EP0341536B1 - Mélanges d'acides alkénylsucciniques, d'acides arylsulfonylanthraniliques et d'alcanolamines et leur utilisation comme inhibiteurs la corrosion dans les systèmes aqueux - Google Patents

Mélanges d'acides alkénylsucciniques, d'acides arylsulfonylanthraniliques et d'alcanolamines et leur utilisation comme inhibiteurs la corrosion dans les systèmes aqueux Download PDF

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Publication number
EP0341536B1
EP0341536B1 EP89107873A EP89107873A EP0341536B1 EP 0341536 B1 EP0341536 B1 EP 0341536B1 EP 89107873 A EP89107873 A EP 89107873A EP 89107873 A EP89107873 A EP 89107873A EP 0341536 B1 EP0341536 B1 EP 0341536B1
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weight
acids
mixture
mixtures
clamed
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EP89107873A
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German (de)
English (en)
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EP0341536A1 (fr
Inventor
Erich Dr. Schwartz
Christos Dr. Vamvakaris
Elmar Getto
Chung-Ji Dr. Tschang
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BASF SE
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BASF SE
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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

Definitions

  • the invention relates to synergistic mixtures of alkenyl succinic acids, arylsulfonylanthranilic acids and alkanolamines and their use as highly effective, low-foaming and water hardness-insensitive corrosion inhibitors in aqueous systems.
  • nitrite is toxic, water-polluting and can form carcinogenic nitrosamines with the amines that are often used for corrosion protection.
  • Boron compounds are only moderately toxic, but under certain conditions are poisonous to plants, pollute water and can adversely affect steel surfaces.
  • p-tert-Butylbenzoic acid has been recognized as chronically toxic in animal experiments. Zinc salts pollute water, sewage sludge and sediments.
  • the desired low application amounts can often not be achieved.
  • Sulfonamidocarboxylic acids according to DE-C2-1298672 and EP-B1-029529 are known as water hardness-stable, low-foam corrosion inhibitors. However, they only work optimally in mixtures with boron compounds, e.g. emerges from DE-C2-2840112. The disadvantages of the boron compounds have already been discussed above.
  • alkenylsuccinic acid derivatives according to DE-A-2943963 achieve good corrosion protection values without the addition of boron, nitrite or zinc with largely no foam.
  • these are sensitive to water hardness, i.e. they form precipitates in hard water, which makes them unusable for many applications and can cause major problems.
  • EP-B1-029529 describes the use of alkanolamine salts, of arylsulfonamide carboxylic acids, preferably of arylsulfonylanthranilic acid, as corrosion inhibitors. Such substances have little foam and are not sensitive to water hardness. However, they do not quite achieve the effectiveness of the above. Succinic acid derivatives.
  • the object of the invention is to provide an aqueous anticorrosive agent in which the properties of good water solubility, high anticorrosive action, insensitivity to the hardness of the water and very good low-foaming properties are achieved in the best possible way.
  • the solution to the problem consists in the use of mixtures of C8- to C9-alkenylsuccinic acids according to DE-A-2 943 963 and arylsulfonylantranilic acids according to EP-B1-29 529 in the presence of alkanolamines or aqueous solutions of these mixtures as corrosion inhibitors. There are unexpected synergistic advantages for these mixtures or solutions.
  • the mixtures to be used according to the invention provide corrosion protection which synergistically exceeds that of the individual compounds described.
  • the aqueous solutions of these mixtures have a low foam level and, moreover, surprisingly also have a reduced sensitivity to water hardness compared to the alkanolamine salts of the individual components A and B. There is an unforeseeable synergism.
  • the mixtures according to the invention are thus able to achieve the above object in an outstanding manner.
  • the di-isobutenylsuccinic acid as described in Example 1 of DE-A1-2943963 is preferred.
  • Preferred arylsulfonylanthranilic acids are those in which R 1 and R 2 are hydrogen or methyl, A is a benzene radical and R 3 is hydrogen. Accordingly, the particularly preferred arylsulfonylanthranilic acids are N-phenylsulfonyl- and N- (o-tolylsulfonyl) -anthranilic acid.
  • Mono-, di- and / or tri- (C2- to C4-alkanol) amines include, in particular, mono-, di- and triethanolamine and mono-, di- and tri-iso-propanolamine.
  • Diethanolamine, trichloramine and mixtures thereof are preferred.
  • these are expediently mixtures of mono-, di- and triethanolamine, preferably of diethanol and triethanolamine, as are obtained in the industrial production processes.
  • a mixture of about 5% by weight mono-, about 55% by weight di- and 40% by weight triethanolamine or, for example, 85% by weight tri- and 15% by weight diethanolamine is particularly preferred.
  • the concentration of the mixture (A + B + C), based on the pure substance and on the total weight of the aqueous solution, is 0.5 to 40, preferably 1 to 10% by weight.
  • the most particularly preferred range is 1 to 4% by weight.
  • the mixtures according to the invention or their aqueous solutions can be used in all aqueous systems which come into contact with iron, its alloys (steels), aluminum, its alloys, zinc or copper or their alloy.
  • aqueous systems which come into contact with iron, its alloys (steels), aluminum, its alloys, zinc or copper or their alloy.
  • Examples include Hydraulic fluids, cooling lubricants, neutral to alkaline technical cleaners or mine water, which are particularly hard and salt-rich, and which are used directly in mining as mixing water, e.g. for hydraulic processes, are used and have a particularly strong corrosive effect.
  • the application concentrations fluctuate depending on the area of application and the type of aqueous medium and the metals to be protected. In general, based on the industrially used aqueous system, 0.01 to 5% by weight, based on the mixture of substances (A + B + C), is used. The concentration should preferably be 0.1 to 5% by weight.
  • the optimal quantitative ratio of components A and B to each other depends on the application. It is expedient to proceed in such a way that a quantitative ratio of 1: 1 is assumed, which generally gives results which are close to the optimum.
  • the most favorable quantitative ratio (A + B): C can be determined very simply by adding such an amount of C that the pH of the aqueous solution is between 7 and 9. This pH range is usually met when the proportion of C in the mixture (A + B + C) is 33 to 75, preferably 50 to 70% by weight.
  • auxiliaries can be added to the mixtures according to the invention or their aqueous solutions which increase their performance properties. This can be used, for example, for wetting improved, the growth of microorganisms suppressed or the loss of precipitation by substances which are dissolved in the aqueous systems can be prevented.
  • Typical additives are, for example, surfactants as wetting agents, such as alkylphenol ethoxylates, dispersants, such as salts of polymeric carboxylic acids, emulsifiers, such as alkyl or alkylarylsulfonates, solubilizers, such as glycols, in particular propylene glycol, lower aliphatic alcohols or sodium cumene sulfonic acid salt, polyglycols, such as polyethylene or polyols or polyethylene / polypropylene block polymers and others
  • the corrosion protection agents according to the invention are tested using the methods described below:
  • the corrosion protection effect was determined by the "gray cast iron filter paper test", DIN 51 360, part 2.
  • the rating scale is as follows:
  • hard water was prepared by mixing fully deionized water with 3.04 mmol / l CaCl2 ⁇ 6H2O and 0.54 mmol / l MgSO4 ⁇ 7H2O. Using this water, solutions of the mixtures according to the invention were prepared in a concentration of 2% by weight, based on the pure substance content. After standing overnight, the following was assessed:
  • the impact method was used based on DIN 53 902. 200 ml of a 1% by weight solution of the mixture according to the invention in deionized water were filled in a graduated glass cylinder of 60 cm in length with an inside diameter of 6 cm. Then the cylinder went vertical and a perforated plate with a diameter of 5.9 cm and 24 holes with a diameter of 4 mm is drawn up and down evenly on a rod 30 times in 30 seconds and then carefully pulled out. The volume of the foam in ml was read after 1.5 and 10 min.

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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)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Glass Compositions (AREA)
  • Catalysts (AREA)

Claims (7)

1. Mélange constitué de
A)   un acide alcényl(C₈ -C₉)succinique,
B)   un acide arylsulfonylanthranilique de la formule I
Figure imgb0005
    dans laquelle R¹ et R² représentent chacun un atome d'hydrogène, de fluor, de chlore, de brome, un radical alkyle ou alcoxy comportant de 1 à 4 atomes de carbone, où la somme des atomes de carbone des radicaux R¹ et R² ne peut dépasser le nombre 7, A représente un reste de benzène ou de naphtalène et R³ représente un atome d'hydrogène ou un radical alkyle qui comporte de 1 à 4 atomes de carbone et
C)   de mono-, di- et/ou tri-(alcanol en C₂ à C₄)-amines, où le rapport pondéral A: B varie de 1: 7 à 4: 1 et le rapport pondéral (A + B): C varie de 3: 1 à 1: 4.

2. Mélange selon la revendication 1, caractérisé en ce que le rapport pondéral A: B varie de 1: 4 à 3: 1 et que le rapport pondéral (A + B): C varie de 2: 1 à 1: 3.
3. Mélange selon la revendication 1 ou 2, caractérisé en ce que le composant C est la diéthanolamine et/ou la triéthanolamine, éventuellement sous forme de leurs mélanges industriels.
4. Mélange selon l'une des revendications 1 à 3, caractérisé en ce que le composant A est l'acide diisobuténylsuccinique et le composant B est l'acide phényl- ou tolylsulfonylanthranilique.
5. Solution aqueuse d'un mélange selon l'une des revendications 1 à 4 dans de l'eau, où la concentration du mélange varie de 0,5 à 40% en poids, par rapport au poids total de la solution aqueuse.
6. Solution aqueuse suivant la revendication 5, caractérisée en ce que la concentration du mélange dans la solution aqueuse varie de 1 à 10% en poids, par rapport au poids total.
7. Utilisation d'un mélange suivant l'une quelconque des revendications 1 à 4, ou d'une solution aqueuse suivant la revendication 5 ou 6, à titre d'agent de protection contre la corrosion dans des systèmes aqueux.
EP89107873A 1988-05-10 1989-04-29 Mélanges d'acides alkénylsucciniques, d'acides arylsulfonylanthraniliques et d'alcanolamines et leur utilisation comme inhibiteurs la corrosion dans les systèmes aqueux Expired - Lifetime EP0341536B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89107873T ATE71158T1 (de) 1988-05-10 1989-04-29 Mischungen aus alkenylbernsteinsaeuren, arylsulfonylanthranilsaeuren und alkanolaminen und deren verwendung als korrosionsschutzmittel fuer waessrige systeme.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3815884A DE3815884A1 (de) 1988-05-10 1988-05-10 Mischungen aus alkanolaminsalzen von alkenylbernsteinsaeuren und arylsulfonylanthranilsaeuren zur verwendung als korrosionsschutzmittel fuer waessrige systeme
DE3815884 1988-05-10

Publications (2)

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EP0341536A1 EP0341536A1 (fr) 1989-11-15
EP0341536B1 true EP0341536B1 (fr) 1992-01-02

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Country Status (3)

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EP (1) EP0341536B1 (fr)
AT (1) ATE71158T1 (fr)
DE (2) DE3815884A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444878A1 (de) * 1994-12-16 1996-06-20 Henkel Kgaa Stickstofffreie Korrosionsinhibitoren mit guter Pufferwirkung
DE69906249T2 (de) * 1999-04-12 2004-01-22 Faborga S.A. Zusammensetzung und Verfahren zur Konditionierung von Industriewasser
WO2001071062A1 (fr) * 2000-03-21 2001-09-27 Holland Novochem Bv Composition anticorrosion et son procede d'utilisation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH629540A5 (de) * 1977-09-19 1982-04-30 Hoechst Ag Wassermischbare korrosionsschutzmittel.
DE2943963A1 (de) * 1979-10-31 1981-05-14 Basf Ag, 6700 Ludwigshafen Verwendung von alkanolaminsalzen von alkenylbernsteinsaeuren als korrosionsinhibitoren in waessrigen systemen
DE2947418A1 (de) * 1979-11-24 1981-06-04 BASF Corp., New York, N.Y. Umsetzprodukte aus sulfon- oder carbonamidocarbonsaeuren mit alkanolaminen und ihre verwendung als schaumarme korrosionsinhibitoren
DE3701719A1 (de) * 1987-01-22 1988-08-04 Basf Ag Korrosionsschutzmittel, enthaltend mischungen mit amidsaeuren

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EP0341536A1 (fr) 1989-11-15
DE58900650D1 (de) 1992-02-13
DE3815884A1 (de) 1989-11-23
ATE71158T1 (de) 1992-01-15

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