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
• • 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

Definitions

• the present invention relates to corrosion inhibiting compositions.
• carboxylic acid compounds are very effective corrosion inhibitors for ferrous metal in contact with aqueous systems.
• One example of a group of carboxylic acid compounds, which are very effective corrosion inhibitors for ferrous metal in contact with aqueous systems, is that described in US 4402907 and comprising compounds of formula: in which Z is e.g. a C1-C11 alkylene group, R1 and R2, independently, are e.g. hydrogen or methyl; and R3 is e.g. a group -NR4R5 in which R4 is C1-C12 alkyl or -Z-COOH in which Z has its previous significance, and R5 is hydrogen or C1-C12 alkyl; or water-soluble salts thereof.
• Z is e.g. a C1-C11 alkylene group, R1 and R2, independently, are e.g. hydrogen or methyl; and R3 is e.g. a group -NR4R5 in which R4 is C1-C12 alkyl or
• o-aminobenzoic acid anthranilic acid
• derivatives thereof c.f. e.g. Kriss et al. Zh. Prikl. Chem., 1989, 62(8), 1844-9.
• EP 341 536 describes an attempt to improve the corrosion protection and hard water sensitivity of anthranilic acid derivatives by combining them with an alkenylsuccinic acid and an alkanolamine.
• the present invention provides a corrosion inhibiting composition
• a corrosion inhibiting composition comprising:
• C1-C11 Alkylene groups Z are, e.g., methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-decylene and n-undecylene.
• Preferred such groups are C1-C5 alkylene groups, especially n-pentylene.
• R6 and/or R7 are, e.g., methyl, ethyl, n-propyl, isopropyl or n-butyl.
• R6 and R7 are independently hydrogen or methyl, R6 being methyl and R7 being hydrogen in especially preferred embodiments.
• C1-C12 Alkyl groups R4, R5, R9, R10, R11, R12 and R13 are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl.
• C1-C12 Alkyl groups R9, R10 and R11 interrupted by an oxygen atom are, e.g., methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 1-or 2-methoxybutyl, 1-methoxyoctyl, 1-methoxydecyl or 1-methoxydodecyl.
• n is preferably 11 and/or 12.
• R4 is C1-C8 alkyl or -Z-COOH where Z is a C1-C5 alkylene group;
• R5 is hydrogen or C1-C4 alkyl;
• R9 and R10 are independently hydrogen, C1-C4 alkyl or a group of formula VIII where R12 and R13 are independently hydrogen or C1-C4 alkyl, while R11 is a group of formula VIII where R12 and R13 are independently hydrogen or C1-C4 alkyl.
• preferred compounds A1) are of formula I where R1 and R2 are independently hydrogen or methyl, R3 is -NR4R5 where R4 is C1-C8 alkyl or -Z-COOH, R5 is hydrogen or C1-C4 alkyl, and Z is C1-C5 alkylene and their water soluble salts; preferred compounds A2) are of formula II where R6 and R7 are independently hydrogen or methyl and their water-soluble salts; and preferred compounds A3) are of formula III where n is 11 or 12, mixtures of an acid where n is 11 with an acid where n is 12, and water-soluble salts of such acids and mixtures of acids.
• Examples of specific compounds of formula I are as follows: 2,4,6-Tris(5'-carboxypentylamino)-1,3,5-triazine, 2,4,6-Tris(carboxymethylamino)-1,3,5-triazine, 2,4,6-Tris(3'-carboxypropylamino)-1,3,5-triazine, 2,4,6-Tris(4'-carboxybutylamino)-1,3,5-triazine, 2,4,6-Tris(11'-carboxyundecylamino)-1,3,5-triazine, 2,4,6-Tris(5'-carboxypentyl-N-methylamino)-1,3,5-triazine, 2,4,6-Tris(carboxymethyl-N-methylamino)-1,3,5-triazine, 2,4,6-Tris(3'-carboxypropyl-N-methylamino)-1,3,5-triazine, 2,
• the compounds of formula I are not new. These compounds and their production are described e.g. in Zhurnal Analiticheskoi Khimii 15 , 419-423 (1960), in DE-OS 1935010, in DE-OS 2819796, in US Patent Specification 3697520 and in J. Prakt Chemie 23 173-85 (1963). Especially preferred compounds are 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and water-soluble salts thereof.
• Examples of compounds of formula II include benzenesulphonamidoacetic acid, benzenesulphonamido-2-propionic acid, benzenesulphonamido-4-butyric acid, benzenesulphonamido-6-n-hexanoic acid, benzenesulphonamido-8-n-octanoic acid, benzenesulphonamido-10-n-decanoic acid, N-methylbenzenesulphonamido acetic acid, 4-toluene sulphonamidoacetic acid and N-methyl-4-toluene sulphonamidoacetic acid.
• Especially preferred compounds are p-toluenesulphonamidocaproic acid and water-soluble salts thereof.
• Compounds of formula III include, e.g. adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonane-1,9-dioic acid, decane-1,10-dioic acid, undecane-1,11-dioic acid and dodecane-1,12-dioic acid, as well as mixtures of these e.g. the commercially - available mixture of undecane-1,11-dioic acid and dodecane-1,12-dioic acid sold as "Alox 232", the last-named being especially preferred.
• aminobenzoic acids of formula IV include anthranilic acid and N-(2-carboxy benzyl)-2-aminobenzoic acid.
• the optional alkanolamine of formula VII may be, e.g., ethanolamine, diethanolamine, triethanolamine, methylelthanolamine, dimethylethanolamine, diethylethanolamine, butylethanolamine, dibutylethanolamine, di-isopropylethanolamine, methyldiethanolamine, ethyldiethanolamine, isopropanolamine, di-isopropanolamine, tri-isopropanolamine, sec.butanolamine, di-sec.butanolamine, tri-sec.butanolamine, or dimethylisopropanolamine.
• An especially preferred alkanolamine is triethanolamine.
• the alkali metal borate may be e.g. sodium borate or potassium borate.
• the water-soluble salts of carboxylic acid compounds of formula I and/or II may be alkali metal salts such as sodium or potassium salts; alkaline earth metal salts such as calcium or magnesium salts; or C1-C12 alkyl amine salts such as methylamine, ethylamine, isopropylamine, dibutylamine, tributylamine, octylamine or dodecylamine salts.
• the C1-C12 amine salt may be hydroxy-substituted and may be, e.g., a mono-, di- or tri-ethanolamine salt.
• the corrosion inhibiting composition according to the present invention provide excellent inhibition against corrosion of ferrous metals in contact with an aqueous medium.
• the present invention also provides a method of inhibiting the corrosion of a ferrous metal in contact with an aqueous system, comprising incorporating into the aqueous system an effective, corrosion-inhibiting amount, preferably 0.001 to 5% by weight, based on the weight of the aqueous system, of a corrosion inhibiting composition as hereinbefore defined.
• the aqueous system which is treated according to the method of the present invention may be a totally aqueous or a partly aqueous medium.
• Aqueous systems which may be effectively treated according to the present invention include e.g. cooling water systems, steam generating systems, sea-water evaporators, reverse osmosis equipment, bottle washing plants, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, aqueous machining fluid formations (e.g.
• aqueous scouring systems for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations
• aqueous scouring systems for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations
• aqueous glycol anti-freeze systems for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations
• aqueous scouring systems for use in boring, milling, reaming, broaching, drawing, turning, cutting, sawing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations
• aqueous scouring systems for use in boring, milling
• the corrosion-inhibiting composition of the present invention may be used in the method of the present invention either alone or in conjunction with other materials known to be useful in water treatment.
• examples of further water treatment additives include one or more of further corrosion inhibitors; metal deactivators; further scale inhibitors/dispersing agents; threshold agents; precipitating agents; oxygen scavengers; sequestering agents; antifoaming agents; and biocides.
• Further corrosion inhibitors which may be used include water-soluble zinc salts; phosphates; polyphosphates; phosphonic acids or their salts, e.g. hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phosphonic acid, methylamino dimethylene phosphonocarboxylic acids and their salts (e.g. those described in DE-OS 2632774), hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and those described in GB-PS 1572406; nitrates e.g. sodium nitrate; nitrites e.g. sodium nitrite; tungstates and molybdates e.g.
• HEDP hydroxyethyl diphosphonic acid
• nitrilotris methylene phosphonic acid methylamino dimethylene phosphonocarboxylic acids and their salts
• sodium tungstate or molybdate silicates e.g. sodium silicate; N-acylsarcosines; N-acylimino diacetic acids; ethanolamines; fatty amines; and polycarboxylic acids, e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts), copolymers of maleic anhydride e.g. with sulphonated styrene, copolymers of acrylic acid e.g. with hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
• silicates e.g. sodium silicate
• N-acylsarcosines N-acylimino diacetic acids
• ethanolamines fatty amines
• polycarboxylic acids e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts)
• copolymers of maleic anhydride e.g. with
• Metal deactivators especially for copper include benzotriazole, 5,5'-methylene bis-benzotriazole or copper - deactivating derivatives of benzotriazole or tolutriazole, or their Mannich base derivatives, or mercaptobenzothiazole.
• Scale inhibitors/dispersing agents include polymerized acrylic acid (or its salts), phosphino-polycarboxylic acids (e.g. those described in GB-PS 1458235), the cotelomers described in EP-PS 0150706, hydrolyzed polyacrylonitrile, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide with acrylic and methacrylic acids, lignin sulphonic acid and its salts , tannin naphthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (e.g. those described in US-PS 4029577) styrene/maleic anhydride copolymers and sulphonated styrene homopolymers (e.g. those described in US-PS 4374733, and combinations of these).
• Specific threshold agents include 2-phosphonobutane-1,2,4-tri-carboxylic acid, HEDP, hydrolyzed polymaleic anhydride and its salts, alkyl phosphonic acids, hydroxyphosphonoacetic acid, 1-aminoalkyl-1,1-diphosphonic acids and their salts, and alkali metal polyphosphates.
• Precipitating agent co-additives which may be used are alkali metal orthophosphates or carbonates; oxygen scavengers include alkali metal sulphites and hydrazines; sequestering agents are nitrilotriacetic acid and its salts; antifoaming agents are silicones, e.g. polydimethylsiloxanes, distearyl sebacimide, distearyl adipamide, and related products derived from ethylene oxide and/or propylene oxide condensations, in addition to fatty alcohols such as capryl alcohol and its ethylene oxide condensates.
• Biocides which may be used are, e.g.
• amines quaternary ammonium compounds, m-chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbonates, isothiazolines, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents, bromine and bromine release agents, and organometailic compounds such as tributyl tin oxide.
• aqueous machining fluid formulation it may be e.g. a water dilutable cutting or grinding fluid.
• aqueous machining fluid formulations of the invention may be e.g. metal working formulations.
• metal working we mean “reaming, broaching, drawing, spinning, cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling”.
• water-dilutable cutting or grinding fluids into which the corrosion inhibiting compound of formula I may be incorporated include:
• the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known further corrosion inhibitors and/or extreme pressure additives.
• corrosion inhibitors which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention include the following groups:
• Nitrogen containing materials particularly triethanolamine, are preferred.
• extreme pressure additives which may be present in the systems of the present invention include sulphur and/or phosphorus and/or halogen containing materials, for instance, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
• triethanolamine When triethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an amount such that the ratio of the corrosion inhibitor composition of the present invention to triethanolamine is from 2:1 to 1:20.
• the partly-aqueous systems treated by the method of the present invention may also be aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
• aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
• the aqueous surface-coating composition may be e.g. a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
• a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
• Sodium nitrite and sodium benzoate have been used to inhibit flash rusting of aqueous based primer paints but, because of related toxicity problems and problems of emulsion stability at the high ionic concentrations used, industry is moving away from sodium nitrite and sodium benzoate.
• the corrosion inhibitor composition of the present invention may be used singly, or in admixture with other additives e.g. known corrosion inhibitors, biocides, emulsifiers and/or pigments.
• the further known corrosion inhibitors which may be used are e.g. those of classes a), b), c) and d) hereinbefore defined.
• biocides which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention, include the following:
• Phenols and alkyl- and halogenated phenols for example pentachlorophenol, o-phenyl phenol, o-phenoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, diamines, triazines and organometailic compounds such as organomercury compounds and organotin compounds.
• pigments which may be used in these aqueous systems, in addition to the corrosion inhibitor composition of the present invention, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
• Staining by cast iron "chips", that lie on a filter paper and which are wetted by a small volume of the test solution, is evaluated according to the following rating scale: 0 no staining 1 traces of staining 2 slight staining 3 moderate staining 4 heavy staining
• a corrosion inhibitor composition is made up by mixing 10 parts by weight of p-toluene sulphonamidocaproic acid and 10 parts by weight of anthranilic acid.
• Table 3 Example Formulation Concentration % by weight Rating - p-toluene sulphonamido-caproic acid 0.9 3 - anthranilic acid 0.9 3 3 3 Product of Example 2(B) 0.9 0
• a corrosion inhibitor composition comprising 10 parts by weight of Alox 232 (a commerically - available mixture of C11/C12 dicarboxylic acids) and 10 parts by weight of anthranilic acid is prepared.
• a corrosion inhibitor composition is prepared comprising 30 parts by weight of 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine and 10 parts by weight of N'-(2-carboxybenzyl)-2-aminobenzoic acid.
• Tables 1, 2, 3, 4 and 5 demonstrate the striking improvement in corrosion inhibitor performance of the compositions of the invention, in alkaline pH ranges.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
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• Organic Chemistry (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)

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Citations (8)

• 1992
  • 1992-01-18 GB GB929201165A patent/GB9201165D0/en active Pending
• 1993
  • 1993-01-12 EP EP93300175A patent/EP0553962A1/fr not_active Withdrawn
  • 1993-01-14 JP JP2181593A patent/JPH05255873A/ja active Pending
  • 1993-01-15 CA CA 2087393 patent/CA2087393A1/fr not_active Abandoned

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