopted for one hour at normal temperature, wherein the rotating speed is 600r/min. And after the emulsification is completed, a reaction device is arranged. Stirring mechanically for 180r/min, introducing nitrogen, condensing water and keeping the constant temperature of the oil bath at 75 ℃. 0.4g of ammonium persulfate initiator was dissolved in 10g of water, and the dropping speed was slowly 0.5g/min by using a peristaltic pump. Until a distinct blue light appears in the four-necked flask. The emulsified shell monomer and an aqueous initiator solution (1.2 g of potassium persulfate initiator dissolved in 20g of water) were initially added dropwise at 8g/min at a rate of 0.4g/min. And then, after finishing dripping the shell monomer, preserving the temperature for 1 hour to obtain the aqueous acrylic resin emulsion. The emulsifying process of the shell monomer is as follows, taking 70g of total mass of the shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate, wherein the mass ratio is 10:7:7:1.5, adding 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature, and the rotating speed is 1000r/min.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the corrosion inhibitor for the water-based anti-corrosion coating is characterized by comprising the following steps of:
firstly, preparing a water-soluble mercaptobenzothiazole-olefine acid compound by using mercaptobenzothiazole to react with olefine acid, and then, preparing the mercaptobenzothiazole-olefine acid-polysulfide oligomer compound by reacting the mercaptobenzothiazole-olefine acid compound with polysulfide oligomer, namely, the corrosion inhibitor which can be used in the water-based anti-corrosion coating;
the olefine acid is vinyl sulfonic acid;
the polysulfide oligomer is a copolymer of elemental sulfur and a terpene; the terpene comprises at least one of beta-pinene, alpha-pinene and limonene.
2. The method for preparing the corrosion inhibitor for the aqueous anti-corrosion coating according to claim 1, which is characterized by comprising the following specific steps:
(1) Dispersing mercaptobenzothiazole in an alkaline aqueous solution, increasing the temperature, adding a catalyst and olefine acid for reaction, and obtaining a water-soluble mercaptobenzothiazole-olefine acid compound after the reaction is finished;
(2) And dissolving the polysulfide oligomer in a solvent, raising the temperature, adding a catalyst and a mercaptobenzothiazole-olefine acid compound for reaction, and obtaining the mercaptobenzothiazole-olefine acid-polysulfide oligomer compound after the reaction is finished, namely the corrosion inhibitor which can be used in the water-based anti-corrosion coating.
3. A method of preparing a corrosion inhibitor for use in aqueous corrosion protection coatings according to claim 1 or 2, characterized in that:
the mass of terpene in the polysulfide oligomer accounts for 5-60% of the total mass of terpene and elemental sulfur.
4. A method of preparing a corrosion inhibitor for use in aqueous corrosion protection coatings according to claim 1 or 2, characterized in that:
the dosage of the olefine acid is equal to the molar quantity of the mercaptobenzothiazole; the polysulfide oligomer is used in an amount equal to the molar amount of mercaptobenzothiazole.
5. The method for preparing the corrosion inhibitor for the aqueous anti-corrosion coating according to claim 2, wherein the method comprises the following steps:
the catalyst in the step (1) comprises at least one of sodium ethoxide, benzyl ammonium bromide and sodium amide, and the dosage of the catalyst is 3-5% of the total mass of mercaptobenzothiazole and olefine acid;
the reaction temperature in the step (1) is 50-70 ℃ and the reaction time is 7-21h;
the alkaline aqueous solution in the step (1) comprises an alkaline aqueous solution formed by at least one of potassium hydroxide, magnesium hydroxide, alkaline aluminum hydroxide and triethylamine, and the pH is more than 8.
6. The method for preparing the corrosion inhibitor for the aqueous anti-corrosion coating according to claim 2, wherein the method comprises the following steps:
the catalyst in the step (2) comprises at least one of AIBN, n-butyllithium and hexamethylenetetramine, and the dosage of the catalyst is 3-5% of the total mass of mercaptobenzothiazole-enoic acid and polysulfide oligomer;
the reaction temperature in the step (2) is 80-110 ℃ and the reaction time is 10-24 hours.
7. A corrosion inhibitor useful in aqueous corrosion-resistant coatings prepared according to the method of any one of claims 1-6.
8. The corrosion inhibitor for use in aqueous corrosion protection coatings of claim 7, wherein: the corrosion inhibitor is formed by compounding mercaptobenzothiazole, olefine acid and polysulfide oligomer; the polysulfide oligomer is a polymer of elemental sulfur and terpene; the olefine acid is vinyl sulfonic acid.
9. Use of a corrosion inhibitor according to claim 7 or 8 for use in aqueous corrosion protection coatings in the field of corrosion protection of metal surfaces.
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