CN87100883A - metal corrosion inhibitor - Google Patents
metal corrosion inhibitor Download PDFInfo
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- CN87100883A CN87100883A CN87100883.1A CN87100883A CN87100883A CN 87100883 A CN87100883 A CN 87100883A CN 87100883 A CN87100883 A CN 87100883A CN 87100883 A CN87100883 A CN 87100883A
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- Prior art keywords
- salt
- acrylic copolymer
- metal
- acid
- water
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000005260 corrosion Methods 0.000 title claims description 49
- 230000007797 corrosion Effects 0.000 title claims description 48
- 239000003112 inhibitor Substances 0.000 title claims description 27
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229920001444 polymaleic acid Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- CDHMFANDVPAILS-UHFFFAOYSA-N 2-but-2-enoyloxyethanesulfonic acid Chemical compound CC=CC(=O)OCCS(O)(=O)=O CDHMFANDVPAILS-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 29
- -1 amine compounds Chemical class 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001018 Cast iron Inorganic materials 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 abstract 1
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000007788 liquid Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000003203 everyday effect Effects 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000892 gravimetry Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PBCKVROHSSNSDY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;sodium Chemical compound [Na].CC(=C)C(O)=O PBCKVROHSSNSDY-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a metal anticorrosive agent, which comprises the following effective components: an acrylic copolymer composed of (meth) acrylic acid and/or a salt thereof (A) and thioethyl (meth) acrylate and/or a salt thereof (B) as main monomer components, or the acrylic copolymer and polymaleic acid and/or a salt thereof (ii). The metal anticorrosive agent has excellent anticorrosive effect on iron, low carbon steel and cast iron. Further, since heavy metal compounds, phosphorus compounds, amine compounds, etc. are not required, there is an advantage of safe use.
Description
The invention relates to corrosion inhibitor for metal and using method thereof.In more detail, be about under metal and corrosive environment that water contacts, add the corrosion inhibitor for metal that water uses.
At so-called water initiating device, as, in steam-generating installation, heating system, chemical reaction equipment, the cooling water system, corrosive nature when contacting with water, takes place in metal (iron, soft steel, cast iron etc.) easily that constitute this type of device.One to since, in order to prevent this corrosion, advise always and adopt all inhibitors.Wherein, particularly inorganic salt such as chromic salt, phosphoric acid salt, nitrite and thanomin etc. are particularly well-known, can add in the recirculated waters such as water coolant and use as water-soluble inhibitor.
But the past is considered to the chromic acid compounds such as potassium bichromate of excellent inhibitor always, but re-uses hardly because of it has toxicity now.And things such as other Tripyrophosphoric acid also because the regulation of public hazards aspect, and limit its use gradually.In addition, also have the material of picture nitrite and low-grade amine and so on,, when using them, also can be subjected to various restrictions in case, generate carcinogenic nitrosamine person simultaneously also with reacting.
The objective of the invention is to develop, neither contain the heavy metal compound, nitrogen compound, the phosphorus compound that cause public hazards, and can bring into play the inhibitor of good corrosion protection result.
Some multipolymer in the used acrylic copolymer among the present invention, past has found to have the fouling of preventing effect in water system, this is well-known, and (Japan, spy open clear 60-41595 communique (promptly " openly speciallyying permit communique " 1985 No. 41595)., this kind multipolymer has the discovery of corrosion protection effect to metal, but is strange.Particularly, prevent that fouling is based on the sequestering action of compound used therefor, thereby suppress the separating out of hardness components (especially calcium component) in the water, the corrosion protection effect of so-called metallic surface then is based on the heterogenetic effect.Therefore, these prevent to there is no dependency between the effect of fouling and the corrosion protection effect, and also do not have migrating property easily in principle between them.
The present inventor, through studying intensively, the result is surprised to find that these acrylic copolymers have very excellent corrosion protection effect.
And, also further examination with this acrylic copolymer and other various medicaments simultaneously and usefulness, the result found again, by it and polymaleic acid class and usefulness, can obtain the fact of more excellent synergy corrosion protection effect.
Therefore the present invention can provide following corrosion inhibitor for metal:
Contain the acrylic copolymer (ⅰ) that constitutes as the principal monomer composition with (methyl) vinylformic acid and/or its salt (A) and (methyl) vinylformic acid sulfo-ethyl ester and/or its salt (B), with this corrosion inhibitor for metal of forming as effective constituent; And contain the corrosion inhibitor for metal of forming as effective constituent with this acrylic copolymer (ⅰ) and polymaleic acid and/or its salt (ⅱ).
In the used acryllic acid based copolymer of the present invention,, can recommend to adopt: vinylformic acid, methacrylic acid and these sour an alkali metal salts etc. as its (methyl) vinylformic acid and/or its salt (A) person who forms unit.
And form in (methyl) vinylformic acid sulfo-ethyl ester and/or its salt (B) of unit as another, can recommend: their sulfo-ethyl ester and an alkali metal salts of these esters etc. separately of vinylformic acid, methacrylic acid.
Above-mentioned multipolymer is made of as main component monomer (A) and monomer (B), and monomer (A) and (B) with 95: 5 to 40: 60 mol ratio and constitutor, better, then better on the corrosion protection effect by 90: 10 to 50: 50 constitutors of mol ratio.
In addition, the molecular weight of above-mentioned multipolymer, being adjusted into about 500-20,000, its corrosion protection effect is good, and is about 1,000-10,000 is then better.
Above-mentioned multipolymer can be made every effort to overcome (ア Network ア リ Star Network) person (registered trademark, Nippon Shokubai Kagaku Kogyo Co., Ltd) by commodity A Kua by name and be obtained, and as for the preparation aspect of inhibitor of the present invention, also is to adopt this commercially available product comparatively easy.But, re-use after also can producing this multipolymer.
In this case,, be prepared by various polymerizations though can adopt common polymerization starter, yet, be easy to the control aspect from reaction and consider that polymerization is better in solvent.
As used in this case solvent, though can select all kinds of SOLVENTS, during from above-mentioned monomer (A) and the consideration of solvability (B), then comparatively suitable with water, lower alcohol.
And, need according to above-mentioned solvent types and selective polymerization initiator suitably.For example, in water solvent, can adopt an alkali metal salt or its ammonium salt of persulfuric acid, perhaps hydrogen peroxide etc.And in the lower alcohol equal solvent time, then can recommend benzoyl peroxide, lauroyl peroxide, hydrogen phosphide cumene, Diisopropyl azodicarboxylate etc.
In above-mentioned polyreaction, also can suitably select suitable promotor or chain-transfer agent,
The temperature of above-mentioned polyreaction can suitably be determined according to condition such as solvent for use and polymerization starter, but normally react in 0-120 ℃ of scope.
As the polymaleic acid among the present invention, though various molecular weights all can be used, consider from being easy to synthetic aspect, then be advisable with the molecular weight junior, can fit for service be that molecular weight is about 300-5000 person generally.And consider from the corrosion protection effect, then molecular weight less than 1000 for good especially.These polymaleic aciies can obtain by following method, for example, in organic solvent, employing is greater than 5% polymerization starter (benzoyl peroxide, Diisopropyl azodicarboxylate etc.), make Maleic Acid, Anhydrous aggregate into poly-Maleic Acid, Anhydrous under with polymerizing condition such as heat additional, then, among water etc., add moisture be situated between it and obtain; Perhaps, in the aqueous solution, toxilic acid or Maleic Acid, Anhydrous are made single alkali metal salts or ammonium salt, adopt polymerization starter (hydrogen peroxide class, dialkyl group peroxide and persulfuric acid salt etc.), additionally wait polymerizing condition acquisition down to heat.And, as polymaleic acid salt, in fact so long as water-soluble person just can use, for example, what can be suitable for using has, the salt that low-grade alkylamine such as an alkali metal salt of lithium, sodium and sylvite and so on, ammonium salt or it and methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, propylamine is combined to.In the middle of these,, use an alkali metal salt for well from the corrosion protection effect.Again, the ester body portion of polymaleic acid, or amine body portion all can make polymkeric substance, promptly can use as long as come down to water-soluble person.
In addition, polymaleic acid class one is to as scale inhibitor (Japan, special public clear 53-20475 communique (i.e. " special permission communique " 1978 No. 20475)) be well-known.And, with specific corrosion compound and time spent, it also is known (spy of Japan opens clear 53-149837 communique (promptly " disclosing the characteristic communique " 1978 No. 149837), and the spy opens clear 53-149836 communique (promptly " openly speciallyying permit communique " 1978 No. 149836)) as the ancillary component role of corrosion protection.But finding also has the document of abundant corrosion protection effect but not have when itself uses separately.
Aforementioned with the inhibitor of acrylic copolymer, can be made into 5-50%(weight usually as the present invention of effective constituent) the aqueous solution used.And in the object water of need corrosion protection, add aforesaid propylene acid based copolymer, to make its content in water be 1-500ppm for well.If, just can not perform to the corrosion protection effect of expection less than prescribing a time limit under this scope.And can not obtain higher effect in limited time greater than last, the result causes waste, and is bad on the contrary.And in above-mentioned scope, the addition preferably of corrosion protection effect is 20-200ppm as bringing into play fully.
On the other hand, be the present invention's of effective constituent inhibitor with above-mentioned acrylic copolymer and polymaleic acid class, the form that generally also can be dissolved in the water and using.At this moment, concerning 1 parts by weight of acrylic multipolymer, polymaleic acid and/or its salt can be decided to be the 0.1-10 weight part, and from the performance synergistic effect, this is suitable.And it is better with the 0.2-5 weight part.Especially good when being decided to be about 1 weight part.And when adding this kind inhibitor in object water, in two kinds of effective constituents, acrylic copolymer content is 1-500ppm for well.Again, in this scope, can further bring into play more abundant corrosion protection effect, addition is 10-100ppm preferably.
Contain the acrylic copolymer inhibitor this, and the inhibitor that contains acrylic copolymer and polymaleic acid class, join in the corrosion protection object water, just can suppress significantly by this or anti-sealing in the corrosion of the metal, particularly ferrous metal that exist.Therefore, if see that with a certain viewpoint the present invention also provides the metal of following characteristics anti-corrosion method.That is, in corrosion protection object water, add: with (methyl) vinylformic acid and/or its salt (A) and (methyl) vinylformic acid sulfo-ethyl ester and/or its salt (B), the acrylic copolymer (ⅰ) that constitutes as main monomer component; Perhaps, add this acrylic copolymer (ⅰ) and toxilic acid and/or its salt (ⅱ).Thus, can prevent or suppress corrosion of metal.
In addition, also can in inhibitor of the present invention, mix, also can suitably add additives such as other dispersion agent, sterilization and sterilant not hinder other anticorrosive composition of its corrosion protection effect.
The present invention can be described in detail by following embodiment, but the present invention can not be limited in view of the above.
The synthetic example of acrylic copolymer:
In the glass reactor that is equipped with thermometer, agitator, dropping funnel, airway and reflux condensing tube, 89.9 parts in the water of packing into the air in the nitrogen replacement reactor, is heated to 95 ℃ under whipped state.Then, 55.8 parts of monomer mixture solutions of being formed of sodium-salt aqueous solution by 94.3 parts of 40% methacrylic acid sodium water solutions and 40% vinylformic acid sulfo-ethyl ester; And 10% 50 parts of ammonium persulfate aqueous solution, with 120 fens clock times, join in the reactor respectively.After having added, add 10 part of 10% ammonium persulfate aqueous solution with 20 fens clock times again.After the monomer interpolation finishes, make temperature remain in boiling point 120 minutes,, obtain multipolymer to finish polyreaction.This multipolymer viscosity is 88 centipoises.In addition, with high-speed liquid chromatography method determining molecular weight, the result is 1100.
Example
Adopt synthetic condensed water as experimental liquid, 1 liter of the experimental liquid that adds the specified amount medicament is equipped with in the test that the corrosion protection effect of soft steel test film is measured, in 1 liter flat bottom beaker.Soft steel test film (commercially available name of an article SPCC is shaped as 30 * 50 * 1 millimeter rectangle sheet) is hung on end with the stirring rod of motor interlock, and be dipped in the experimental liquid.Set up thermostatted, made the liquid temperature remain in 40 ℃, above-mentioned test film is rotated so that 100 rev/mins speed is lasting, carried out five days test with the heating liner plate.After the off-test, take out test film, gravimetry after pickling, washing, drying is by the weight determination MDD(millimeter/decimetre that is reduced
2Day), i.e. the corrosion decrement of each day.The water quality of used synthetic condensed water is shown in (table 1).
The water quality of (table 1) synthetic condensed water
The menu bit value
PH - 8.3
Calcium hardness mg/litre 200
M basicity mg/litre 200
P basicity mg/litre 0
Chlorion mg/litre 200
Sulfate ion mg/litre 100
At first, what Fig. 1 represented is, make the mole of sodium acrylate ((A) composition) and vinylformic acid sulfo-ethyl ester ((B) composition) liken many variations to and the multipolymer that is modulated into, and (A Kua makes every effort to overcome (registered trademark to molecular weight about 4000, LS) and molecular weight about 10 Nippon Shokubai Kagaku Kogyo Co., Ltd), 000 (A Kua makes every effort to overcome (the same) NS) person, use this multipolymer, and be the concentration of 40ppm when adding with its solid state component, the MDD(of determination test sheet is the corrosion decrement of every day) the result.
Fig. 2 represents to adopt the molecular weight of multipolymer to be respectively the multipolymer that is modulated in the above-mentioned synthetic example of about 1000(), about 4000 (A Kua makes every effort to overcome (the same) LS), about 7000 (A Kua makes every effort to overcome (the same) PS) and about 10,000 (A Kua makes every effort to overcome (the same) NS), and (A) composition in this multipolymer and (B) mol ratio between the composition with (A): (B)=80: the 20(tagger), 50: 50(△ tagger), with 30: the 70(* tagger) multipolymer that is constituted, when the solid state component of this multipolymer added with the concentration of 40ppm, the determination test sheet corroded the result of decrement MDD every day.
Fig. 3 represents, adopt about 4000 (A Kua makes every effort to overcome (the same) LS) of molecular weight of copolymer, and with (A) composition in this multipolymer and (B) mol ratio between composition be, (A): (B)=80: the 20(tagger), 50: 50(△ tagger) and 30: the 70(* tagger) multipolymer that is constituted, when changing the interpolation concentration of this multipolymer, the determination test sheet corrodes the result of decrement MDD every day.
From above result, at first, show that the mol ratio of sodium acrylate (A) and vinylformic acid sulfo-ethyl ester (B) can be brought into play its effective corrosion protection effect with in 95: 5 to 40: 60 the multipolymer that scope was constituted by Fig. 1.
Secondly, as shown in Figure 2, the molecular weight of this multipolymer, can be kept effective corrosion protection effect at 000 o'clock at about 1000-10.
And then illustrate by Fig. 3, when using this inhibitor,, when making composition that it exists, just can give full play to its effect in liquid greater than 20ppm if add multipolymer, as if further adding 40ppm to when above, just can bring into play its corrosion protection effect to greatest extent.
Example 2
Adopt the Osaka City water that concentrates 5 times as experimental liquid, the soft steel test film is carried out the determination test of corrosion protection effect.In the beaker of the peaceful end, 1 liter of the experimental liquid of packing into and being added with the specified amount medicament.Soft steel test film (commercially available name of an article spcc is shaped as 30 * 50 * 1 millimeter rectangle thin slice) is hung on stirring rod end with the motor interlock, and be dipped in the experimental liquid.Attached do not have a thermostatted, makes the liquid temperature remain in 40 ℃ or 50 ℃ with the heating liner plate.Make above-mentioned test film with the lasting rotation of 100 rev/mins speed, tested three days.After the off-test, take out test film, after pickling, washing, drying, gravimetry.By the weight determination MDD(milligram/decimetre that is reduced
2Day), i.e. the corrosion decrement of each day.The used water quality that concentrates 5 times Osaka City is shown in (table 2), and MDD result then is shown in (table 3) and (table 4).
Again, (table 3) expression is that 40 ℃ of liquid temperature, difference is added the per 1 day corrosion decrements of MDD(under the ratio) result.As acrylic copolymer, adopt by (A) composition sodium acrylate and (B) sale on the market formed of composition vinylformic acid sulfo-ethyl ester (registered trademark A Kua makes every effort to overcome: following multipolymer Nippon Shokubai Kagaku Kogyo Co., Ltd):
Commodity label mol ratio molecular weight
(A): (B) (average viscosity)
KS-20 80∶20 1000
LS-15 85∶15 4000
LS-20 80∶20 4000
LS-30 70∶30 4000
LS-70 30∶70 4000
PS-20 80∶20 7000
NS-20 80∶20 10000
Then adopt various molecular weight as polymaleic acid salt, promptly molecular weight is about the polymkeric substance of 300-400 and about 900.
On the other hand, (table 4) expression is that 50 ℃ of liquid temperature, and various interpolation is about adopting above-mentioned LS-15, LS-20 and LS-30(molecular weight 4000 than corroding decrement (MDD) every day under the condition) as the result of acrylic copolymer.
The water quality of (table 2) Osaka City water (* 5 times) condensed water
The menu bit value
PH - 8.45
The little Siemens/cm 940 of conductivity
Total hardness CaCO
3Mg/litre 242.8
Calcium hardness CaCO
3Mg/litre 197.0
M basicity CaCO
3Mg/litre 80.5
P basicity CaCO
3Mg/litre 0
Chlorion CI mg/litre 97.7
Sulfate ion SO
4Mg/litre 172.0
Silicon oxide component S iO
2Mg/litre 33.5
In addition, for the purpose of reference, when the interpolation concentration of embodiment in above-mentioned (table 3) and (table 4) was 25 mg/litre and 50 mg/litre, the relation of adding ratio and corroding decrement (MDD) every day all was illustrated among Fig. 4 and Fig. 5 with the relation of the molecular weight of acrylic copolymer.
From above-mentioned (table 3) and (table 4) and Fig. 4 and Fig. 5 as can be known, by acrylic copolymer and polymaleic acid salt and usefulness, can make and corrode decrement (MDD) every day and significantly reduce when using respectively separately, synergistic effect has been brought into play in this explanation.Especially, the former: the latter=1: 5-5: 1 o'clock (during the former 1 weight part, the latter should be 0.2-5 mutually), this effect is more remarkable.
The present invention's corrosion inhibitor for metal is based on the effect of specific acrylic copolymer itself, perhaps based on the synergism between this multipolymer and the polymaleic acid class, thereby iron, soft steel, cast iron etc. is presented excellent corrosion protection effect.And, owing to do not need heavy metal compound, phosphorus compound, aminated compounds etc., and have the advantage that can use safely.
Fig. 1 is the copolymerization ratio difference of expression along with the acrylic copolymer of main component in the inhibitor of the present invention, the graphic representation that its corrosion protection effect also changes thereupon.Fig. 2 is the difference of expression along with the acrylic copolymer molecular weight of main component in the inhibitor of the present invention, the curve that its corrosion protection effect is also different.Fig. 3 is the difference of expression along with inhibitor of the present invention addition in the aqueous solution, the graphic representation that its corrosion protection result is also different.Fig. 4 and Fig. 5 are expressions because of acrylic copolymer and Malaysia acids and with the graphic representation that presents different efficacies.
(table 3) test-results (40 ℃ of liquid temperature)
(table 3) test-results (40 ℃ of liquid temperature) (continuing)
(table 4) test-results (50 ℃ of liquid temperature) (continuing)
(table 4) test-results (50 ℃ of liquid temperature) (continuing)
Claims (4)
1, a kind of corrosion inhibitor for metal, the effective constituent that wherein contains is, with (methyl) vinylformic acid and/or its salt (A), and (methyl) vinylformic acid sulfo-ethyl ester and/or its salt (B), the acrylic copolymer (i) that constitutes as the principal monomer composition, or aforesaid propylene acid based copolymer (i) and polymaleic acid and/or its salt are (ii).
2, according to the corrosion inhibitor for metal of claim 1, in the acrylic copolymer, composition (A) is 95 with the copolymerization ratio of composition (B): 5-40: 60.
3, according to the corrosion inhibitor for metal of claim 1, the molecular weight of acrylic copolymer is about 500-20000.
4, according to the corrosion inhibitor for metal of claim 1, the molecular weight of polymaleic acid or its salt is about 300-5000.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61008632A JPS62167894A (en) | 1986-01-17 | 1986-01-17 | Anticorrosive for metal |
| JP8632/86 | 1986-01-17 | ||
| JP61119694A JPH0751758B2 (en) | 1986-05-23 | 1986-05-23 | Metal anticorrosive |
| JP119694/86 | 1986-05-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100883A true CN87100883A (en) | 1987-08-05 |
| CN1033178C CN1033178C (en) | 1996-10-30 |
Family
ID=26343189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87100883A Expired - Fee Related CN1033178C (en) | 1986-01-17 | 1987-01-17 | Corrosion inhibitor for metal |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR930011415B1 (en) |
| CN (1) | CN1033178C (en) |
-
1987
- 1987-01-17 CN CN87100883A patent/CN1033178C/en not_active Expired - Fee Related
- 1987-01-17 KR KR1019870000378A patent/KR930011415B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR870007301A (en) | 1987-08-18 |
| KR930011415B1 (en) | 1993-12-06 |
| CN1033178C (en) | 1996-10-30 |
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