EP0341536B1 - Mixtures of alkenylsuccinic acids, arylsulfonylanthranilic acids and alkanol amines and their use as corrosion inhibitors in aqueous systems - Google Patents
Mixtures of alkenylsuccinic acids, arylsulfonylanthranilic acids and alkanol amines and their use as corrosion inhibitors in aqueous systems Download PDFInfo
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- 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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- 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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Abstract
Description
Die Erfindung betrifft synergistische Mischungen von Alkenylbernsteinsäuren, Arylsulfonylanthranilsäuren und Alkanolaminen sowie deren Verwendung als hochwirksame, schaumarme und wasserhärteunempfindliche Korrosionsinhibitoren in wäßrigen Systemen.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.
In technischen Prozessen, die sich in Gegenwart von Wasser abspielen, stellt sich immer das Problem des Korrosionsschutzes, wenn korrosionsgefährdete Metalle, wie Eisen, Aluminium, Zink, Kupfer oder deren Legierungen, beispielsweise durch Reinigungsprozesse, Kühlwasser, Kühlschmierstoffe, Hydraulikflüssigkeiten und andere funktionelle Lösungen und Emulsionen betroffen sind.In technical processes that take place in the presence of water, the problem of corrosion protection always arises when metals at risk of corrosion, such as iron, aluminum, zinc, copper or their alloys, for example through cleaning processes, cooling water, cooling lubricants, hydraulic fluids and other functional solutions and Emulsions are affected.
Häufig tritt bei solchen Verfahren und der Anwendung von Korrosionsschutzmitteln das Problem einer zu starken Schaumbildung auf, beispielsweise bei Emulsionen durch die verwendeten Emulgatoren und bei Lösungen durch Korrosionsschutzmittel mit Tensideigenschaften. So sind oft zusätzliche Schaumdämpfer notwendig, die neue Probleme ergeben: Sie stören häufig die technischen Prozesse und sie beeinträchtigen in vielen Fällen die Korrosionsschutzwirkung. In Umlaufanlagen werden wasserunlösliche Schaumdämpfer oft herausfiltriert.Frequently, the problem of excessive foaming occurs in such processes and the use of anti-corrosion agents, for example in the case of emulsions due to the emulsifiers used and in solutions using anti-corrosion agents with surfactant properties. Additional foam dampers are often necessary, which create new problems: they often disrupt the technical processes and in many cases impair the corrosion protection effect. Water-insoluble foam dampers are often filtered out in circulation systems.
Außerdem stehen die Anforderungen an die Arbeitssicherheit und Umweltverträglichkeit weiterhin im Gegensatz zu denen an die hohe Korrosionsschutzwirkung bei geringen Einsatzmengen, d.h., daß es wünschenswert ist, mit möglichst geringen Mengen auszukommen. In der Regel wird heute versucht, mit Korrosionsschutzmitteln auf der Basis Nitrit, Borsäure und ihren Estern, Boraten, p-tert.-Butylbenzoesäure und teilweise Zink-Salzen diese Anforderungen zu erfüllen.In addition, the requirements for occupational safety and environmental compatibility continue to be in contrast to those for the high corrosion protection effect with small amounts, i.e. that it is desirable to get by with the smallest possible amounts. As a rule, attempts are currently being made to meet these requirements with anti-corrosion agents based on nitrite, boric acid and their esters, borates, p-tert-butylbenzoic acid and, in some cases, zinc salts.
Nitrit ist aber toxisch, wasserverschmutzend und kann mit den häufig für Korrosionsschutz verwendeten Aminen cancerogene Nitrosamine bilden. Bor-Verbindungen sind zwar nur mäßig toxisch, unter bestimmten Bedingungen aber pflanzengiftig, wasserverschmutzend und können Stahloberflächen ungünstig verändern. p-tert.-Butylbenzoesäure ist im Tierversuch als chronisch toxisch erkannt worden. Zinksalze belasten Gewässer, Klärschlamm und Sedimente.However, 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.
Mit den in der Praxis verwendeten Korrosionsinhibitoren lassen sich häufig die gewünschten niederen Anwendungsmengen nicht erreichen.With the corrosion inhibitors used in practice, the desired low application amounts can often not be achieved.
Als wasserhärtestabile, schaumarme Korrosionsinhibitoren sind beispielsweise Sulfonamidocarbonsäuren gemäß der DE-C2-1298672 und der EP-B1-029529 bekannt. Optimal wirken sie allerdings nur in Mischungen mit Borverbindungen, wie z.B. aus der DE-C2-2840112 hervorgeht. Auf die Nachteile der Borverbindungen wurde bereits oben eingegangen.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.
Gute Korrosionsschutzwerte ohne Zusätze von Bor, Nitrit oder Zink bei weitgehender Schaumfreiheit erreichen beispielsweise die Alkenylbernsteinsäurederivate gemäß der DE-A-2943963. Diese sind allerdings wasserhärteempfindlich, d.h. sie bilden Ausfällungen in hartem Wasser, was sie für viele Anwendungsfälle unbrauchbar macht und große Probleme verursachen kann.The alkenylsuccinic acid derivatives according to DE-A-2943963, for example, achieve good corrosion protection values without the addition of boron, nitrite or zinc with largely no foam. However, 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.
In der EP-B1-029529 wird die Verwendung von Alkanolamin-Salzen, von Arylsulfonamidcarbonsäuren, bevorzugt von Arylsulfonylanthranilsäure, als Korrosionsinhibitoren beschrieben. Derartige Substanzen sind schaumarm und wenig wasserhärteempfindlich. Sie erreichen jedoch nicht ganz die Wirksamkeit der o.g. Bernsteinsäurederivate.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.
Aufgabe der Erfindung ist es, ein wäßriges Korrosionsschutzmittel zur Verfügung zu stellen, bei dem die Eigenschaften gute Wasserlöslichkeit, hohe Korrosionsschutzwirkung, Unempfindlichkeit gegen die Härte des Wassers und sehr gute Schaumarmut in möglichst optimaler Weise erreicht werden.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.
Die Lösung der Aufgabe besteht in der Verwendung von Mischungen aus C₈- bis C₉-Alkenylbernsteinsäuren gemäß der DE-A-2 943 963 und Arylsulfonylantranilsäuren gemäß der EP-B1-29 529 in Gegenwart von Alkanolaminen oder wäßrigen Lösungen dieser Mischungen als Korrosionsinhibitoren. Für diese Mischungen oder Lösungen ergeben sich unerwartete synergistische Vorteile.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.
Gegenstand der vorliegenden Erfindung sind Mischungen aus
- A)
- einer C₈- bis C₉-Alkenylbernsteinsäure,
- B)
- einer Arylsulfonylanthranilsäure der Formel I
- in der R¹ und R² Wasserstoff, Fluor, Chlor, Brom, einen Allyl- oder Alkoxy-Rest mit 1 bis 4 Kohlenstoffaotmen, wobei die Summe der Kohlenstoffatome der Reste R¹ und R² die Zahl 7, vorzugsweise 3, nicht übersteigen soll, A einen Benzol- oder Naphthalinrest und R³ Wasserstoff oder einen Alkylrest mit 1- bis 4-C-Atomen bedeuten, und
- C)
- Mono-, Di- und/oder Tri-(C₂- bis C₄-alkanol)-aminen, wobei das Gewichtsverhältnis A: B 1: 7 bis 4: 1, bevorzugt 1: 4 bis 3: 1, beträgt und das Gewichtsverhältnis (A + B): C 3: 1 bis 1: 4, bevorzugt 2: 1 bis 1: 3, beträgt. Weiterhin sind Gegenstand der vorliegenden Erfindung wäßrige Lösungen der genannten Mischungen, die diese Mischungen in einer Konzentration, bezogen auf das Gesamtgewicht, von 0,5 bis 40 Gew.%, bevorzugt 1 bis 10 Gew.%, enthalten. Schließlich ist Gegenstand der Erfindung die Verwendung der genannten Mischungen und ihrer wäßrigen Lösungen als Korrosionsschutzmittel in wäßrigen Systemen.
The present invention relates to mixtures of
- A)
- a C₈ to C₉ alkenyl succinic acid,
- B)
- an arylsulfonylanthranilic acid of the formula I.
- in which R¹ and R² are hydrogen, fluorine, chlorine, bromine, an allyl or alkoxy radical having 1 to 4 carbon atoms, the sum of the carbon atoms of the radicals R¹ and R² not exceeding 7, preferably 3, A being a benzene - Or naphthalene radical and R³ is hydrogen or an alkyl radical having 1 to 4 carbon atoms, and
- C)
- Mono-, di- and / or tri- (C₂- to C₄-alkanol) amines, the weight ratio A: B being 1: 7 to 4: 1, preferably 1: 4 to 3: 1, and the weight ratio (A + B): C 3: 1 to 1: 4, preferably 2: 1 to 1: 3. The present invention furthermore relates to aqueous solutions of the mixtures mentioned which contain these mixtures in a concentration, based on the total weight, of 0.5 to 40% by weight, preferably 1 to 10% by weight. Finally, the invention relates to the use of the mixtures mentioned and their aqueous solutions as corrosion inhibitors in aqueous systems.
Mit den erfindungsgemäß zu verwendenden Mischungen wird ein Korrosionsschutz bewirkt, der den der beschriebenen Einzelverbindungen in synergistischer Weise übertrifft. Die wäßrigen Lösungen dieser Mischungen weisen hohe Schaumarmut auf und darüber hinaus überraschenderweise auch eine gegenüber den Alkanolaminsalzen der Einzelkomponenten A und B verringerte Wasserhärteempfindlichkeit. Es liegt ein nicht vorhersehbarer Synergismus vor. Die erfindungsgemäßen Mischungen sind damit in der Lage, die obengestellte Aufgabe in hervorragender Weise zu erfüllen.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.
Von den C₈- bis C₉-Alkenylbernsteinsäuren ist die Di-isobutenylbernsteinsäure, wie sie im Beispiel 1 der DE-A1-2943963 beschrieben wird, bevorzugt.Of the C₈ to C₉ alkenylsuccinic acids, the di-isobutenylsuccinic acid as described in Example 1 of DE-A1-2943963 is preferred.
Bevorzugte Arylsulfonylanthranilsäuren, wie sie in dem obengenannten europäischen Patent beschrieben werden, sind solche, in denen R¹ und R² Wasserstoff oder Methyl, A einen Benzolrest und R³ Wasserstoff bedeuten. Demnach sind die besonders bevorzugt verwendeten Arylsulfonylanthranilsäuren N-Phenylsulfonyl- und N-(o-Tolylsulfonyl)-anthranilsäure.Preferred arylsulfonylanthranilic acids, as described in the above-mentioned European patent, 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.
Als Mono-, Di- und/oder Tri-(C₂- bis C₄-alkanol)-amine sind insbesondere Mono-, Di- und Triethanolamin und Mono-, Di- und Tri-iso-propanolamin zu nennen. Diethanolamin, Trichloramin und deren Mischungen sind bevorzugt. Dabei handelt es sich in der Praxis neben den reinen Aminen zweckmäßig um Gemische von Mono-, Di- und Triethanolamin, vorzugsweise von Diethanol und Triethanolamin, wie sie bei den technischen Herstellverfahren anfallen. Besonders bevorzugt ist eine Mischung aus ca. 5 Gew.% Mono-, ca. 55 Gew.% Di- und 40 Gew.% Triethanolamin oder beispielsweise von 85 Gew.% Tri- und 15 Gew.% Diethanolamin.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. In practice, in addition to the pure amines, 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.
Wie oben erwähnt, beträgt die Konzentration der Mischung (A + B + C), bezogen auf Reinsubstanz und auf das Gesamtgewicht der wäßrigen Lösung, 0,5 bis 40, bevorzugt 1 bis 10 Gew.%. Der ganz besonders bevorzugte Bereich liegt bei 1 bis 4 Gew.%.As mentioned above, 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.
Die erfindungsgemäßen Mischungen oder ihre wäßrigen Lösungen können in allen wäßrigen Systemen eingesetzt werden, die mit Eisen, dessen Legierungen (Stählen), Aluminium, dessen Legierungen, Zink oder Kupfer oder deren Legierung in Berührung kommen. Zu nennen sind z.B. Hydraulikflüssigkeiten, Kühlschmierstoffe, neutrale bis alkalische technische Reiniger oder Grubenwässer, die besonders hart und salzreich sind, und die im Bergbau direkt als Anmischwasser, z.B. für hydraulische Prozesse, verwendet werden und besonders stark korrosiv wirken.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. 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.
Die Anwendungskonzentrationen schwanken je nach Anwendungsbereich und Art des wäßrigen Mediums sowie der zu schützenden Metalle. Im allgemeinen setzt man, bezogen auf das technisch verwendete wäßrige System, 0,01 bis 5 Gew.%, bezogen auf das Gemisch der Substanzen (A + B+ C), ein. Vorzugsweise soll die Konzentration 0,1 bis 5 Gew.% betragen.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.
Das optimale Mengenverhältnis der Komponenten A und B zueinander richtet sich nach dem Anwendungszweck. Dabei wird zweckmäßigerweise so vorgegangen, daß von einem Mengenverhältnis 1: 1 ausgegangen wird, womit in der Regel Ergebnisse erzielt werden, die in der Nähe des Optimums liegen. Das günstigste Mengenverhältnis (A + B): C läßt sich sehr einfach dadurch ermitteln, daß eine solche Menge an C zugegeben wird, daß der pH-Wert der wäßrigen Lösung zwischen 7 und 9 liegt. Dieser pH-Bereich wird üblicherweise getroffen, wenn der Anteil von C an der Mischung (A + B + C) 33 bis 75, bevorzugt 50 bis 70 Gew.% beträgt.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.
Den erfindungsgemäßen Mischungen oder ihren wäßrigen Lösungen können je nach Bedarf zusätzliche Hilfsmittel zugesetzt werden, die ihre Gebrauchseigenschaften erhöhen. Dadurch kann beispielsweise die Benetzung verbessert, das Wachstum von Mikroorganismen unterdrückt oder der Ausfall von Niederschlägen durch Substanzen, die in den wäßrigen Systemen gelöst sind, verhindert werden.Depending on requirements, additional 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.
Übliche Zusätze sind beispielsweise Tenside als Netzmittel, wie Alkylphenolethoxylate, Dispergiermittel, wie Salze von polymeren Carbonsäuren, Emulgatoren, wie Alkyl- oder Alkylarylsulfonate, Solubilisatoren, wie Glykole, insbesondere Propylenglykol, niedere aliphatische Alkohole oder Cumolsulfonsäure-Natriumsalz, Polyglykole, wie Polyethylen- oder Polyproylenglykole oder Polyethylen/Polypropylen-Blockpolymere u.a.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
Die Prüfung der erfindungsgemäßen Korrosionsschutzmittel erfolgt nach den im folgenden beschriebenen Verfahren:The corrosion protection agents according to the invention are tested using the methods described below:
Die korrosionsschützende Wirkung wurde durch den "Grauguß-Filterpapier-Test", DIN 51 360, Teil 2, bestimmt.The corrosion protection effect was determined by the "gray cast iron filter paper test", DIN 51 360, part 2.
- 4 =4 =
- sehr starke Korrosionvery strong corrosion
- 3 =3 =
- starke Korrosionsevere corrosion
- 2 =2 =
- mäßige Korrosionmoderate corrosion
- 1 =1 =
- geringe Korrosionlow corrosion
- 0 =0 =
- keine Korrosionno corrosion
Entsprechend DIN 51360, Teil 2, Punkt 8, wurde hartes Wasser durch Mischen von vollentsalztem Wasser mit 3,04 mmol/l CaCl₂ · 6H₂O und 0,54 mmol/l MgSO₄ · 7H₂O hergestellt. Unter Verwendung dieses Wassers wurden Lösungen der erfindungsgemäßen Mischungen in einer Konzentration von 2 Gew.%, bezogen auf den Gehalt an Reinsubstanz, hergestellt. Nach dem Stehenlassen über Nacht wurde beurteilt:According to DIN 51360, part 2, point 8, 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:
Lösung klar/fast klar/opak/trüb. kein Niederschlag/geringer Niederschlag/Bodensatz.Solution clear / almost clear / opaque / cloudy. no precipitation / low precipitation / sediment.
Es wurde in Anlehnung an die DIN 53 902 die Schlagmethode verwendet. 200 ml 1 gew.%ige Lösung der erfindungsgemäßen Mischung in vollentsalztem Wasser wurden in einem graduierten Glaszylinder von 60 cm Länge mit einem Innendurchmesser von 6 cm gefüllt. Dann wurde der Zylinder senkrecht gestellt und eine Lochplatte mit einem Durchmesser von 5,9 cm und 24 Löchern à 4 mm Durchmesser an einem Stab 30 mal in 30 sec gleichmäßig auf- und abgeführt und dann vorsichtig herausgezogen. Das Volumen des Schaums in ml wurde nach 1,5 und 10 min abgelesen.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.
Die folgenden in der Tabelle zusammengestellten Beispiele und erhaltenen Ergebnisse erläutern die Erfindung. In der Tabelle bedeuten:
- A:
- Di-isobutylenbernsteinsäure
- B:
- Phenylsulfonyulanthranilsaure
- DEA-TEA:
- Mischung aus 5 Gew.% Monoethanolamin, 55 Gew.% Diethanolamin und 40 Gew.% Triethanolamin
- TEA:
- Triethanolamin.
- A:
- Di-isobutylene succinic acid
- B:
- Phenylsulfonyulanthranilic acid
- DEA-TEA:
- Mixture of 5% by weight monoethanolamine, 55% by weight diethanolamine and 40% by weight triethanolamine
- TEA:
- Triethanolamine.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89107873T ATE71158T1 (en) | 1988-05-10 | 1989-04-29 | MIXTURES OF ALKENYLBUTRIC ACIDS, ARYLSULFONYLANTHRANIL ACIDS AND ALKANOLAMINES AND THEIR USE AS ANTI-CORROSION AGENTS FOR AQUEOUS SYSTEMS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3815884 | 1988-05-10 | ||
DE3815884A DE3815884A1 (en) | 1988-05-10 | 1988-05-10 | MIXTURES OF ALKANOLAMINE SALTS OF ALKENYLBERNIC ACIDS AND ARYLSULFONYLANTHRANILIC ACIDS FOR USE AS CORROSION PROTECTION AGENTS FOR WAESSED SYSTEMS |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0341536A1 EP0341536A1 (en) | 1989-11-15 |
EP0341536B1 true EP0341536B1 (en) | 1992-01-02 |
Family
ID=6354034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89107873A Expired - Lifetime EP0341536B1 (en) | 1988-05-10 | 1989-04-29 | Mixtures of alkenylsuccinic acids, arylsulfonylanthranilic acids and alkanol amines and their use as corrosion inhibitors in aqueous systems |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0341536B1 (en) |
AT (1) | ATE71158T1 (en) |
DE (2) | DE3815884A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4444878A1 (en) * | 1994-12-16 | 1996-06-20 | Henkel Kgaa | Nitrogen-free corrosion inhibitors with a good buffer effect |
DE69906249T2 (en) * | 1999-04-12 | 2004-01-22 | Faborga S.A. | Composition and process for conditioning industrial water |
WO2001071062A1 (en) * | 2000-03-21 | 2001-09-27 | Holland Novochem Bv | Corrosive preventive composition and method of using the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH629540A5 (en) * | 1977-09-19 | 1982-04-30 | Hoechst Ag | WATER-MIXABLE ANTI-CORROSIVE AGENT. |
DE2943963A1 (en) * | 1979-10-31 | 1981-05-14 | Basf Ag, 6700 Ludwigshafen | Iron corrosion inhibition - with aq. system contg. alkanolamine salt(s) of alkenyl succinic acid(s) |
DE2947418A1 (en) * | 1979-11-24 | 1981-06-04 | BASF Corp., New York, N.Y. | IMPLEMENTATION PRODUCTS OF SULPHONE OR CARBONAMIDOCARBONIC ACIDS WITH ALKANOLAMINES AND THEIR USE AS LOW-FOAM CORROSION INHIBITORS |
DE3701719A1 (en) * | 1987-01-22 | 1988-08-04 | Basf Ag | Corrosion protection agent, containing mixtures with amido acids |
-
1988
- 1988-05-10 DE DE3815884A patent/DE3815884A1/en not_active Withdrawn
-
1989
- 1989-04-29 DE DE8989107873T patent/DE58900650D1/en not_active Expired - Lifetime
- 1989-04-29 AT AT89107873T patent/ATE71158T1/en not_active IP Right Cessation
- 1989-04-29 EP EP89107873A patent/EP0341536B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ATE71158T1 (en) | 1992-01-15 |
EP0341536A1 (en) | 1989-11-15 |
DE3815884A1 (en) | 1989-11-23 |
DE58900650D1 (en) | 1992-02-13 |
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