CN114015048A - Corrosion inhibitor for water-based anticorrosive coating and preparation method and application thereof - Google Patents
Corrosion inhibitor for water-based anticorrosive coating and preparation method and application thereof Download PDFInfo
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- CN114015048A CN114015048A CN202111286474.3A CN202111286474A CN114015048A CN 114015048 A CN114015048 A CN 114015048A CN 202111286474 A CN202111286474 A CN 202111286474A CN 114015048 A CN114015048 A CN 114015048A
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- mercaptobenzothiazole
- corrosion inhibitor
- olefine acid
- water
- reaction
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- 238000005260 corrosion Methods 0.000 title claims abstract description 78
- 230000007797 corrosion Effects 0.000 title claims abstract description 78
- 239000003112 inhibitor Substances 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 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 20
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000002253 acid Substances 0.000 claims abstract description 70
- 229920001021 polysulfide Polymers 0.000 claims abstract description 47
- 239000005077 polysulfide Substances 0.000 claims abstract description 37
- 150000008117 polysulfides Polymers 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 29
- 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
- 238000000034 method Methods 0.000 claims description 14
- 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
- -1 polythio Polymers 0.000 claims description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 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
- 229910006069 SO3H Inorganic materials 0.000 claims 2
- 239000011253 protective coating Substances 0.000 claims 1
- 238000005536 corrosion prevention Methods 0.000 abstract description 7
- 238000012650 click reaction Methods 0.000 abstract description 4
- 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
- 238000012018 process simulation test Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 238000001035 drying Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000004925 Acrylic resin Substances 0.000 description 14
- 229920000178 Acrylic resin Polymers 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000758 substrate Substances 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
- 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
- 239000003999 initiator Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007654 immersion Methods 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
- 239000010410 layer Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000003973 paint Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 230000009286 beneficial effect Effects 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
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 229910021645 metal ion Inorganic materials 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
- 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
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-
- 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)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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 a water-based anticorrosive coating, and a preparation method and application thereof. The invention uses olefine acid and mercaptobenzothiazole to react to prepare mercaptobenzothiazole-olefine acid compound, and then the compound reacts with PST to prepare mercaptobenzothiazole-olefine 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 click reaction between PST and olefine acid. The olefine acid has good solubility, the hydrophilic chain segment is added into the molecular structure of the mercaptobenzothiazole to increase the water solubility of the mercaptobenzothiazole, and meanwhile, the corrosion resistance of the mercaptobenzothiazole is increased by introducing the polysulfide Polymer (PST), so that the corrosion inhibitor has good corrosion resistance and excellent solubility, and is widely applied to 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 a water-based anticorrosive coating, and a preparation method and application thereof.
Background
The preservation of utensils is of great significance to the daily life of human beings. Various composite materials made of metal and other substances in daily necessities are widely applied in various environments. However, even though the composite metal has excellent properties, it is susceptible to electrochemical corrosion of the microcell caused by oxygen and water in humid air, so that the use of the organic corrosion inhibitor is very necessary. Benzotriazole (BTA) and mercaptobenzothiazole are mostly adopted in the existing metal corrosion inhibitor, because the BTA and mercaptobenzothiazole can generate a complex reaction with metal to form a bonding layer 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 abundant pi bond electrons, and the structure endows the thiazole ring with special performance, so that hydrogen bonds are easily formed, the thiazole ring can be complexed with metal ions, pi-pi electron accumulation and the like can be formed, and the thiazole ring can interact with various non-covalent bonds. The pi bond electrons of mercaptobenzothiazole can generate adsorption with the metal surface to form a metal protective layer, so that the mercaptobenzothiazole becomes one of important materials for researching metal corrosion inhibitors at present, but the solubility of mercaptobenzothiazole in water is very limited, the solubility at normal temperature is more less than 0.1g/100ml, and the application of mercaptobenzothiazole in water-based paint is limited.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a corrosion inhibitor used in a water-based anticorrosive coating
The invention also aims to provide the corrosion inhibitor prepared by the method.
The invention also aims to provide the application of the corrosion inhibitor in the field of metal surface corrosion prevention.
The purpose of the invention is realized by the following scheme:
a method for preparing corrosion inhibitor used in water-based anticorrosive coating, which comprises the steps of firstly using mercaptobenzothiazole to react with olefine acid to prepare water-soluble mercaptobenzothiazole-olefine acid compound, and then reacting the mercaptobenzothiazole-olefine acid compound with polysulfide oligomer to prepare mercaptobenzothiazole-olefine acid-polysulfide oligomer compound, namely the corrosion inhibitor used in water-based anticorrosive coating. The method specifically comprises the following steps:
(1) dispersing mercaptobenzothiazole in an alkaline aqueous solution, raising 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) dissolving 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 used in the water-based anticorrosive coating.
The dosage of the olefine acid in the step (1) is equal to the molar weight of the mercaptobenzothiazole.
The olefine 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 value 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 the 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 the stirring speed of 200-500r/min, raising the temperature after the mercaptobenzothiazole is uniformly dispersed, introducing nitrogen for protection after the temperature is constant, and introducing condensed water; and (3) dropwise adding a certain amount of catalyst, dropwise adding olefine acid with the mole number equal to that of the 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 terpene; the terpene comprises at least one of beta-pinene, alpha-pinene and limonene; the dosage of the terpene accounts for 5-60% of the total mass of the terpene and the elemental sulfur.
The polysulfide oligomer obtained in step (2) has an average molecular weight of 1100, and is used in an amount equal to the molar amount of the mercaptobenzothiazole obtained in 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-olefine 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 polysulfide oligomer into a four-neck flask, wherein the average molecular weight of the polysulfide oligomer is 1100; raising the temperature, stirring at the speed of 160-280r/min, introducing nitrogen, condensing water, adding a catalyst and a mercaptobenzothiazole-olefine acid compound for reaction after the temperature is constant, and washing and drying a product after the reaction is finished to obtain the corrosion inhibitor for the water-based anticorrosive coating.
The corrosion inhibitor for the water-based anticorrosive coating prepared by the method is compounded by mercaptobenzothiazole, olefine acid and polysulfide oligomer. The olefine acid has the following molecular structure:
the polysulfide oligomer (PST) is a polymer of elemental sulfur and a terpene.
PST has rich disulfide bonds and sulfhydryl groups at the tail ends of chain segments, and has very good solubility in solvents such as tetrahydrofuran, dichloromethane, methacrylic acid and the like. The polysulfide oligomer contains abundant sulfydryl, and can be used as a curing agent of epoxy resin and a substrate for providing sulfydryl in a sulfydryl-alkene click reaction.
The corrosion inhibitor which can be used in the water-based anticorrosive coating is applied to the field of metal surface corrosion prevention. The corrosion inhibitor prepared by the invention is added into acrylic resin to obtain the 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 remarkably improved by the modified acrylic resin containing the corrosion inhibitor through a saline soaking experiment test.
The mechanism of the invention is as follows:
according to the invention, olefine acid and mercaptobenzothiazole react to prepare mercaptobenzothiazole-olefine acid compound, and the solubility of the mercaptobenzothiazole in water is improved by utilizing the water solubility of the olefine acid; and then the compound reacts with PST to prepare the mercaptobenzothiazole-olefine 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 click reaction between PST and olefine acid. The corrosion inhibitor prepared by the invention contains sulfonic group or carboxyl which is easy to dissolve in water, the good solubility of olefine acid is that hydrophilic chain segment is added in the molecular structure of mercaptobenzothiazole to increase the water solubility of 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 experiment process proves that the prepared corrosion inhibitor has certain solubility in water. 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 and beneficial effects:
1. the corrosion inhibitor for the water-based anticorrosive coating, prepared by the invention, introduces olefine acid and polysulfide oligomer into mercaptobenzothiazole, and has better corrosion inhibition performance due to the introduction of sulfur element in the polysulfide oligomer while increasing the water solubility of the mercaptobenzothiazole, so that the corrosion inhibitor is an excellent anticorrosive 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 and can be used as a filler in coating emulsion to improve the corrosion inhibition performance of the coating.
4. The corrosion inhibitor has the advantages of novel structure, rich raw material sources, simple preparation method, convenience for large-scale production and easiness in realization of industrialization.
Drawings
FIG. 1 is a graph showing the change in absorbance during the reaction of the olefinic acid and mercaptobenzothiazole with PST in example 1.
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-enoate-PST.
FIG. 3 is a graph of the corrosion prevention effect of the metal substrate coated with the modified acrylic resin containing the corrosion inhibitor prepared in example 1 of the present invention in a salt water immersion test, wherein the left side is a graph of the corrosion prevention effect without adding the corrosion inhibitor, and the right side is a graph of the corrosion prevention effect with adding the corrosion inhibitor.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The polythiooligomers used in the examples were prepared according to the method of example 1 of chinese patent publication CN201710617001.4, and the Polythiooligomers (PST) used were the final product elemental sulfur/terpene copolymers. Wherein the PST is prepared by using beta-pinene and elemental sulfur according to the mass ratio of 5-60%. It is also clear from published articles L.Sun, et al.European Polymer Journal 123(2020)109440 that PST contains a large amount of thiol groups in the molecular chain.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) 0.5mol of mercaptobenzothiazole is dispersed in an aqueous alkaline solution (pH >8), heated, stirred at 200r/min and nitrogen is passed through. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of sodium ethoxide which accounts for 3% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid which is equal to mercaptobenzothiazole in mole, reacting for 7 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) A polysulfide Polymer was prepared according to the method of preparation of polysulfide oligomers described in example 1 of patent application No. CN201710617001.4, where β -pinene represents 40% of the total mass of elemental sulfur and terpene, and was identified as the desired compound by measuring the IR spectrum (i.e., b in FIG. 2) against the IR spectrum data in the article L.Sun, et al.European Polymer Journal 123(2020) 109440. Dissolving 0.5mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 160r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the adding amount is 3% of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after 24 hours of reaction, and obtaining the mercaptobenzothiazole-olefine acid-polythio oligomer which can be used as a corrosion inhibitor in a water-based anticorrosive coating. By comparison of the IR spectrum of mercaptobenzothiazole-enoate-polysulfide oligomer (c in FIG. 2) with the IR spectrum of mercaptobenzothiazole (a in FIG. 2) and the IR spectrum of PST (b in FIG. 2), 1732.08cm in C in FIG. 2-1The absorption peak of hydroxyl in carboxyl appears at the position, and the fact that olefine acid and PST form a covalent bond through alkene-sulfydryl click reaction can be deduced.
Example 2
(1) 1mol of mercaptobenzothiazole is dispersed in an aqueous alkaline solution (pH >8), heated, stirred at 200r/min and nitrogen is passed through. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide which accounts for 3.5% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid which is equal to mercaptobenzothiazole in mole, reacting for 11 hours, obtaining mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, and beta-pinene accounts for 5% of the total mass of elemental sulfur and terpene. Dissolving 1mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the adding amount is 3% of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after the reaction is finished for 24 hours to obtain the mercaptobenzothiazole-olefine acid-polythio oligomer, which can be used as a corrosion inhibitor in a water-based anticorrosive coating.
Example 3
(1) Mercaptobenzothiazole, 1.5mol, was dispersed in an aqueous alkaline solution (pH >8), heated at a stirring rate of 300r/min and purged with nitrogen. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide which accounts for 3% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid which is equal to mercaptobenzothiazole in mole, reacting for 13 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, wherein beta-pinene accounts for 10% of the total mass of elemental sulfur and terpene. Dissolving 1.5mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the addition amount is 3.5 percent of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after the reaction is finished for 24 hours to obtain the mercaptobenzothiazole-olefine acid-polythio oligomer product, and the product can be used as a corrosion inhibitor in an aqueous anticorrosive coating.
Example 4
(1) Mercaptobenzothiazole, 1.2mol, was dispersed in an aqueous alkaline solution (pH >8), heated at a stirring rate of 300r/min and purged with nitrogen. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 4% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid with the same mole as mercaptobenzothiazole, reacting for 15 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, beta-pinene accounts for 15% of the total mass of elemental sulfur and terpene. Dissolving 1.2mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 180r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the adding amount is 3.5 percent of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after the reaction is finished for 24 hours to obtain the mercaptobenzothiazole-olefine acid-polythio oligomer product, and the product can be used as a corrosion inhibitor in an aqueous anticorrosive coating.
Example 5
(1) 0.8mol of mercaptobenzothiazole is dispersed in an aqueous alkaline solution (pH >8), heated, stirred at 350r/min and nitrogen is passed through. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide accounting for 4.5% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid with the same mole as mercaptobenzothiazole, reacting for 15 hours, obtaining mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, wherein beta-pinene accounts for 20% of the total mass of elemental sulfur and terpene. Dissolving 0.8mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 220r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the adding amount is 3.5 percent of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after the reaction is finished for 24 hours to obtain the mercaptobenzothiazole-olefine acid-polythio oligomer product, and the product can be used as a corrosion inhibitor in an aqueous anticorrosive coating.
Example 6
(1) Mercaptobenzothiazole, 1.8mol, was dispersed in an aqueous alkaline solution (pH >8), heated at a stirring rate of 350r/min and purged with nitrogen. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide which accounts for 3% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid which is equal to mercaptobenzothiazole in mole, reacting for 17 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, and beta-pinene accounts for 25% of the total mass of elemental sulfur and terpene. Dissolving 1.8mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 220r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the addition amount is 4% of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after 24 hours of reaction, and obtaining the mercaptobenzothiazole-olefine acid-polythio oligomer which can be used as a corrosion inhibitor in a water-based anticorrosive coating.
Example 7
(1) 2mol of mercaptobenzothiazole are dispersed in an aqueous alkaline solution (pH >8), heated and stirred at 400r/min and nitrogen is passed through. Setting the reaction temperature to be 50 ℃, dropwise adding a certain amount of catalyst sodium ethoxide which accounts for 3% of the total mass of mercaptobenzothiazole and olefine acid after the temperature is constant, dropwise adding vinylsulfonic acid which is equal to mercaptobenzothiazole in mole, reacting for 19 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, the polysulfide polymer is prepared, and beta-pinene accounts for 30% of the total mass of elemental sulfur and terpene. Dissolving 2mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the mixture in an oil bath to 80 ℃, stirring at the speed of 240r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the addition amount is 3.5 percent of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after the reaction is finished for 24 hours to obtain the mercaptobenzothiazole-olefine acid-polythio oligomer product, and the product can be used as a corrosion inhibitor in an aqueous anticorrosive coating.
Example 8
(1) Mercaptobenzothiazole, 1.5mol, was dispersed in an aqueous alkaline solution (pH >8), heated at a stirring rate of 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 vinylsulfonic acid with the same mole as mercaptobenzothiazole, reacting for 21 hours, obtaining a mercaptobenzothiazole-olefine acid compound after complete reaction, washing, and drying for later use.
(2) According to the preparation method of polysulfide oligomer in example 1 of patent application No. CN201710617001.4, polysulfide polymer is prepared, wherein beta-pinene accounts for 35% of the total mass of elemental sulfur and terpene. Dissolving 1.5mol of polythio oligomer in a toluene solvent, adding the mercaptobenzothiazole-olefine acid compound prepared in the step (1), heating the oil bath to 80 ℃, stirring at the speed of 240r/min, introducing nitrogen and condensed water, adding a catalyst hexamethylenetetramine to initiate a reaction after the temperature is constant, wherein the adding amount is 3.5 percent of the total mass of mercaptobenzothiazole-olefine acid and PST, washing and drying after 24 hours of reaction, and obtaining the product mercaptobenzothiazole-olefine acid-polythio oligomer which can be used as a corrosion inhibitor in a water-based anticorrosive coating.
Example 9
The corrosion inhibitor prepared in the embodiment 1 of the invention is added into the water-based acrylic resin, and the addition amount is 3% of the mass of the water-based 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, the metal matrix is tinplate, and surface treatment such as zinc protective layer removal, dust removal and rust removal is performed in advance before coating. Acrylic resin is coated twice by using a 25mm wire rod, then the acrylic resin is dried for 12 hours at the constant temperature of 80 ℃ by an oven, and after the acrylic resin is taken out and cooled on the surface of the metal, a brine experiment is started, namely the metal material is soaked in 3.5 wt.% sodium chloride solution for 96 hours at the constant temperature of 40 ℃ to test the anticorrosion effect of the metal material. As shown in fig. 3, the left control group was an acrylic coating to which no corrosion inhibitor was added, and the right experimental group was an acrylic coating to which a corrosion inhibitor was added. The left control group started to develop rust spots 12 hours after the saline experiment and continued to deepen the immersion corrosion until the surface was completely rusted 48 hours later. The right experimental group starts to generate film micro-bubbling after being soaked for 52 hours, small rusty spots appear on the wrapping edge of the metal substrate, and the metal substrate is not obviously corroded until the soaking is finished.
The aqueous acrylic resin used in this example was prepared by the following method:
firstly, emulsifying a nuclear monomer: 250ml of four-neck flask is added with core monomers of hexadecyl methyl methacrylate, dodecyl methacrylate and styrene in the mass ratio of 1:1:3, the total mass of the core monomers is 30g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added in 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 180r/min, introducing nitrogen, condensing water, and carrying out oil bath at the constant temperature of 75 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. The emulsified shell monomer and aqueous initiator solution (1.2g of potassium persulfate as initiator dissolved in 20g of water) were initially added dropwise at a rate of 0.4g/min at 8 g/min. And then after the shell monomer is dripped, preserving the heat for 1 hour to obtain the water-based acrylic resin emulsion. The shell monomer is prepared by taking 70g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a corrosion inhibitor used in a water-based anticorrosive coating is characterized by comprising the following steps:
the method 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 polysulfide oligomer to prepare a mercaptobenzothiazole-olefine acid-polysulfide oligomer compound, namely the corrosion inhibitor used in the water-based anticorrosive coating.
2. The preparation method of the corrosion inhibitor used in the water-based anticorrosive coating according to claim 1, characterized by comprising the following steps:
(1) dispersing mercaptobenzothiazole in an alkaline aqueous solution, raising 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) dissolving 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 used in the water-based anticorrosive coating.
3. A method of preparing a corrosion inhibitor for use in aqueous corrosion resistant coatings according to claim 1 or 2, characterized in that the olefinic acid has the following molecular structure:
wherein x is-COOH or-SO3H, n is a positive integer from 1 to 12.
4. A method for preparing a corrosion inhibitor for use in aqueous corrosion resistant coatings according to claim 1 or 2, characterized in that:
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; the mass of the terpene accounts for 5-60% of the total mass of the terpene and the elemental sulfur.
5. A method for preparing a corrosion inhibitor for use in aqueous corrosion resistant coatings according to claim 1 or 2, characterized in that:
the dosage of the olefine acid is equal to the molar weight of the mercaptobenzothiazole; the polythio oligomer is used in an amount equal to the molar amount of mercaptobenzothiazole.
6. The preparation method of the corrosion inhibitor used in the water-based anticorrosive coating according to claim 2, characterized in that:
the catalyst in the step (1) comprises at least one of sodium ethoxide, benzyl ammonium bromide and sodium amide, and the using amount 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 7-21 h;
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 value is more than 8.
7. The preparation method of the corrosion inhibitor used in the water-based anticorrosive coating according to claim 2, characterized in that:
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-olefine acid and the polysulfide oligomer;
the reaction temperature in the step (2) is 80-110 ℃, and the reaction time is 10-24 hours.
8. A corrosion inhibitor prepared according to the method of any one of claims 1 to 7 for use in aqueous corrosion resistant coatings.
9. The corrosion inhibitor useful in aqueous corrosion protective coatings according to claim 8, characterized in that: the corrosion inhibitor is compounded by mercaptobenzothiazole, olefine acid and polysulfide oligomer; the polysulfide oligomer is a polymer of elemental sulfur and terpene; the olefine acid has the following molecular structure:
wherein x is-COOH or-SO3H, n is a positive integer from 1 to 12.
10. Use of the corrosion inhibitor according to claim 8 or 9 for use in aqueous corrosion protection coatings for the protection of metal surfaces against corrosion.
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