JPH0420440B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for inhibiting corrosion of metal surfaces and/or scale deposition on metal surfaces. In UK Patent Application No. 2112370A:
Applicants describe an aqueous system as having metals in contact with it,
In particular, a method of treating iron-based metals to inhibit corrosion and/or scale deposition from an aqueous system, the method comprising: A method comprising adding 0.1 to 50,000 ppm of 2-hydroxy-phosphonoacetic acid or a water-soluble salt thereof represented by is described and claimed. The inventors have now discovered that certain 2-amino-phosphonoacetic acid compounds can be added to aqueous systems in contact with metal surfaces and used as pre-treatments on metal surfaces prior to contact with corrosive or scaling environments. , found that the compounds are effective as corrosion inhibitors and/or scale deposition inhibitors. The present invention therefore provides a method for conditioning metal surfaces to inhibit corrosion of metal surfaces, particularly iron, copper (or alloys thereof) and/or to inhibit scale deposition on metal surfaces. A) before contacting the metal surface with a corrosive or scaling environment: [In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and optionally one or more hydroxy and/or carboxyl groups. C 3 -C 12 straight-chain or branched alkenyl radicals, substituted and/or optionally interrupted with one or more oxygen atoms, C 7 -C
15 aralkyl group or -CH ₂ PO ₃ H ₂ or R ₁ and R ₂ together with the nitrogen atom to which they are each attached form an optionally substituted heterocyclic ring Often R ₃ represents a hydrogen atom, a C 1 -C 12 straight-chain or branched alkyl group or an optionally substituted C 6 -C 10 aryl group, and R ₄ represents a C 6 -C 10 aryl group; 4 alkyl group,
or preferably represents a hydrogen atom. ] or a water-soluble salt (or partial ester or salt) thereof; and optionally ) a metal ion component, which synergistically enhances the individual conditioning effects of the compound of the formula and the metal ion. a) a compound of the above formula or its a water-soluble salt (or partial salt); and optionally b) a metal ion as defined in ) above,
The present invention provides a method for conditioning said metal surface by treating said metal surface with a metal surface. Treatments A and B are carried out by cathodically polarizing the metal surface to be treated, for example using conventional contact pressure flow techniques (see, for example, Chapter 11, "Corrosion", L.
L. Sheir, Newnes-Butterworth 1976). Examples of R ₁ and/or R ₂ as C 1 -C 12 straight-chain or branched alkyl (optionally hydroxy- or carboxy-substituted) are methyl, ethyl, n-propyl, isopropyl, n -butyl, isobutyl, t-butyl,
n-pentyl, n-hexyl, n-octyl, n
-nonyl, n-decyl, n-undecyl and n
-dodecyl group; 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, and 2,3-dihydroxypropyl group: and carboxymethyl, 2-carboxyethyl, 2-carboxypropyl, 3-carboxybutyl and 1,
Includes 2-dicarboxyethyl group. Examples of R ₁ and/or R ₂ as C 3 -C 12 straight-chain or branched alkenyl are prop-2-enyl, n-but-2-enyl, 2-methyl-prop-2 -enyl, n-pent-2-enyl, n-hex-2-enyl, n-
Includes hex-2,4-dienyl, n-dec-10-enyl and n-dodec-12-enyl. C 7 -C 15 aralkyl groups R ₁ and/or R ₂ include benzyl, α-methylbenzyl, α,α-dimethyl-benzyl, α- and β-phenylethyl, benzhydryl or naphthylmethyl groups. . When R ₁ and R ₂ together with the nitrogen atom to which they are each attached form an optionally substituted heterocyclic ring, these are, for example, pyrrolidone, viveridine, morpholine or 2,5-dimethylmorpholine rings; It's okay. Straight-chain or branched alkyl radicals R ₃ having 1 to 4 carbon atoms are, for example, methyl, ethyl, n
-propyl, isopropyl, n-butyl or t
-butyl; and optionally substituted C6 -C10 aryl R ₃ is phenyl;
Includes tolyl, xylyl, tamil, butylphenyl and naphthyl groups. Preferred compounds of the formula are those in which R ₁ and R ₂ represent a hydrogen atom or a C 1 -C 4 alkyl group, R ₃ represents a hydrogen atom and R ₄ represents a hydrogen atom. Water-soluble salts or partial salts of compounds of formula include, for example, alkali metal salts such as lithium, sodium and potassium salts; calcium, magnesium,
alkaline earth metal salts such as strontium and barium; other metal ions such as cobalt, iron, zinc, chromium, nickel, manganese, cadmium and cerium () ions; ammonia; and C1-C20 alkyl amines Salts (optionally substituted with 1 to 6 hydroxy groups) such as methylamine, ethylamine, n-propylamine, trimethylamine, triethylamine, n-butylamine, n-hexylamine, octylamine, ethanolamine and triethanolamine It is salt. Many of the compounds of formula are new. However, compounds in which R ₁ , R ₂ , R ₃ and R ₄ all represent hydrogen atoms are described by Nissan Chemical Industries, Ltd. in Japanese Patent No. 5408027. Compounds of formula can be prepared, for example, by the methods outlined in the reaction scheme below. In this case, R ₁ , R ₂ and R ₃ have the above meanings, R ₄ represents a hydrogen atom or an alkyl group,
And R ₅ and R ₆ are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Conventional hydrolysis techniques, which are optionally carried out, produce various intermediate esters such as R ₄ ,
When R ₅ and R ₆ represent something other than a hydrogen atom,
Applicable. The various catalysts required are mineral acids, e.g.
HCl, organic acids or Lewis acids e.g. AlCl ₃ ,
It can be _ZnCl2 or _BF3 . This type of conventional technique is described by D. Redmore in J.Org.
Chem, 43 992 (1987): In this case, R ₃ , R ₄ , R ₅ and R ₆ have the above meanings, and R ₇ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. This technique is described by Oleksyszyn and Gruszeeka in Tetrahedron Letters 36 , 3537 (1981). In this case R ₁ , R ₂ and R ₃ have the above meanings. This method, which is utilized only for preliminary reactions using formaldehyde as the carbonyl reactant,
J.Org substantially by Moedritzer and Irani.
Described in Chem. 31 , 1603 (1966): In this case, R ₄ has the abovementioned meaning, R ₈ represents H or a C 1 -C 4 alkyl group, and X represents Cl or Br. Suitable bases are sodium or potassium hydroxide or tertiary amines such as triethyleneamine. 5) In the formula, R and/or R ₂ is -
The compound representing CH ₂ PO ₃ H ₂ (phosphonomethylene) was described by Moedritzer and Irani in J.Org.
As described in Chem. 31 , 1603 (1966),
It may be produced by reacting a compound in which R ₁ and R ₂ each represent a hydrogen atom with formaldehyde and phosphorous acid. Regarding the treatment carried out under item (A), corrosion inhibition and/or
Alternatively, they may be contacted in combination with metal ions b) which have a synergistic effect on scale inhibition. Some typical applications of the treatment A) carried out in the preferred mode of application of contact pressure flow technology include: temporary protection of metal surfaces exposed to corrosive atmospheres, e.g. atmospheric air; pretreatment of metal surfaces to be subsequently painted; phosphates; Co-treatment for sealing metal surfaces;
and a compound of the formula (or a salt thereof) and optionally a metal ion component b), and then the paint is applied to the metal surface to be conditioned by, for example, spraying, brushing, dipping, or cathodic electrodeposition. applying by. In each case of a typical application of treatment A), a metal surface, such as a phosphated mild steel surface, is immersed in a solution of a compound of formula (or a water-soluble salt thereof), optionally containing metal ionic component b); Alternatively, the solution may be painted or sprayed onto the phosphated metal surface. In the treatment according to the invention as item A) or B), the metal ionic component can be used as an independent metal salt or as a preformed salt of a compound of formula or as a combination of both. Suitable metal ion components b include, for example, cobalt, iron, barium, calcium, zinc, chromium, nickel, strontium, manganese, cadmium, cerium () and magnesium ions. Some of these metal ions, such as calcium and barium, do not by themselves provide corrosion inhibition or scale control. The ratio of the compound of the formula (its water-soluble salt) to the metal ion component b) used for the corrosion and/or scale inhibiting composition used in the conditioning method of the invention is, for example, from 100:1 to 1:
It may vary within a wide range of 100, more preferably 10:1 to 1:10 parts by weight. In practice, the amount of a crude product consisting of a compound of formula and metal ions used to treat a metal surface, for example by adding the composition to be added to an aqueous system in contact with the metal surface, It should be varied depending on the protective function that the object is supposed to perform. For corrosion inhibiting protective treatments, optionally combined with scale inhibiting treatments, the amount of composition added to the aqueous system may range from 0.1 to 0.1 based on the aqueous system.
50000ppm (or 0.00001 to 5% by weight) preferably 1 to 500ppm (or 0.0001 to 0.5
% by weight) is convenient. If anti-scaling is the only objective, the amount of composition used is conveniently from 1 to 200 ppm, preferably from 1 to 30 ppm, based on the aqueous system. The aqueous systems treated by the present invention, particularly those important in the combination treatment of corrosion control and scale prevention, include cooling water systems, steam generation systems, seawater evaporators,
water-based kettles, gas scrubbing systems, closed-circuit heating systems, aqueous cooling systems, and stand-up well systems; for corrosion control treatments only, particularly important aqueous systems include aqueous machining fluid formulations (e.g., boring, milling,
engine coolants, including water-based scouring systems, water-based glycol antifreeze systems; , water/glycol hydraulic fluids; and aqueous polymer surface coating systems or solvent-borne polymer systems such as tetrahydrofuran,
Includes those containing ketones or alkoxyalkanols. The synergistic inhibitor compositions used in accordance with the present invention may be used alone or in conjunction with other known compounds useful in the treatment of aqueous systems. In the treatment of systems that are entirely aqueous, such as cooling water systems, air conditioning systems, steam generation systems, seawater evaporation systems, still water furnaces, and closed circuit heating or cooling systems, other corrosion inhibitors include, for example, water-soluble zinc. Salts; Phosphates; Polyphosphates; Phosphonic acids and their salts, such as acetodiphosphonic acid,
Nitrilotrismethylenephosphonic acid and methylaminodimethylenephosphonic acid; 2-hydroxy-
Phosphonoacetic acid or other phosphonocarboxylic acids and their salts, such as those described in DE 2632774, 2-phosphonobutane-1,
2,4-tricarboxylic acid and British patent no.
Chromates, such as sodium chromates; nitrates, such as sodium nitrite; molybdates, such as sodium molybdate; silicates, such as sodium silicate; benzotriazoles, bis-benzotriazole or Copper-deactivated benzotriazole or tritriazole derivatives or Mannitz base derivatives thereof; N-acylsarcosine; N-acylaminodiacetic acid; ethanolamine; aliphatic amine;
and polycarboxylic acids, such as polymaleic acid and polyacrylic acid, and their alkali metal salts, copolymers of maleic anhydride, copolymers of acrylic acid, and substituted derivatives of polymaleic acid, polyacrylic acid, and copolymers thereof; things can be used. Furthermore, in this completely aqueous system, the inhibitor used according to the invention can be combined with other dispersants and/or
or limit processing agents, such as polymeric acrylic acids (or salts thereof), phosphinopolycarboxylic acids (as described and claimed in British Patent No. 1458235), hydrolyzed polyacrylonitrile, polymeric methacrylic acid and its salt,
Polyacrylamides and their copolymers with acrylic and methacrylic acids, ligninsulfonic acid and its salts, tannins, naphthalenesulfonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid/lower alkyl hydroxyacrylate copolymers, e.g. No. 4,029,577, sulfonated styrene/maleic anhydride copolymers, styrene/maleic anhydride copolymers and sulfonated styrene homopolymers such as those described in U.S. Pat. No. 4,374,733, and combinations thereof; May be used together. For example, 2-phosphonobutane-
1,2,4-tricarboxylic acid, acetodiphosphonic acid, hydrolyzed polymaleic anhydride and its salts, alkylphosphonic acid, 1-aminoalkyl-1,1-diphosphonic acid and its salts, and alkali metal polyphosphates. Special limit processing agents may be used, such as. Precipitating agents such as alkali metal ortho-phosphates and carbonates; Oxygen scavengers such as alkali metal sulfites and hydrazine; Sequestering agents such as nitrilotriacetic acid and its salts; Defoamers such as silicones, e.g. polydimethyl Siloxanes, distearyl sebaamide, distearyl sebaamide, distearyl adipamide and related products derived from ethylene oxide and/or propylene oxide condensations, as well as fatty alcohols such as caprylic alcohol and its ethylene oxide condensates; Biocides, such as amines, quaternary ammonium compounds, chlorophenols, sulfur-containing compounds such as sulfones, methylene bisthiocyanates and carbamates, isothiazolones, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine releasing agents and tributyltin oxide. Organometallic compounds such as may also be used. If the system to be treated by the method of the invention is not completely aqueous, for example an aqueous machining fluid formulation, it may for example be a cutting or grinding fluid that can be diluted with water. The aqueous machining fluid formulations of the present invention may be, for example, metalworking formulations. The term “metal processing” refers to processes such as reaming, broaching, drawing,
spinning, cutting, grinding, drilling, pulverization, turning,
means "sawn, uncut, shaped or rolled".
Examples of water-diluted cutting or grinding fluids that may be impregnated with corrosion-inhibiting compositions include: a) one or more corrosion inhibitors according to the invention, and optionally one or more corrosion-inhibiting agents; of anti-wear additives, typically 1:50 to 1:100 as a grinding fluid.
b) an aqueous concentrate containing a biocide, a corrosion inhibitor according to the invention and an antiwear additive, used at a dilution of 1:20 to 1:40 for cutting operations; polyglycols used at a dilution of 1:60 to 1:80 for milling purposes; c) a fluid similar to b) above, but with sufficient water to give a translucent product when further diluted with water; Semi-synthetic cutting fluids containing 10 to 23% oil with emulsifiers: d) E.g. emulsifiers, corrosion inhibitors according to the invention, high pressure/anti-wear additives, biocides, defoamers, coupling agents, etc. Contains emulsifying mineral oil concentrate. These are usually 1:10 to 1:1 with water.
It is diluted 50 parts to give an opaque white emulsion. e) A product analogous to d) above, comprising 1:
A product containing less oil and more emulsifier than the fluid of d) above, which is made into a clear emulsion for cutting or milling operations at dilutions ranging from 50 to 1:100. the aqueous system component is an aqueous machining fluid formulation;
In these partially aqueous systems, the inhibitors of the invention may be used alone or in admixture with other additives, such as other known corrosion inhibitors and/or extreme pressure additives. Examples of other corrosion inhibitors that can be used with the inhibitor compositions according to the invention in these aqueous systems include the following groups: a) organic acids, their esters or ammonium, amines, alkanolamines and metal salts; , for example, benzoic acid, p-tert-butylbenzoic acid, disodium sebacate, triethanolamine laurate, isononanoic acid, (p-
Toluenesulfonamide triethanolamine salt of caproic acid, triethanolamine salt of benzenesulfonamide caproic acid, triethanolamine salt of 5-ketocarboxylic acid derivative described in European Patent Application No. 41927, sodium N-lauroylsarcosinate, or nonylphenoxyacetic acid; b) nitrogen-containing substances such as the following types: fatty acid alkanolamides; imidazolines, e.g.
-hydroxy-ethyl-2-oleyl-imidazolines; oxazolines; triazoles, such as benzotriazole; or Mannitz base derivatives thereof; triethanolamine, fatty amines; and inorganic salts, such as sodium nitrate; c) phosphorus-containing compounds such as the following types: Substances: phosphoric acid amines, phosphonic acids or inorganic salts, such as sodium hydrogen phosphate or zinc phosphate; d) Sulfur-containing compounds, such as the following types: sodium, calcium or barium petroleum sulfonates, or heterocyclic compounds, such as sodium mercapto. Benzothiazole. Nitrogen-containing substances are preferred, especially triethanolamine. Examples of extreme pressure additives that may be present in the system treated according to the invention include sulfur- and/or phosphorus- and/or halogen-containing substances such as sulfurized pine oil, sulfurized fats, tritolyl phosphates, chlorinated Includes paraffins or ethoxylated phosphates. When triethanolamine is present in the aqueous system treated according to the present invention, the ratio of inhibitor composition to triethanolamine is from 2:1 to 1:20.
It is preferable to make it exist in an amount such that . The partially aqueous systems treated by the method of the invention can be aqueous surface coating compositions, such as emulsion paints and aqueous powder coatings for metal substrates. The aqueous surface coating composition is a paint, such as a styrene-acrylic copolymer emulsion paint, resin, latex, or other waterborne polymeric surface coating system for coating metal substrates. The inhibitor compositions used in accordance with the present invention are effective against flash rust of metal substrates during surface coating applications.
rusting) and subsequent corrosion during use of the painted metal. In the aqueous surface coating compositions treated by the method of the invention, the inhibitor compositions can be used alone or mixed with other additives such as known corrosion inhibitors, biocides, emulsifiers and/or pigments. . Other known corrosion inhibitors which may be used are, for example, those of classes a), b), c) and d) mentioned above. Examples of biocides that can be used in these aqueous systems with compounds of formula include: phenols, and alkyl- and halogenated phenols such as pentachlorophenol, o-phenylphenol, o- Phenoxyphenols and chlorinated o-phenoxyphenols; salicylanilides; diamines; triazines;
and organometallic compounds, such as organomercury compounds and organotin compounds. Examples of pigments that can be used in these aqueous systems with compounds of formula include organic pigments such as titanium diacid, zinc chromate, iron oxide, and phthalocyanine. The present invention will be further described in detail with reference to the following examples. Example 1 A solution containing 16.3 parts by weight of diethylamine hydrochloride, 16.6 parts by weight of orthophosphorous acid and 29.6 parts by weight of glyoxylic acid (50% aqueous solution) in 50 parts by volume of 18% hydrochloric acid is heated under reflux for 18 hours. The volatiles are then removed by vacuum distillation and the residual oil is triturated with acetone to remove impurities. As a result,
28 parts by weight of 2-diethylaminophosphonic acetic acid hydrochloride monohydrate having the following gravimetric analysis values are obtained: Actual value: P11.54%; Calculated value (C ₆ H ₁₂ NO ₅ P.HCl.H ₂ O): P11. 67% moreover, _H3PO4 (in water) in _the ^31P −nmr spectrum
15.8ppm downfield signal (JP
-CH=18Hz). Example 2 11.8 parts by weight of acetamide and orthophosphorous acid
A solution containing 16.4% by weight in 40 parts by volume of acetic anhydride is heated to 45° C. with stirring. To this solution, 22.2 parts by weight of glyoxylic acid hydride is added in several portions over 15 minutes. The reaction temperature rises to 80° C. during the addition and is maintained for a further 3 hours by external heating. The acetic anhydride was distilled off under reduced pressure and the viscous residue was dissolved in 100 parts by volume of concentrated hydrochloric acid. The solution was heated under reflux for 4 hours and then evaporated to dryness to give a brown crystalline solid, which Dissolution in 600 parts by volume of % aqueous methanol followed by addition of propylene oxide gives 9.3 parts by weight of 2-aminophosphonoacetic acid hydrate which melts with decomposition at 195°C and has the following gravimetric elemental analysis: : Actual value: C13.92; H4.57; N7.97; P17.79% Calculated value (C ₂ H ₆ NO ₃ PH ₂ O): C13.88; H4.66 N8.10; P17.90% Example 3 9.2 parts by weight of glyoxylic acid hydride, morpholine
Example 1 A solution containing 8.7 parts by weight and 8.2 parts by weight of orthophosphorous acid in 100 parts by volume of 18% hydrochloric acid
When treated in the same manner as above, 24.5 parts by weight of 2-N-morpholinophosphonoacetic acid is obtained. In the ³¹ P-nmr spectrum (in water), a 13.8 ppm downfield signal (Jp-CH = 18 Hz) is observed compared to H ₃ PO ₄ . Example 4 By reacting and evaporating a solution containing 8.9 parts by weight of sarcosine and 8.2 parts by weight of orthophosphorous acid in 100 parts by weight of 18% hydrochloric acid, ³¹ 2-(N-Methyl-N-carboxymethylamino)phosphonosine as a pale yellow amorphous solid with a signal (Jp-CH = 18 Hz) 13.3 ppm downfield than H ₃ PO ₄ in water in the P-nmr spectrum. 25.8 parts by weight of acetic acid hydrochloride are obtained. Example 5 A solution containing 7.8 parts by weight of 2-aminophosphonoacetic acid, 4.5 parts by weight of P-formaldehyde and 8.2 parts by weight of orthophosphorous acid in 40 parts by volume of concentrated acid salt is heated under reflux for 8 hours. When the solvent was removed by vacuum distillation at 90°C/12 mmHg, ^{the 31} P-nmr spectrum changed to 2-(N,N-bisphosphonomethyleneamino).
Consistent with the structure of phosphonoacetic acid, 9.7 ppm downfield for H ₃ PO ₄ (triplet J = 13 Hz)
and 14.6ppm downfield (double J = 18
Dark red viscous oil with two peaks of Hz) 16.2
Obtain parts by weight. Example 6 The corrosion inhibitor activity of the active compound of the formula was determined in a standard corrosion water formulated as follows: CaSO ₄ .2H ₂ O 20 g MgSO ₄ .7H ₂ O 15 g NaHCO ₃ 4.6 g CaCl ₂ .6H ₂ O 7.7 g. Using distilled water 205, prove the Aerated Solution Bottle Test using the following procedure: Mild steel piece scraped with pumice (5cm ² × 2.5cm)
is soaked in hydrochloric acid for 1 minute, then washed with water, dried and weighed. The additive composition in the desired proportions is dissolved in 200 ml of standard corrosive water. Two pieces of mild steel are suspended in a solution,
The whole is stored at 40°C in a closed bolt in a temperature controller. Air is passed through the solution at 500 ml/min during the storage period. In this case, the air passage is screened from the mild steel billet; evaporative water loss is compensated by additional distilled water. After 64 hours, the mild steel pieces are removed, scrubbed without pumice, immersed in hydrochloric acid suppressed with 1% by weight hexamine for 1 minute, then rinsed with water, dried, and reweighed. A certain weight loss will occur. A blank test, i.e. immersion of a mild steel billet in test water without the presence of any potential corrosion inhibitors.
Perform each test in the series. Corrosion rate loss weight milligrams/square decimeter/day (hereinafter mdd
say. ), but for convenience, the results are shown as percent protection defined as below: % protection = Corrosion rate in blank test (mdd) - Corrosion rate in example (mdd) / Corrosion rate in blank test (mdd
)×100 The results obtained in a series of tests using compounds of the formula as corrosion inhibitors are shown in the table.

[Table] Example 7 Limit test for calcium carbonate Prepare the following solutions (a), (b) and (c): a) Calcium nitrate solution Dissolve 1.470 g of calcium nitrate tetrahydrate in deionized water and dissolve. b) Sodium carbonate solution Dissolve 0.646 g of sodium carbonate in deionized water and make the solution 1; c) 2-amino-phosphonoacetic acid solution 2-amino-phosphonoacetic acid obtained in Example 2 -Dissolve the hydrate in water to release the active ingredient.
A solution containing 1000ppm. Place 50ml of calcium nitrate solution into a 120g glass bottle sealed with a screw cap. To this solution is added the volume of solution (c) required to obtain a 2-amino-phosphonoacetic acid-hydrate concentration of 5 ppm, 7.5 ppm or 10 ppm, respectively, in the final volume of test solution (100 ml) ( For example 0.1% solution
When c is 1.0 ml, the concentration of 2-amino-phosphonoacetic acid hydrate in the test solution is 10 ppm. ). Add 50 ml of solution b) and shake the mixture. The test solution is stored for 24 hours in a constant temperature bath maintained at 25°C. Remove 25mls of test solution and
Reader’s Reagent [2-hydroxy-1-(2-
Hydroxy-4-sulfo-1-naphthylazo)-
3-naphthoic acid] followed by two pellets of sodium hydroxide. Add the resulting solution to 0.01M of ethylenediaminetetraacetic acid disodium salt.
Titrate with standard solution. The results shown in Table 4 below are expressed as % calcium carbonate precipitation inhibitor relative to the blank test (i.e., containing no 2-amino-phosphonoacetic acid). Suppression % = Example titration - Blank test titration / 7.78 - Blank test titration x 100 The numerical value "7.78" is the maximum possible titration value at 100% suppression.

【table】

Claims (1)

[Scope of Claims] 1. A method of conditioning a metal surface to inhibit metal surface corrosion and/or to inhibit scale deposition on a metal surface, comprising: A) corrosion or Before contacting the scaling environment, ) the following equation: [In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, a straight or branched alkyl group having 1 to 12 carbon atoms, and optionally one or more hydroxy and/or carboxyl groups. and/or optionally interrupted with one or more oxygen atoms, C3 -C12 straight-chain or branched alkenyl groups, C7 -C15 aralkyl groups or _{−CH2PO3H2 _ _}
or R ₁ and R ₂ together with the nitrogen atom to which they are each attached may form an optionally substituted heterocyclic ring, and R ₃ is a hydrogen atom, with 1 to 1 carbon atoms; 12 straight-chain or branched alkyl or optionally substituted C6 -C10 aryl, and R ₄ is hydrogen or C1 -C4 alkyl. ] or a water-soluble salt (or partial ester or -salt) thereof; and optionally ) a metal ion component which synergizes the individual conditioning effects of the compound of the formula and the metal ion. a) a compound of the above formula or its a water-soluble salt (or partial salt); and optionally b) a metal ion as defined in ) above,
A method of conditioning said metal surface, the method comprising: treating said metal surface with said metal surface; 2. The method according to claim 1, wherein R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ each represent a hydrogen atom. 3. The method according to claim 1, which treats iron, copper, or an alloy thereof. 4. The method according to claim 1, wherein the metal surface to be treated is cathodically polarized. 5. Process according to claim 1, characterized in that the metal surface is treated beforehand with an aqueous solution of a compound of formula (or a water-soluble salt thereof) and optionally with metal ion component b) before coming into contact with the corrosive environment. 6. A method according to claim 5, using metal salts, in which the compounds of formula 6 are combined to provide metal ions that provide a synergistic corrosion-inhibiting and/or scaling-inhibiting effect. 7 Temporary protection of metal surfaces exposed to corrosive atmospheres; pretreatment of metal surfaces to be painted; co-treatment for sealing phosphated metal surfaces; or compounds of the formula (or water-soluble salts thereof) and optionally metal ions. 6. The method of claim 5, which comprises formulating a paint containing component b) and then applying the paint onto the metal surface to be conditioned. 8. The metal surface is coated with one or more of cobalt, iron, barium, calcium as component b),
Claim 1 Contacting with zinc, chromium, nickel, strontium, manganese, cadmium, cerium () or magnesium ions
The method described in section. 9. The method according to claim 1, wherein the ratio of the compound of formula (or its water-soluble salt) to metal ion component b) is within the range of 100:1 to 1:100. 10. The method according to claim 9, wherein the ratio of the compound of formula (or a water-soluble salt thereof) to component b) is from 10:1 to 1:10. 11. An inhibitor composition consisting of components a) and b) is contacted in an aqueous system with a metal surface requiring corrosion inhibition and optionally scale inhibition protection treatment in an amount of 1 to 500 ppm based on the aqueous system; Use of the method according to claim 1. 12. The method of claim 11, wherein the inhibitor composition consisting of components a) and b) is added in an amount of 1 to 100 ppm, based on the aqueous system. 13. An inhibitor composition consisting of components a) and b) is brought into contact with a metal surface requiring only scale inhibition treatment in an aqueous system to form a 1-
2. A method according to claim 1, wherein the amount of 200 ppm is added. 14. The method of claim 13, wherein the inhibitor composition consisting of components a) and b) is added to the aqueous system in an amount of 1 to 30 ppm, based on the aqueous system. 15. Where the aqueous system is contacted with metal surfaces requiring only a corrosion control system, such as an aqueous machining fluid, an aqueous scouring system, an aqueous glycol antifreeze system,
14. The method of claim 13, which is a water/glycol hydraulic fluid or an aqueous surface coating. 16 Claim 1, wherein the aqueous machining fluid formulation is a cutting or grinding fluid that can be diluted with water.
The method described in Section 5. 17. Cooling water systems, steam generation systems, seawater evaporators, still water kettles, gas scrubbing systems, closed-circuit heating systems, water-based systems, where aqueous systems are brought into contact with metal surfaces requiring a combination of corrosion control and anti-scaling treatment. The method according to claim 1, which is a cooling system or a falling well system. 18. Process according to claim 1, in which the inhibitor combination consisting of components a) and b) is used alone or together with other known compounds useful in the treatment of wholly or partially aqueous systems. . 19 The aqueous system is a completely aqueous system, a cooling water system, an air conditioning system, a steam generation system, a seawater evaporator, a still water kettle, a gas scrubbing system, or a closed circuit heating or cooling system, and the components a) and b ) along with one or more other corrosion inhibitors, dispersing and/or threshold treating agents, precipitants, oxygen scavengers, sequestrants and defoamers, and biocides. 19. A method according to claim 18 for use. 20 The partially aqueous system is an aqueous surface coating and the inhibitor composition consisting of components a) and b) is used together with one or more corrosion inhibitors, biocides, emulsifiers and/or pigments A method according to claim 18. 21 The aqueous system is only partially aqueous and is an aqueous machining fluid and components a) and b)
19. The method of claim 18, wherein an inhibitor formulation consisting of is used together with one or more other corrosion inhibitors and/or extreme pressure additives. 22. The method of claim 21, wherein the other corrosion inhibitor is triethanolamine. 23. The method of claim 22, wherein triethanolamine is present in an amount such that the ratio of the inhibitor composition of components a) and b) to triethanolamine is from 2:1 to 1:20.