US2881139A - Corrosion preventing compositions and process - Google Patents
Corrosion preventing compositions and process Download PDFInfo
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- US2881139A US2881139A US529913A US52991355A US2881139A US 2881139 A US2881139 A US 2881139A US 529913 A US529913 A US 529913A US 52991355 A US52991355 A US 52991355A US 2881139 A US2881139 A US 2881139A
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- Prior art keywords
- water
- corrosion
- guanidino
- acid
- copper
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- Expired - Lifetime
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- 238000005260 corrosion Methods 0.000 title claims description 33
- 230000007797 corrosion Effects 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 title description 14
- 239000003599 detergent Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 description 12
- -1 hydrocarbon radicals Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 5
- 239000010953 base metal Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 4
- 239000010956 nickel silver Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- IFYPQHGXCVZZMW-UHFFFAOYSA-N 2-(6-chloro-1h-benzimidazol-2-yl)guanidine Chemical group C1=C(Cl)C=C2NC(N=C(N)N)=NC2=C1 IFYPQHGXCVZZMW-UHFFFAOYSA-N 0.000 description 2
- JJWCTKUQWXYIIU-UHFFFAOYSA-N 2-Benzimidazolylguanidine Chemical compound C1=CC=C2NC(N=C(N)N)=NC2=C1 JJWCTKUQWXYIIU-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 239000001226 triphosphate Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- UNAQOMVIYOSKDN-UHFFFAOYSA-N 2-(6-methoxy-1h-benzimidazol-2-yl)guanidine Chemical group COC1=CC=C2N=C(NC(N)=N)NC2=C1 UNAQOMVIYOSKDN-UHFFFAOYSA-N 0.000 description 1
- NFVKSWJIGKATLV-UHFFFAOYSA-N 2-(6-methyl-1h-benzimidazol-2-yl)guanidine Chemical group CC1=CC=C2N=C(N=C(N)N)NC2=C1 NFVKSWJIGKATLV-UHFFFAOYSA-N 0.000 description 1
- NAGIDXZSUSERRK-UHFFFAOYSA-N 2-(6-nitro-1h-benzimidazol-2-yl)guanidine Chemical group C1=C([N+]([O-])=O)C=C2NC(N=C(N)N)=NC2=C1 NAGIDXZSUSERRK-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—Organic inhibitors
Definitions
- the present invention concerns a process for the protection of copper and copper alloys with base metals against corrosion when in contact with water or aqueous' alkaline solutions. It also concerns agents, in particular cleansing agents, the aqueous or aqueousaalkaline solutions of which, due to a content of the protective agents against corrosion usable according to the present invention, have no or only an inconsiderable corrosive action on scoured surfaces of copper and alloys thereof with base metals.
- 2-guanidino-aryloimidazole can contain as aryl radicals,v for. example, thebenzeneor the naphthalene ring whichcan, be further substituted, for example with halogen,. alkyl, alkoxy, nitro, acylamino, alkylsulphonyl, arylsul phonyl or sulphonic acid amide groups. They may not contain, however, any groups either as such or in the form of their watersolubilising salts which dissociate acid in neutral water such, as, for example, carboxyl, sulphonic acidor phosphonic acidgroups. As they. must.
- Z-guanidino-aryloimidazole compounds useableaccording to the present invention are knownbut. all canbe produced easily according to known methods. from aromatic o-diamiuocompounds bycondensation, with dicyanodiamide in acid solution.
- guanidino-arylo-imidazole compounds for example 01 to 100mg. per litre; protect scoured copper and alloys thereof with base metals such as, e.g. brass. or nickel silver,xfrom corrosive action when in contact with water-or aqueous alkaline solutions, in particular in a pH range of from 8 to 12.
- the aqueous alkaline solutions can contain forexample: lithium, sodium or potassium salts ofcarbonic acid'or' the-oxyacids of boron,- silicium or phosphorus hHViflgB basic reaction. They may also contain neutralisalts' suchas sodium sulphate, sodium chloride, potassium sulphate or potassium chloride etc.
- capillary active cleansing agents such-as are the usual additives to capillary active cleansing agents as well as capillary active wetting, dispersing and cleansing agents which contain lipophilic hydrocarbon radicals and hydrophilici groups.
- capillary active agents afei the fatty alcohol polyglycol ethers, the alkyl phenol poly glycol ethers, the fatty acid alkanol amides and polyglycol ethers thereof, the alkali and ammonium salts ofthe sulphuric acid half esters offatty alcohols, of the sulphated mono-fatty acid esters of polyalcohols, the alkali and ammonium salts of alkyl and alkylaryl s'ul' phonic acids; of sulph'osuccinic' acid esters" and of fatty? acids which contain lipophilic radicals.
- dispersing and cleansing agents which contain the usual; alkali salts of polyphosphoric acids which make calciumions unharmful, such as e.g. tetrasodium pyrophospha'te',i' pentasodium triphosphate, sodium hexametaphosphate' or mixtures of the alkali saltsof such polyphosphoric acids; the 2-guanidino-arylo-imidazole compounds used accord ing to the present invention protect scoured copper and alloys thereof with base metals from corrosion when in contact with these solutions. They also protectco'pper from attack by aqueous ammonia 'and' amines.
- themin alkaline cleansing agents made up from saltshaving an alkalin'e reaction such as alkali carbonates, alkalisilicates,alkali borates and alkali polyphosphates-or incleansingiagents which. contain. such salts as Well as; possibly, capillarieactive wetting and cleansing agents and neutral salts: which are used for the treatment-of. scoured copper and alloys thereof with base metals.
- cor-r'osion protective agents'according'tothe present invention depends to a great extent-on thespecific activity of'the Z-guanidino-aryloimidazole compound used, on the alkalinity of the treatment liquor, and onthe tempera ture and duration ofthe treatment. Generally amounts of up to 1% calculated on the non-aqueous" componen of such cleansing.v compositions are sufficient but also considerably less or more can be incorporated',-for'example 0.05 to 5%.
- Example 10 An aqueous solution containing 4.0 g. tech. tetrasodium pyrophosphate 1.0 g.. 2.4-di-tert. amylphenol polyglycol ether perilitre attacks brasspiate and nickelsilver plate-while forming strong oxidation tints; in addition som'eof themetal dissolves. At a temperature of to over'a' period of 24 hours, the loss in weight of' elementary metal is Brass 7.0 g] sq..'m./ 24 hours.” Nickel silver 14.6 g./ sq; m'.'/24 hours.
- Example 2 Brass plate and nickel silver plate are treated with 8 g. of the following composition of washing agents in a tiitre of tap water:
- alkylaryl sulphonate consisting chiefly of dodecyl benzene sulphonate
- the loss in weight of the vessel was 0.50 g. elementary copper for each square metre.
- the composition of washing agents was implemented by the addition of 0.05 part (calculated on the solid substances) of Z-guanidinobenzir'nidazole and the same procedure was followed. In this case, the loss of metal was only 0.06 g. for each square metre. In addition the surface of the copper remained completely scoured.
- Example 4 0n contact with scoured copper of a washing liquor containing 8 g. per litre of a compositlon of washing agents made up from 6 parts of sodium carbonate, 2 parts of higher fatty acids, 01 part of carboxymethyl cellulose, 018 part of sodium perborate,
- a process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions which com prises bringing said coppery metal surfaces into contact with alkaline aqueous solutions containing from 1 to parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
- a process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions of a watersoluble cleansing agent normally tending in aqueous solution to cause corrosion of coppery metal which comprises bringing said coppery metal surfaces into contact with alkaline'aqueous solutions of a water-soluble cleansing agent containing from 1 to 100 parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group" consisting of o-phenylene and o-naph'thylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
- a process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions of a water soluble cleansing agent containing a surface-active agent and alkali metal phosphates which comprises bringing said coppery metal surfaces into contact with alkaline aqueous solutions of a water-soluble cleansing agent containing a surface-active agent, alkali metal phosphates and from 1 to 100 parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which disrosion inhibitor is 6-methyI-Z-guanidino-benzamidazole.
- the corrosion inhibitor is 6-chloro-2-guanidino-benzimidazole.
- a corrosion preventing composition consisting of a water-soluble cleansing agent dissolving in water with an alkaline reaction, the aqueous solutions of which tend to cause corrosion of coppery metal on contact, and of 0.05 to 1%, calculated on the dry weight of said cleansing agent, of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid inneutral water.
- a corrosion preventing composition consisting of a water-soluble cleansing agent, which comprises a surface-active agent and alkali metal phosphates and which dissolves in water with an alkaline reaction, the aqueous solutions of which tend to cause corrosion of coppery metal on contact, and of 0.05 to 1%, calculated on the dry weight of said cleansing agent, of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General 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)
- Detergent Compositions (AREA)
Description
United States Patent CORROSION PREVENTING COMPOSITIONS AND PROCESS Hermann Gysling, Basel, Switzerland, assignor to J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm No Drawing. Application August 22, 1955 Serial No. 529,913
Claims priority, application Switzerland September 16, 1954 15 Claims. (Cl. 252-137) The present invention concerns a process for the protection of copper and copper alloys with base metals against corrosion when in contact with water or aqueous' alkaline solutions. It also concerns agents, in particular cleansing agents, the aqueous or aqueousaalkaline solutions of which, due to a content of the protective agents against corrosion usable according to the present invention, have no or only an inconsiderable corrosive action on scoured surfaces of copper and alloys thereof with base metals.
It has been found that scoured surfaces of copper andlalloys of copper and base. metals; can be protected' against corrosion in contact with water and. imparticular with: aqueous alkaline'solutions if slight amounts of:- such 2-guanidino-aryloimidazole1' compounds? containing. no watersolubilising, groups which dissociate. acid. in neutral water and which are at least very slightly soluble in..water or in aqueous solutions, are added tothe water or, to. the solutions.
2-guanidino-aryloimidazole. compounds used according to the present invention can contain as aryl radicals,v for. example, thebenzeneor the naphthalene ring whichcan, be further substituted, for example with halogen,. alkyl, alkoxy, nitro, acylamino, alkylsulphonyl, arylsul phonyl or sulphonic acid amide groups. They may not contain, however, any groups either as such or in the form of their watersolubilising salts which dissociate acid in neutral water such, as, for example, carboxyl, sulphonic acidor phosphonic acidgroups. As they. must. be, water soluble, even if only slightly so, the benzimidazolevcomp ounds are to be preferredito those-withliiglier condensed rings. For example,v 2-guanidinorbenzimidae zole, 2 guanidino-6-chloro-., -6-methyl=,. -6.-methoxyor -6-ethoxy-benzimidazole, 2-guanidino-4- or. -6=nitro-benz= imidazole, 2-guanidino-4- or, -6racetylamino-benzimidazole, 2-.guanidino-6-methylsulphonyl-, -ethylsulphonyl:, or. -nbuty1sulphonybbenzimidazole, Z-guanidiho-henzimidazole 6-sulphonic acid dimethylamide,. -diethylamide,. -piperidide ,or -morpholide, Z-guanidino- LS:1.2Gnaphthimidazole can be used. Because of itseasy accessibility andfavourable water solubility, 2-guanidino-benzimidazole isto bepreferred to all other, compounds.
Some of, the Z-guanidino-aryloimidazole compounds useableaccording to the present invention, are knownbut. all canbe produced easily according to known methods. from aromatic o-diamiuocompounds bycondensation, with dicyanodiamide in acid solution.
Very small amounts of these.2 guanidino-arylo-imidazole compounds, for example 01 to 100mg. per litre; protect scoured copper and alloys thereof with base metals such as, e.g. brass. or nickel silver,xfrom corrosive action when in contact with water-or aqueous alkaline solutions, in particular in a pH range of from 8 to 12. The aqueous alkaline solutions can contain forexample: lithium, sodium or potassium salts ofcarbonic acid'or' the-oxyacids of boron,- silicium or phosphorus hHViflgB basic reaction. They may also contain neutralisalts' suchas sodium sulphate, sodium chloride, potassium sulphate or potassium chloride etc. such-as are the usual additives to capillary active cleansing agents as well as capillary active wetting, dispersing and cleansing agents which contain lipophilic hydrocarbon radicals and hydrophilici groups. Examples of such capillary active agents afei the fatty alcohol polyglycol ethers, the alkyl phenol poly glycol ethers, the fatty acid alkanol amides and polyglycol ethers thereof, the alkali and ammonium salts ofthe sulphuric acid half esters offatty alcohols, of the sulphated mono-fatty acid esters of polyalcohols, the alkali and ammonium salts of alkyl and alkylaryl s'ul' phonic acids; of sulph'osuccinic' acid esters" and of fatty? acids which contain lipophilic radicals.
Particularly in aqueous-alkaline solutions of wetting. dispersing and cleansing agents which contain the usual; alkali salts of polyphosphoric acids which make calciumions unharmful, such as e.g. tetrasodium pyrophospha'te',i' pentasodium triphosphate, sodium hexametaphosphate' or mixtures of the alkali saltsof such polyphosphoric acids; the 2-guanidino-arylo-imidazole compounds used accord ing to the present invention protect scoured copper and alloys thereof with base metals from corrosion when in contact with these solutions. They also protectco'pper from attack by aqueous ammonia 'and' amines. Irisof advantage therefore, to incorporate themin alkaline cleansing agents made up from saltshaving an alkalin'e reaction such as alkali carbonates, alkalisilicates,alkali borates and alkali polyphosphates-or incleansingiagents which. contain. such salts as Well as; possibly, capillarieactive wetting and cleansing agents and neutral salts: which are used for the treatment-of. scoured copper and alloys thereof with base metals. The content of cor-r'osion protective agents'according'tothe present invention depends to a great extent-on thespecific activity of'the Z-guanidino-aryloimidazole compound used, on the alkalinity of the treatment liquor, and onthe tempera ture and duration ofthe treatment. Generally amounts of up to 1% calculated on the non-aqueous" componen of such cleansing.v compositions are sufficient but also considerably less or more can be incorporated',-for'example 0.05 to 5%. I
The following examples illustrate the invention vtiitli out limiting it in any way. Wherenototherwi'se state parts are given as parts by weight and the'temperatui's are in degrees centigrade.
Example] An aqueous solution containing 4.0 g. tech. tetrasodium pyrophosphate 1.0 g.. 2.4-di-tert. amylphenol polyglycol ether perilitre attacks brasspiate and nickelsilver plate-while forming strong oxidation tints; in addition som'eof themetal dissolves. At a temperature of to over'a' period of 24 hours, the loss in weight of' elementary metal is Brass 7.0 g] sq..'m./ 24 hours." Nickel silver 14.6 g./ sq; m'.'/24 hours.
If 3 mg. of Z-guanidi'nobenzimida'zole"is added for ever litre of the above treatment liquor and a parallelte' is "made then, under the same conditions, there are "the" following losses in weight:
the secured shining appearance of "themntreateclpl'ati'n is retained.
Example 2 Brass plate and nickel silver plate are treated with 8 g. of the following composition of washing agents in a tiitre of tap water:
3.0 parts of tetrasodium pyrophosphate,
1.0 part of the sodium salt of ethylendiamine tetraacetic acid,
2.0 parts of soap (sodium salt of stearic acid),
0.5 part-of the sodium salt of a secondary alkyl sulphate :(Shells Teepol) Example 3 Qwashing is done in a scoured copper vessel with a composition of washing agents made vup as follows:
10. parts of a usual marketed pentasodium triphosphate, 15.,parts of tetrasodium pyrophosphate,
5 parts of sodium silicate (waterglass),
l5.parts of sodium carbonate,
5 parts of alkylaryl sulphonate (consisting chiefly of dodecyl benzene sulphonate),
15 parts of fatty alcohol sulphate (laurel-sulphuric acid ester),
115 parts ,of carboxymethyl cellulose,
0.2 part of an optical brightening agent of the 1.4-bisr,triazinylaminostilbene-2.2'-disulphonic acid class, 33-.3parts of. sodium sulphate cryst.
After washing 30 times at 80-90 for 30 minutes each time, the loss in weight of the vessel was 0.50 g. elementary copper for each square metre. In a parallel trial the composition of washing agents was implemented by the addition of 0.05 part (calculated on the solid substances) of Z-guanidinobenzir'nidazole and the same procedure was followed. In this case, the loss of metal was only 0.06 g. for each square metre. In addition the surface of the copper remained completely scoured.
The other 2-guauidinobenzimidazole compounds listed in Example 2 can be used in this test with the same result.
Example 4 0n contact with scoured copper of a washing liquor containing 8 g. per litre of a compositlon of washing agents made up from 6 parts of sodium carbonate, 2 parts of higher fatty acids, 01 part of carboxymethyl cellulose, 018 part of sodium perborate,
a strongly coloured oxide layer is formed on the metal even at room temperature and particularly at higher temperatures. If, however, a few milligrammes per litre of one of the inhibitors listed below is added to this washing liquor, then the copper remains completely scoured:
*Z-guanidinobenzimidazole, 6-chloro 2 guanidinobenzimidazole, 6-methyl-Z-guanidinobenzimidazole, G-ethyl- 2-guanidinobenzimidazole, 6-nitro-2-guanidinobenzimidazole, 6-acetylamino-Lguanidinobenzimidazole, 6-methoxy-Z-guanidinobenzimidazole, 6-ethoxy 2 guanidinobenzimidazole, 6 -methyl sulphonyl-Z-guanidinobenzimidazole, 6-ethyl sulphonyl-Z-guanidinobenzimidazole, 6-
butyl sulphonyl-Z-guanidinobenzimidazole, Z-guanidino 4.5: 1'.2'- naphthimidazole, 2 guanidino 5'- ch1oro-4.5 1'.2'-naphthimidazole.
What I claim is:
1. A process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions, which com prises bringing said coppery metal surfaces into contact with alkaline aqueous solutions containing from 1 to parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
2. A process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions of a watersoluble cleansing agent normally tending in aqueous solution to cause corrosion of coppery metal, which comprises bringing said coppery metal surfaces into contact with alkaline'aqueous solutions of a water-soluble cleansing agent containing from 1 to 100 parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group" consisting of o-phenylene and o-naph'thylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
3. A process of preventing the corrosion of coppery metal surfaces by alkaline aqueous solutions of a water soluble cleansing agent containing a surface-active agent and alkali metal phosphates, which comprises bringing said coppery metal surfaces into contact with alkaline aqueous solutions of a water-soluble cleansing agent containing a surface-active agent, alkali metal phosphates and from 1 to 100 parts per million of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which disrosion inhibitor is 6-methyI-Z-guanidino-benzamidazole. 8. A process according to claim 1, in which the corrosion inhibitor is 6-chloro-2-guanidino-benzimidazole.
9. A corrosion preventing composition consisting of a water-soluble cleansing agent dissolving in water with an alkaline reaction, the aqueous solutions of which tend to cause corrosion of coppery metal on contact, and of 0.05 to 1%, calculated on the dry weight of said cleansing agent, of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid inneutral water.
10. A corrosion preventing composition consisting of a water-soluble cleansing agent, which comprises a surface-active agent and alkali metal phosphates and which dissolves in water with an alkaline reaction, the aqueous solutions of which tend to cause corrosion of coppery metal on contact, and of 0.05 to 1%, calculated on the dry weight of said cleansing agent, of a corrosion inhibitor of the formula wherein Ar represents a member selected from the group consisting of o-phenylene and o-naphthylene radicals which contain no water-solubilizing groups which dissociate acid in neutral water.
11. A corrosion preventing composition according to claim 9, wherein the corrosion inhibitor is Z-guanidinobenzimidazole.
12. A corrosion preventing composition according to claim 9, wherein the corrosion inhibitor is 6-nitro-2- guanidino-benzimidazole.
13. A corrosion preventing composition according to claim 9, wherein the corrosion inhibitor is 6-methoxy-2- guanidino-benzimidazole.
14. A corrosion preventing composition according to claim 9, wherein the corrosion inhibitor is 6-methyl-2- guanidino-benzimidazole.
15. A corrosion preventing composition according to claim 9, wherein the corrosion inhibitor is 6-chloro-2- guanidino-benzimidazole.
References Cited in the file of this patent UNITED STATES PATENTS 2,618,603 Schaefier Nov. 18, 1952. 2,618,606 Schaeffer Nov. 18, 1952 2,706,179 Tundermann Apr. 12, 1955
Claims (1)
1. 2. A PROCESS OF PREVENTING THE CORROSION OF COPPERY METAL SURFACES BY ALKALINE AQUEOUS SOLUTIONS OF A WATER SOLUBLAE CLEANSING AGENT NORMALLY TENDING IN AQUEOUS SOLUBLE TO CAUSE CORROSION OF COPPER METAL, WHICH COMPRISES BRINGING SAID COPPERY METAL SURFACES INTO CONTACT WITH ALKALINE AQUEOUS SOLUTIONS OF A WATER-SOLUBLE CLEANSING AGENT CONTAINING FROM 1 TO 100 PARTS PER MILLION OF A CORROSION INHIBITOR OF THE FORMULA
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2881139X | 1954-09-16 |
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| US2881139A true US2881139A (en) | 1959-04-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| US529913A Expired - Lifetime US2881139A (en) | 1954-09-16 | 1955-08-22 | Corrosion preventing compositions and process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993861A (en) * | 1958-07-24 | 1961-07-25 | Procter & Gamble | Detergent compositions |
| US3008898A (en) * | 1959-06-26 | 1961-11-14 | Cities Service Res & Dev Co | Method of inhibiting corrosion |
| US3172854A (en) * | 1965-03-09 | Corrosion inhibition process | ||
| US3222285A (en) * | 1962-07-23 | 1965-12-07 | Union Oil Co | Non-corrosive detergent compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618603A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2618606A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2706179A (en) * | 1951-05-02 | 1955-04-12 | Colgate Palmolive Co | Aromatic biguanide compounds in detergent compositions |
-
1955
- 1955-08-22 US US529913A patent/US2881139A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2618603A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2618606A (en) * | 1949-02-04 | 1952-11-18 | Procter & Gamble | Detergent compositions containing metal discoloration inhibitors |
| US2706179A (en) * | 1951-05-02 | 1955-04-12 | Colgate Palmolive Co | Aromatic biguanide compounds in detergent compositions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3172854A (en) * | 1965-03-09 | Corrosion inhibition process | ||
| US2993861A (en) * | 1958-07-24 | 1961-07-25 | Procter & Gamble | Detergent compositions |
| US3008898A (en) * | 1959-06-26 | 1961-11-14 | Cities Service Res & Dev Co | Method of inhibiting corrosion |
| US3222285A (en) * | 1962-07-23 | 1965-12-07 | Union Oil Co | Non-corrosive detergent compositions |
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