EP0028674A1 - Use of acidic phosphoric acid esters or their salts as corrosion inhibitors for metals - Google Patents

Use of acidic phosphoric acid esters or their salts as corrosion inhibitors for metals Download PDF

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EP0028674A1
EP0028674A1 EP80104291A EP80104291A EP0028674A1 EP 0028674 A1 EP0028674 A1 EP 0028674A1 EP 80104291 A EP80104291 A EP 80104291A EP 80104291 A EP80104291 A EP 80104291A EP 0028674 A1 EP0028674 A1 EP 0028674A1
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alcohol
use according
acid
glycol
metals
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EP0028674B1 (en
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Günther Sorbe
Horst-Dieter Dr. Wasel-Nielen
Lothar Westermann
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Hoechst AG
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Hoechst AG
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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
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds

Definitions

  • the inhibition of the corrosion of metals includes the processes of corrosion reduction by one or more substances which are added to the corrosion-causing corrosion-reducing agent or which can be contained in whole or in part from the outset.
  • the substances that reduce the corrosion of the metals in this way are called corrosion inhibitors.
  • the corrosiveness of these acids or their aqueous solutions to metals can be reduced or eliminated entirely by suitable inhibitors, for example by forming protective films or cover layers on the metal surfaces. It is not the applied films or layers that have an inhibiting effect, but only those substances from which such deposits in the corrosion agent, for example organic adsorptives, chromates, phosphates, nitrites, etc., can arise.
  • alkali and amine salts of straight-chain aliphatic, saturated or unsaturated carboxylic acids can be used in an aqueous medium as effective corrosion inhibitors for metals. This creates a coherent, firmly adhering film that protects the metal surface from the attack of aggressive liquids. Salts of aliphatic carboxylic acids or nucleus-substituted arylsulfonamide carboxylic acids and their salts are also known as corrosion inhibitors.
  • the aforementioned phosphoric acid esters can only be used in a few special areas of application due to their more or less strong tendency to foam.
  • defoaming agents at For example, silicone defoamers
  • the resulting foam can be partially or completely removed, but the usability of the phosphoric acid esters is then further limited by the side effects of the defoamers.
  • the present invention is intended to overcome the disadvantages of the known corrosion inhibitors.
  • the invention relates to the use of acidic phosphoric acid esters or salts thereof as agents for preventing corrosion of metals and consists in that the agent used to prevent corrosion of metals caused by inorganic and / or organic acids or their aqueous solutions Reaction of phosphorus V-oxide with a mixture consisting of a monohydric alcohol and an alkane polyol with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, while maintaining a molar ratio of phosphorus V-oxide to monohydric alcohol to alkane polyol of 1 to 2 to 4 / n, where n is the number of hydroxyl groups in the alkane polyol molecule or a stoichiometric excess of the alcoholic components, and also mixing or kneading of the reaction components at a temperature between about 0 ° C. and 120 ° C. with the exclusion of moisture and in the presence of an inert gas in the course of about 1 - was obtained 6 hours.
  • the corrosion protection provided by the agents according to the invention extends in particular to steel, stainless steel, copper, aluminum, to aluminum / magnesium / silicon alloys or to aluminum / zinc / magnesium alloys, the acid which causes corrosion being orthophosphoric acid, formic acid, hydrochloric acid, sulfuric acid, Amidosulfuric acid or nitric acid can be.
  • the monohydric alcohol is an aliphatic alcohol having 1 to 22 carbon atoms or the reaction product of an aliphatic alcohol having 1 to 22 carbon atoms or a phenol having 6 to 18 carbon atoms with 2 to 20 moles of ethylene oxide , such as B.
  • the agents suitable according to the invention can be produced by the processes of German Offenlegungsschriften Nos. 26 45 211 and 27 39 916.
  • the reaction of phosphorus V-oxide with the monohydric alcohol and an alkanediol can be carried out while maintaining a molar ratio of 1: 2: 2. If an alkane tetrol takes the place of the alkane diol, the molar ratio is preferably 1: 2: 1.
  • the inorganic and / or organic acids or their aqueous solutions can contain the agent dissolved or suspended in a ratio of acid to inhibitor such as 100: 0.5 to 1: 1.
  • the acidic phosphoric acid esters according to the invention have the advantage that, when mixed with inorganic and / or organic acids or their aqueous solutions, they are absolutely foam-free and have a corrosion-reducing effect regardless of the concentration used and the pH of the acids or their aqueous solutions.
  • Example 4 The procedure was analogous to Example 1, but aqueous solutions were prepared in the quantity ratios shown in Table 3 and the corrosion removal on steel sheets ST 37-2 was determined in accordance with the test conditions specified in Example 1. By comparison, aqueous orthophosphoric acid without the addition of inhibitor was tested (Table 4).
  • aqueous solutions were tested in the proportions according to Table 5 for metals and metal alloys with the designations I to VI analogously to Example 1 for corrosion.
  • Table 5 shows that the corrosion inhibitor according to Example 1 has a corrosion-inhibiting effect on metals both in aqueous solutions of inorganic and organic acids.
  • the reaction product of P 4 O 10 , n-butanol and ethylene glycol according to Example 1 was processed with further mixture components to form a cleaning agent of the following composition.
  • Example 5 The procedure was analogous to Example 4, but the reaction product of P4010 with ethanol and ethylene glycol as in Example 5 was used as the corrosion inhibitor.
  • the reaction product was prepared by the process of DE-OS 27 39 916, Example 1.
  • the reaction product according to Example 1 was mixed with nitric acid (65%) in the proportions according to Table 9 and tested according to the test conditions according to Example 1 for metals and metal alloys with the designations I to VI. The test results are shown in Table 9.

Abstract

1. Use of acid phosphoric acid esters or their salts as agents inhibiting the corrosion of metals, characterised in that, in order to inhibit the corrosion of metals caused by inorganic and/or organic acids or their aqueous solutions, use is made of that agent which has been obtained by subjecting phosphorus(V)oxide to reaction with a mixture consisting of a monohydric alcohol and an alkane polyol having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups while respecting a molar ratio of phosphorus(V)oxide to monohydric alcohol to alkane polyol of 1 : 2 : 4/n, n standing for the number of hydroxyl groups in the alkane polyol molecule, or while using a stoichiometric excess of the alcoholic component, and mixing or kneading the reaction components at a temperature between about 0 degree C and 120 degrees C with exclusion of moisture and in the presence of an inert gas, within a period of about 1 to 6 hours.

Description

Die Inhibierung der Korrosion von Metallen umfaßt die Vorgänge einer Korrosionsminderung durch einen oder mehrere Stoffe, die dem Korrosion verursachenden Mittel zur Korrosionsminderung zugesetzt werden oder in ihm bereits von vornherein ganz oder teilweise enthalten sein können. Die Stoffe, die die Korrosion der Metalle auf diese Weise vermindern, nennt man Korrosionsinhibitoren.The inhibition of the corrosion of metals includes the processes of corrosion reduction by one or more substances which are added to the corrosion-causing corrosion-reducing agent or which can be contained in whole or in part from the outset. The substances that reduce the corrosion of the metals in this way are called corrosion inhibitors.

Eisen, Stahl oder andere eisenhaltige Metalle, aber auch Leichtmetalle, wie Aluminium oder aluminiumhaltige Legierungen, werden durch anorganische oder organische Säuren mehr oder minder korrodiert. Die Korrosivität dieser Säuren oder deren wäßrigen Lösungen gegenüber Metallen kann durch geeignete Inhibitoren vermindert oder ganz aufgehoben werden, indem beispielsweise auf den Metalloberflächen Schutzfilme oder Deckschichten gebildet werden. Nicht die aufgebrachten Filme oder Schichten wirken inhibierend, sondern allein jene Stoffe, aus denen solche Beläge im Korrosionsmittel, beispielsweise organische Adsorptiva, Chromate, Phosphate,Nitrite u. a., entstehen können. Ferner ist bekannt, daß Alkali- und Aminsalze geradkettiger aliphatischer, gesättigter oder ungesättigter Carbonsäuren in wässerigem Medium als wirksame Korrosionsschutzmittel für Metalle eingesetzt werden können. Hierbei bildet sich ein zusammenhängender, festhaftender Film, der die Metalloberfläche vor dem Angriff aggressiver Flüssigkeiten schützt. Weiterhin sind Salze aliphatischer Carbonsäuren oder kernsubstituierte Arylsulfonamidcarbonsäuren-sowie deren Salze als Korrosionsinhibitoren bekannt.Iron, steel or other ferrous metals, but also light metals, such as aluminum or aluminum-containing alloys, are more or less corroded by inorganic or organic acids. The corrosiveness of these acids or their aqueous solutions to metals can be reduced or eliminated entirely by suitable inhibitors, for example by forming protective films or cover layers on the metal surfaces. It is not the applied films or layers that have an inhibiting effect, but only those substances from which such deposits in the corrosion agent, for example organic adsorptives, chromates, phosphates, nitrites, etc., can arise. It is also known that alkali and amine salts of straight-chain aliphatic, saturated or unsaturated carboxylic acids can be used in an aqueous medium as effective corrosion inhibitors for metals. This creates a coherent, firmly adhering film that protects the metal surface from the attack of aggressive liquids. Salts of aliphatic carboxylic acids or nucleus-substituted arylsulfonamide carboxylic acids and their salts are also known as corrosion inhibitors.

Diese Verbindungen haben jedoch Nachteile. So ist beispielsweise die Wirksamkeit der Fettaminsalze als Korrosionsschutzmittel stark vom umgebenden Flüssigkeitsmedium, den Korrosionsbedingungen und der Art der Metalle abhängig. Außerdem besitzen sie häufig die unerwünschte Eigenschaft zu schäumen. Daher ist ihr Einsatz stets auf bestimmte Metalle und Anwendungsgebiete beschränkt.However, these connections have disadvantages. For example, the effectiveness of fatty amine salts as anti-corrosion agents depends heavily on the surrounding liquid medium, the corrosion conditions and the type of metals. In addition, they often have the undesirable property of foaming. Therefore, their use is always limited to certain metals and areas of application.

Wie aus der europäischen Patentanmeldung 0 002 530 A1 bekannt ist, werden neuerdings auch saure Ester aus Phosphorsäuren und alkoxylierten aliphatischen Alkoholen als Korrosionsschutzmittel für Metalle eingesetzt.As is known from European patent application 0 002 530 A1, acidic esters from phosphoric acids and alkoxylated aliphatic alcohols have recently also been used as corrosion inhibitors for metals.

Weiterhin ist bekannt, daß Phosphorsäureester von ethoxylierten Alkoholen oder Alkylphenolen oder ethoxylierten und propoxylierten Fettalkoholen oder Alkylphenolen korrosionsmindernde Eigenschaften aufweisen.It is also known that phosphoric acid esters of ethoxylated alcohols or alkylphenols or ethoxylated and propoxylated fatty alcohols or alkylphenols have corrosion-reducing properties.

Vorgenannte Phosphorsäureester können aber nur auf wenigen, speziellen Anwendungsgebieten aufgrund ihrer mehr oder weniger starken Schaumneigung eingesetzt werden. Durch Zugabe von Entschäumungsmitteln, beispielsweise Siliconentschäumer, kann der entstehende Schaum teilweise oder ganz entfernt werden, jedoch wird dann die Verwendbarkeit der Phosphorsäureester durch die Nebenwirkungen der Entschäumer noch weiter begrenzt.The aforementioned phosphoric acid esters can only be used in a few special areas of application due to their more or less strong tendency to foam. By adding defoaming agents, at For example, silicone defoamers, the resulting foam can be partially or completely removed, but the usability of the phosphoric acid esters is then further limited by the side effects of the defoamers.

Schließlich ist zu erwähnen, daß die Schutzwirkung der allgemein bekannten Korrosionsinhibitoren in wäßrigen, säurehaltigen Lösungen oder Säuren gegenüber Metallen stark von der Einsatzkonzentration sowie der Temperatur und dem pH-Wert der Lösung abhängig ist.Finally, it should be mentioned that the protective effect of the generally known corrosion inhibitors in aqueous, acidic solutions or acids against metals is strongly dependent on the concentration used and on the temperature and the pH of the solution.

Durch vorliegende Erfindung sollen die Nachteile der bekannten Korrosionsinhibitoren überwunden werden.The present invention is intended to overcome the disadvantages of the known corrosion inhibitors.

Die Erfindung betrifft die Verwendung von sauren Phosphorsäureestern oder deren Salze als Mittel zur Verhinderung der Korrosion von Metallen und besteht darin, daß man zur Verhinderung der durch anorganische und/ oder organische Säuren bzw. deren wäßrigen Lösungen verursachten Korrosion von Metallen das Mittel verwendet, das durch Umsetzung von Phosphor-V-oxid mit einem Gemisch,bestehend aus einem einwertigen Alkohol sowie einem Alkanpolyol mit 2 bis 12 C-Atomen und 2 bis 6 Hydroxylgruppen, unter Einhaltung eines Molverhältnisses von Phosphor-V-oxid zu einwertigem Alkohol zu Alkanpolyol von 1 zu 2 zu 4/n, wobei n die Anzahl der Hydroxylgruppen im Alkanpolyolmolekül bedeutet oder eines stöchiometrischen Überschusses der alkoholischen Komponenten, sowie Mischen oder Kneten der Reaktionskomponenten bei einer Temperatur zwischen etwa 0°C und 120°C unter Ausschluß von Feuchtigkeit und in Gegenwart eines inerten Gases im Verlauf von etwa 1 - 6 Stunden erhalten wurde.The invention relates to the use of acidic phosphoric acid esters or salts thereof as agents for preventing corrosion of metals and consists in that the agent used to prevent corrosion of metals caused by inorganic and / or organic acids or their aqueous solutions Reaction of phosphorus V-oxide with a mixture consisting of a monohydric alcohol and an alkane polyol with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, while maintaining a molar ratio of phosphorus V-oxide to monohydric alcohol to alkane polyol of 1 to 2 to 4 / n, where n is the number of hydroxyl groups in the alkane polyol molecule or a stoichiometric excess of the alcoholic components, and also mixing or kneading of the reaction components at a temperature between about 0 ° C. and 120 ° C. with the exclusion of moisture and in the presence of an inert gas in the course of about 1 - was obtained 6 hours.

Der durch die erfindungsgemäßen Mittel bewirkte Korrosionsschutz erstreckt sich insbesondere auf Stahl, Edelstahl, Kupfer, Aluminium, auf Aluminium/Magnesium/ Silicium-Legierungen oder auf Aluminium/Zink/Magnesium-Legierungen, wobei die Korrosion verursachende Säure Orthophosphorsäure, Ameisensäure, Chlorwasserstoffsäure, Schwefelsäure, Amidoschwefelsäure oder Salpetersäure sein kann.The corrosion protection provided by the agents according to the invention extends in particular to steel, stainless steel, copper, aluminum, to aluminum / magnesium / silicon alloys or to aluminum / zinc / magnesium alloys, the acid which causes corrosion being orthophosphoric acid, formic acid, hydrochloric acid, sulfuric acid, Amidosulfuric acid or nitric acid can be.

Nach einer bevorzugten Ausführungsform der Erfindung ist der einwertige Alkohol ein aliphatischer Alkohol mit 1 bis 22 C-Atomen oder das Umsetzungsprodukt eines aliphatischen Alkohols mit 1 - 22 C-Atomen bzw. eines Phenols mit 6 - 18 C-Atomen mit 2 - 20 Molen Ethylenoxid, wie z. B. Methanol, Ethanol, Isopropanol, n-Butanol, Isotridecylalkohol, Stearylalkohol, Oleylalkohol, ein technisches Gemisch aliphatischer Alkohole, 2-Chlorethanol, 2,3-Dibrompropanol-1, 3-Methoxybutanol-1 oder 2-Phenylpropanol-1 sowie das Ethylenoxid-Addukt von Methylglykol, Ethylglykol, Butylglykol oder Butyldiglykol oder das Addukt aus 4 Molen Ethylenoxid und 1 Mol Laurylalkohol, aus 8 Molen Ethylenoxid und 1 Mol Stearylalkohol, aus 6 Molen Ethylenoxid und 1 Mol Phenol bzw. aus 8 Molen Ethylenoxid und 1 Mol Nonylphenol.According to a preferred embodiment of the invention, the monohydric alcohol is an aliphatic alcohol having 1 to 22 carbon atoms or the reaction product of an aliphatic alcohol having 1 to 22 carbon atoms or a phenol having 6 to 18 carbon atoms with 2 to 20 moles of ethylene oxide , such as B. methanol, ethanol, isopropanol, n-butanol, isotridecyl alcohol, stearyl alcohol, oleyl alcohol, a technical mixture of aliphatic alcohols, 2-chloroethanol, 2,3-dibromopropanol-1, 3-methoxybutanol-1 or 2-phenylpropanol-1 and the ethylene oxide Adduct of methyl glycol, ethyl glycol, butyl glycol or butyl diglycol or the adduct of 4 moles of ethylene oxide and 1 mole of lauryl alcohol, of 8 moles of ethylene oxide and 1 mole of stearyl alcohol, of 6 moles of ethylene oxide and 1 mole of phenol or of 8 moles of ethylene oxide and 1 mole of nonylphenol.

Andererseits umfaßt die Alkanpolyol-Komponente bei der Herstellung des sauren Phosphorsäureesters vorzugsweise folgende Verbindungen:

  • Ethylenglykol, Propandiol-1,2, Propandiol-1,3, Butandiol-1,3, Butandiol-1,4, Diethylenglykol, Polyethylenglykol, Neopentylglykol, Dibromneopentylglykol, Glycerin, Trimethylolpropan, Mannit oder Pentaerythrit.
On the other hand, the alkane polyol component in the preparation of the acidic phosphoric acid ester preferably comprises the following compounds:
  • Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, polyethylene glycol, neopentyl glycol, dibromoneopentyl glycol, glycerol, trimethylol propane, mannitol or pentaerythritol.

Die Herstellung der erfindungsgemäß geeigneten Mittel kann grundsätzlich nach den Verfahren der Deutschen Offenlegungsschriften Nr. 26 45 211 und 27 39 916 erfolgen. Wie in diesen Offenlegungsschriften bereits ausgeführt, kann die Umsetzung von Phosphor-V-oxid mit dem einwertigen Alkohol und einem Alkandiol unter Einhaltung eines Molverhältnisses von 1 : 2 : 2 durchgeführt werden. Tritt an die Stelle des Alkandiols ein Alkantetrol, so beträgt das Molverhältnis vorzugsweise 1 : 2 : 1.In principle, the agents suitable according to the invention can be produced by the processes of German Offenlegungsschriften Nos. 26 45 211 and 27 39 916. As already stated in these published documents, the reaction of phosphorus V-oxide with the monohydric alcohol and an alkanediol can be carried out while maintaining a molar ratio of 1: 2: 2. If an alkane tetrol takes the place of the alkane diol, the molar ratio is preferably 1: 2: 1.

Nach einer weiteren bevorzugten Ausführungsform der Erfindung können die anorganischen und/oder organischen Säuren bzw. deren wäßrige Lösungen das Mittel gelöst oder suspendiert in einem Verhältnis von Säure zu Inhibitor wie 100 : 0,5 bis 1 : 1 enthalten.According to a further preferred embodiment of the invention, the inorganic and / or organic acids or their aqueous solutions can contain the agent dissolved or suspended in a ratio of acid to inhibitor such as 100: 0.5 to 1: 1.

Gegenüber den bekannten Korrosionsinhibitoren besitzen die erfindungsgemäßen sauren Phosphorsäureester den Vorteil, daß sie im Gemisch mit anorganischen und/oder organischen Säuren oder deren wäßrigen Lösungen absolut schaumfrei sind und unabhängig von der Einsatzkonzentration und dem pH-Wert der Säuren oder deren wäßrigen Lösungen korrosionsmindernd wirken.Compared to the known corrosion inhibitors, the acidic phosphoric acid esters according to the invention have the advantage that, when mixed with inorganic and / or organic acids or their aqueous solutions, they are absolutely foam-free and have a corrosion-reducing effect regardless of the concentration used and the pH of the acids or their aqueous solutions.

Dieser Effekt war nicht zu erwarten, da die Schutzwirkung bekannter Korrosionsinhibitoren, wie sie beispielsweise in der Europäischen Patentanmeldung Nr. 0 002 530 A1 beschrieben werden, sich nur auf einen begrenzten pH-Bereich erstreckt, und darüberhinaus diese als schaumarm bezeichneten Inhibitoren nicht völlig frei von Schaumbildung sind.This effect was not to be expected, since the protective action of known corrosion inhibitors, as described, for example, in European Patent Application No. 0 002 530 A1, only extends to a limited pH range, and moreover these inhibitors, which are referred to as low-foaming, are not completely free of Are foaming.

Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie jedoch im einzelnen zu beschränken.The following examples are intended to explain the invention in greater detail, but without restricting it in detail.

Beispiel 1example 1

Es wurden Lösungen aus Wasser, Orthophosphorsäure und dem Umsetzungsprodukt aus P4010 mit n-Butanol und Ethylenglykol im Molverhältnis von 1 : 2 : 2, wie in Beispiel 1 der DE-OS 2 645 211 beschrieben, als Korrosionsinhibitor in folgenden Mengenverhältnissen hergestellt:

  • a) 10 Teile Orthophosphorsäure, 0 Teile Inhibitor und 90 Gew.-Teile Wasser
  • b) 9 Teile Orthophosphorsäure, 1 Teil Inhibitor und 90 Gew.-Teile Wasser
  • c) 8 Teile Orthophosphorsäure, 2 Teile Inhibitor und 90 Gew.-Teile Wasser
  • d) 7 Teile Orthophosphorsäure, 3 Teile Inhibitor und 90 Gew.-Teile Wasser
  • e) 6 Teile Orthophosphorsäure, 4 Teile Inhibitor und 90 Gew.-Teile Wasser
  • f) 5 Teile Orthophosphorsäure, 5 Teile Inhibitor und 90 Gew.-Teile Wasser und in Kontakt mit folgenden Metallen bzw. Metalllegierungen in Form von Probeblechen gebracht:
    • I Edelstahl, Werkstoff-Nr. 1.4571
    • II Stahl, Werkstoff-Nr. ST 37-2 (gesandstrahlt)
    • III Kupfer, rein
    • IV Aluminium,reinst
    • V Aluminiumlegierung Al Mg Si 1
    • VI Aluminiumlegierung Al Zn Mg 1

    indem die Probenbleche in die Lösungen mit der Bezeichnung a - f über einen Zeitraum von 24 Stunden bei 20° C eingetaucht wurden. Anschließend wurden die Probenbleche mit Wasser abgespült, getrocknet und durch Wägung die Gewichtsdifferenz in g/m2/Tag ermittelt. Die erhaltenen Ergebnisse sind in Tabelle 1 dargestellt.
    Figure imgb0001
Solutions of water, orthophosphoric acid and the reaction product of P 4 0 10 with n-butanol and ethylene glycol in a molar ratio of 1: 2: 2, as described in Example 1 of DE-OS 2 645 211, were prepared as corrosion inhibitors in the following proportions:
  • a) 10 parts of orthophosphoric acid, 0 parts of inhibitor and 90 parts by weight of water
  • b) 9 parts of orthophosphoric acid, 1 part of inhibitor and 90 parts by weight of water
  • c) 8 parts of orthophosphoric acid, 2 parts of inhibitor and 90 parts by weight of water
  • d) 7 parts of orthophosphoric acid, 3 parts of inhibitor and 90 parts by weight of water
  • e) 6 parts of orthophosphoric acid, 4 parts of inhibitor and 90 parts by weight of water
  • f) 5 parts of orthophosphoric acid, 5 parts of inhibitor and 90 parts by weight of water and brought into contact with the following metals or metal alloys in the form of test sheets:
    • I stainless steel, material no. 1.4571
    • II steel, material no. ST 37-2 (sandblasted)
    • III copper, pure
    • IV aluminum, ultra pure
    • V aluminum alloy Al Mg Si 1
    • VI Al Zn Mg 1 aluminum alloy

    by immersing the sample sheets in the solutions labeled a - f over a period of 24 hours at 20 ° C. The sample sheets were then rinsed with water, dried and the weight difference in g / m 2 / day is determined by weighing. The results obtained are shown in Table 1.
    Figure imgb0001

Mit Lösungen aus Orthophosphorsäure und Wasser in den folgenden Mengenverhältnissen wurde entsprechend obigen Prüfungsbedingungen eine Vergleichsprüfung durchgeführt.

Figure imgb0002
Aus den Prüfergebnissen gemäß Tabelle 1 im Vergleich zu Tabelle 2 geht hervor, daß das Umsetzungsprodukt aus P4O10 mit n-Butanol und Etylenglykol im Molverhältnis von 1 : 2 : 2 trotz des stark sauren Charakters der Lösung (pH-Wert einer 1 %igen wäßrigen Lösung 1,7) korrosionsmindernde Eigenschaften gegenüber Metallen und Metallegierungen aufweist.A comparison test was carried out with solutions of orthophosphoric acid and water in the following proportions in accordance with the test conditions above.
Figure imgb0002
 The test results according to Table 1 in comparison to Table 2 show that the reaction product of P 4 O 10 with n-butanol and ethylene glycol in a molar ratio of 1: 2: 2 despite the strongly acidic nature of the solution (pH value of 1% aqueous solution 1.7) has corrosion-reducing properties against metals and metal alloys.

Beispiel 2Example 2

Es wurde analog Beispiel 1 verfahren, jedoch wurden wäßrige Lösungen in den Mengemerhältnissen gemäß Tabelle 3 hergestellt und nach den in Beispiel 1 angegebenen Prüfbedingungen der Korrosionsabtrag an Stahlblechen ST 37-2 ermittelt. Vergleichsweise wurde wäßrige Orthophosphorsäure ohne Inhibitorzusatz geprüft (Tabelle 4).

Figure imgb0003
Figure imgb0004
 The procedure was analogous to Example 1, but aqueous solutions were prepared in the quantity ratios shown in Table 3 and the corrosion removal on steel sheets ST 37-2 was determined in accordance with the test conditions specified in Example 1. By comparison, aqueous orthophosphoric acid without the addition of inhibitor was tested (Table 4).
Figure imgb0003
Figure imgb0004

Die Wirkung des Korrosionsinhibitors ist anhand der Korrosionsabtragswerte in Tabelle 3 im Vergleich zu Tabelle 4 deutlich zu ersehen.The effect of the corrosion inhibitor can be seen clearly from the corrosion removal values in Table 3 in comparison to Table 4.

Beispiel 3Example 3

Es wurde analog Beispiel 1 verfahren, wobei jedoch die wäßrigen Lösungen anstelle von Phosphorsäure eine der nachstehenden Säuren enthielten:

  • A) Ameisensäure
  • B) Salzsäure
  • C) Schwefelsäure
  • D) Amidoschwefelsäure
The procedure was analogous to Example 1, except that the aqueous solutions contained one of the following acids instead of phosphoric acid:
  • A) Formic acid
  • B) hydrochloric acid
  • C) sulfuric acid
  • D) Amidosulfuric acid

Die wäßrigen Lösungen wurden in den Mengenverhältnissen gemäß Tabelle 5 gegenüber Metallen und Metallegierungen mit der Bezeichnung I bis VI analog Beispiel 1 auf Korrosion geprüft.

Figure imgb0005
Figure imgb0006
Tabelle 5 zeigt, daß der Korrosionsinhibitor nach Beispiel 1 sowohl in wäßrigen Lösungen anorganischer als auch organischer Säuren gegenüber Metallen korrosionsinhibierend wirkt.The aqueous solutions were tested in the proportions according to Table 5 for metals and metal alloys with the designations I to VI analogously to Example 1 for corrosion.
Figure imgb0005
Figure imgb0006
 Table 5 shows that the corrosion inhibitor according to Example 1 has a corrosion-inhibiting effect on metals both in aqueous solutions of inorganic and organic acids.

Beispiel 4Example 4

Das Umsetzungsprodukt aus P4O10, n-Butanol und Ethylenglykol gemäß Beispiel 1 wurde mit weiteren Gemischkomponenten zu einem Reinigungsmittel nachfolgender Zusammensetzung verarbeitet.

Figure imgb0007
The reaction product of P 4 O 10 , n-butanol and ethylene glycol according to Example 1 was processed with further mixture components to form a cleaning agent of the following composition.
Figure imgb0007

10 gew%ige wässerige Lösungen des Reinigungsmittels wurden mit Aluminium bzw. Aluminiumlegierungen gemäß den Prüfungsbedingungen nach Beispiel 1 in Kontakt gebracht.10% by weight aqueous solutions of the cleaning agent were brought into contact with aluminum or aluminum alloys in accordance with the test conditions according to Example 1.

Die Prüfergebnisse sind in Tabelle 6 verzeichnet.

Figure imgb0008
The test results are shown in Table 6.
Figure imgb0008

Beispiel 5Example 5

Das Umsetzungsprodukt von P4010 mit Ethanol und Ethylenglykol in einem Molverhältnis von 1 : 2 : 2 wurde mit den in Tabelle 7 genannten anorganischen und organischen Säuren in einem Mengenverhältnis von 6 Teilen Säure : 4 Teilen Umsetzungsprodukt : 90 Teilen Wasser gelöst und die Korrosivität der Lösung nach den Prüfbedingungen gemäß Beispiel 1 gegenüber Metallen und Metallegierungen mit der Bezeichnung I bis IV analog Beispiel 1 geprüft.

Figure imgb0009
The reaction product of P 4 0 10 with ethanol and ethylene glycol in a molar ratio of 1: 2: 2 was dissolved with the inorganic and organic acids mentioned in Table 7 in a ratio of 6 parts acid: 4 parts reaction product: 90 parts water and the corrosiveness tested the solution according to the test conditions according to Example 1 against metals and metal alloys with the designations I to IV analogously to Example 1.
Figure imgb0009

Beispiel 6Example 6

Es wurde analog Beispiel 4 verfahren, wobei jedoch als Korrosionsinhibitor das Umsetzungsprodukt von P4010 mit Ethanol und Ethylenglykol entsprechend Beispiel 5 verwendet wurde.The procedure was analogous to Example 4, but the reaction product of P4010 with ethanol and ethylene glycol as in Example 5 was used as the corrosion inhibitor.

Die Korrosivität der aus dem Reinigungsmittel hergestellten wäßrigen Lösungen gegenüber Metallen wurde analog Beispiel 1 getestet. Das Ergebnis ist in Tabelle 8 dargestellt.

Figure imgb0010
The corrosiveness of the aqueous solutions produced from the cleaning agent to metals was tested analogously to Example 1. The result is shown in Table 8.
Figure imgb0010

Die Herstellung des Umsetzungsproduktes erfolgte nach dem Verfahren der DE-OS 27 39 916, Beispiel 1.The reaction product was prepared by the process of DE-OS 27 39 916, Example 1.

Beispiel 7Example 7

Das Umsetzungsprodukt nach Beispiel 1 wurde mit Salpetersäure (65 %ig) in den Mengenverhältnissen lt. Tabelle 9 gemischt und nach den Prüfungsbedingungen gemäß Beispiel 1 auf Metalle und Metallegierungen mit der Bezeichnung I bis VI getestet. Die Prüfungsergebnisse sind in Tabelle 9 dargestellt.

Figure imgb0011
The reaction product according to Example 1 was mixed with nitric acid (65%) in the proportions according to Table 9 and tested according to the test conditions according to Example 1 for metals and metal alloys with the designations I to VI. The test results are shown in Table 9.
Figure imgb0011

Claims (10)

1. Verwendung von sauren Phosphorsäureestern oder deren Salze als Mittel zur Verhinderung der Korrosion von Metallen, dadurch gekennzeichnet, daß man zur Verhinderung der durch anorganische und/oder organische Säuren bzw. deren wäßrigen Lösungen verursachten Korrosion von Metallen das Mittel verwendet, das durch Umsetzung von Phosphor-V-oxid mit einem Gemisch, bestehend aus einem einwertigen Alkohol sowie einem Alkanpolyol mit 2 bis 12 C-Atomen und 2 bis 6 Hydroxylgruppen, unter Einhaltung eines Molverhältnisses von Phosphor-V-oxid zu einwertigem Alkohol zu Alkanpolyol von 1 zu 2 zu 4/n, wobei n die Anzahl der Hydroxylgruppen im Alkanpolyolmolekül bedeutet oder eines stöchiometrischen Überschusses der alkoholischen Kompo-nenten sowie Mischen oder Kneten der Reaktionskomponenten bei einer Temperatur zwischen etwa 0°C und 120°C unter Ausschluß von Feuchtigkeit und in Gegenwart eines inerten Gases im Verlauf von etwa 1 - 6 Stunden erhalten wurde.1. Use of acidic phosphoric acid esters or salts thereof as agents for preventing corrosion of metals, characterized in that the agent used to prevent corrosion of metals caused by inorganic and / or organic acids or their aqueous solutions is the agent which is obtained by reacting Phosphorus V-oxide with a mixture consisting of a monohydric alcohol and an alkane polyol with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, while maintaining a molar ratio of phosphorus V-oxide to monohydric alcohol to alkane polyol of 1 to 2 to 4 / n, n being the number of hydroxyl groups in Alkanpolyolmolekül means or a stoichiometric excess of the alcoholic com p o-components as well as mixing or kneading the reaction components at a temperature between about 0 ° C and 120 ° C under exclusion of moisture and in the presence of a inert gas was obtained in the course of about 1-6 hours. 2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß das Metall Stahl, Edelstahl, Kupfer, Aluminium, eine Aluminium/Magnesium/Silicium-Legierung oder eine Aluminium/ Zink/Magnesium-Legierung ist.2. Use according to claim 1, characterized in that the metal is steel, stainless steel, copper, aluminum, an aluminum / magnesium / silicon alloy or an aluminum / zinc / magnesium alloy. 3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Säure Orthophosphorsäure, Ameisensäure, Chlorwasserstoffsäure, Schwefelsäure, Amidoschwefelsäure oder Salpetersäure ist.3. Use according to claim 1 or 2, characterized in that the acid is orthophosphoric acid, formic acid, hydrochloric acid, sulfuric acid, amidosulfuric acid or nitric acid. 4. Verwendung nach Anspruch 1 - 3, dadurch gekennzeichnet, daß der einwertige Alkohol ein aliphatischer Alkohol mit 1 - 22 C-Atomen oder das Umsetzungsprodukt eines aliphatischen Alkohols mit 1 - 22 C-Atomen bzw. eines Phenols mit 6 - 18 C-Atomen mit 2-20 Molen Ethylenoxid ist.4. Use according to claims 1-3, characterized in that the monohydric alcohol is an aliphatic alcohol having 1 to 22 carbon atoms or the reaction product of an aliphatic alcohol having 1 to 22 carbon atoms or a phenol having 6 to 18 carbon atoms with 2-20 moles of ethylene oxide. 5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß der einwertige Alkohol Methanol, Ethanol, Isopropanol, n-Butanol, Isobutanol, Cyclohexanol, 2-Ethylhexanol, Laurylalkohol, Isotridecylalkohol, Stearylalkohol, Oleylalkohol, ein technisches Gemisch aliphatischer Alkohole, 2-Chlorethanol, 2,3-Dibrompropanol-1, 3-Methoxybutanol-1 oder 2-Phenylpropanol-1 ist.5. Use according to claim 4, characterized in that the monohydric alcohol is methanol, ethanol, isopropanol, n-butanol, isobutanol, cyclohexanol, 2-ethylhexanol, lauryl alcohol, isotridecyl alcohol, stearyl alcohol, oleyl alcohol, a technical mixture of aliphatic alcohols, 2-chloroethanol, 2,3-dibromopropanol-1, 3-methoxybutanol-1 or 2-phenylpropanol-1. 6. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß der einwertige Alkohol ein Addukt aus Ethylenoxid und Methylglykol bzw. Ethylglykol, Butylglykol oder Butyldiglykol oder ein Addukt aus 4 Molen Ethylenoxid und 1 Mol Laurylalkohol, aus 8 Molen Ethylenoxid und 1 Mol Stearylalkohol, aus 6 Molen Ethylenoxid und 1 Mol Phenol oder aus 8 Molen Ethylenoxid und 1 Mol Nonylphenol ist.6. Use according to claim 4, characterized in that the monohydric alcohol is an adduct of ethylene oxide and methyl glycol or ethyl glycol, butyl glycol or butyl diglycol or an adduct of 4 moles of ethylene oxide and 1 mole of lauryl alcohol, of 8 moles of ethylene oxide and 1 mole of stearyl alcohol, from 6 Moles of ethylene oxide and 1 mole of phenol or of 8 moles of ethylene oxide and 1 mole of nonylphenol. 7. Verwendung nach Anspruch 1 - 6, dadurch gekennzeichnet, daß das Alkanpolyol Ethylenglykol, Propandiol-1,2, Propandiol-1,3, Butandiol-1,3, Butandiol-1,4, Diethylenglykol, Polyethylenglykol, Neopentylglykol, Dibromneopentylglykol, Glycerin, Trimethylolpropan, Mannit oder Pentaerythrit ist.7. Use according to claims 1-6, characterized in that the alkane polyol ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, polyethylene glycol, neopentyl glycol, dibromoneopentyl glycol, glycerol , Trimethylolpropane, mannitol or pentaerythritol. 8. Verwendung nach Anspruch 1 - 7, dadurch gekennzeichnet, daß das Molverhältnis von Phosphor-V-oxid zu einwertigem Alkohol zu Alkandiol 1 : 2 : 2 beträgt.8. Use according to claims 1-7, characterized in that the molar ratio of phosphorus V-oxide to monohydric alcohol to alkanediol is 1: 2: 2. 9. Verwendung nach Anspruch 1 - 8, dadurch gekennzeichnet, daß das Molverhältnis von Phosphor-V-oxid zu einwertigem Alkohol zu Alkantetrol 1 : 2 : 1 beträgt.9. Use according to claims 1-8, characterized in that the molar ratio of phosphorus V-oxide to monohydric alcohol to alkane tetrol is 1: 2: 1. 10. Verwendung nach Anspruch 1 - 9,,dadurch gekennzeichnet, daß die anorganischen und/oder organischen Säuren bzw. deren wäßrigen Lösungen das Mittel gelöst oder suspendiert in einem Verhältnis von Säure zu Inhibitor wie 100 : 0,5 bis 1 : 1 enthalten.1 0 . Use according to claims 1-9, characterized in that the inorganic and / or organic acids or their aqueous solutions contain the agent dissolved or suspended in a ratio of acid to inhibitor such as 100: 0.5 to 1: 1.
EP80104291A 1979-10-12 1980-07-22 Use of acidic phosphoric acid esters or their salts as corrosion inhibitors for metals Expired EP0028674B1 (en)

Priority Applications (1)

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AT80104291T ATE3781T1 (en) 1979-10-12 1980-07-22 USE OF ACIDIC PHOSPHORIC ACID ESTERS OR THEIR SALTS AS AN AGENT TO PREVENT CORROSION OF METALS.

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DE19792941419 DE2941419A1 (en) 1979-10-12 1979-10-12 USE OF ACID PHOSPHORIC ACID ESTERS OR THEIR SALTS AS AN AGENT TO PREVENT CORROSION OF METALS
DE2941419 1979-10-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454110A1 (en) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluids based on glycol compounds, for metal corrosion inhibiting brakes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUE056796T2 (en) 2012-12-20 2022-03-28 Chemische Fabrik Dr Weigert Gmbh & Co Kg Instrument spray

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3276916A (en) * 1961-09-22 1966-10-04 Lubrizol Corp Inhibition of corrosion of metal surfaces
US3580855A (en) * 1969-04-09 1971-05-25 Rohm & Haas Process for inhibition of scale and corrosion using a polyfunctional phosphated polyol ester having at least 75% primary phosphate ester groups
FR2093177A5 (en) * 1970-04-23 1972-01-28 Witco Chemical Corp
DE2739916A1 (en) * 1977-09-05 1979-03-15 Hoechst Ag Mixed acid orthophosphate ester prodn. - from phosphorus pent-oxide and excess of alkanol and poly-ol, useful e.g. in cleaning compsns.
EP0002530A1 (en) * 1977-12-20 1979-06-27 BASF Aktiengesellschaft Use of acid esters of phosphoric acids and alkoxylated aliphatic polyols as corrosion inhibitors and lubricants

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3276916A (en) * 1961-09-22 1966-10-04 Lubrizol Corp Inhibition of corrosion of metal surfaces
US3580855A (en) * 1969-04-09 1971-05-25 Rohm & Haas Process for inhibition of scale and corrosion using a polyfunctional phosphated polyol ester having at least 75% primary phosphate ester groups
FR2093177A5 (en) * 1970-04-23 1972-01-28 Witco Chemical Corp
DE2739916A1 (en) * 1977-09-05 1979-03-15 Hoechst Ag Mixed acid orthophosphate ester prodn. - from phosphorus pent-oxide and excess of alkanol and poly-ol, useful e.g. in cleaning compsns.
EP0002530A1 (en) * 1977-12-20 1979-06-27 BASF Aktiengesellschaft Use of acid esters of phosphoric acids and alkoxylated aliphatic polyols as corrosion inhibitors and lubricants

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454110A1 (en) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluids based on glycol compounds, for metal corrosion inhibiting brakes

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DE3063771D1 (en) 1983-07-21
ATE3781T1 (en) 1983-06-15
DE2941419A1 (en) 1981-04-23
EP0028674B1 (en) 1983-06-15

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