EP0222311B1 - Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil - Google Patents

Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil Download PDF

Info

Publication number
EP0222311B1
EP0222311B1 EP86115325A EP86115325A EP0222311B1 EP 0222311 B1 EP0222311 B1 EP 0222311B1 EP 86115325 A EP86115325 A EP 86115325A EP 86115325 A EP86115325 A EP 86115325A EP 0222311 B1 EP0222311 B1 EP 0222311B1
Authority
EP
European Patent Office
Prior art keywords
general formula
atoms
oils
compounds
fatty acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86115325A
Other languages
German (de)
French (fr)
Other versions
EP0222311A2 (en
EP0222311A3 (en
Inventor
Gerhard Dr. Borggrefe
Alfred Dr. Meffert
Bert Dr. Gruber
Karl-Heinz Dr. Schmid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86115325T priority Critical patent/ATE60083T1/en
Publication of EP0222311A2 publication Critical patent/EP0222311A2/en
Publication of EP0222311A3 publication Critical patent/EP0222311A3/en
Application granted granted Critical
Publication of EP0222311B1 publication Critical patent/EP0222311B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/22—Acids obtained from polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working

Definitions

  • oils and oil-containing emulsions come into contact with metal surfaces at high temperatures, the liquid media containing more or less large amounts of water. These result in part from the particular process taking place, as is the case, for example, with steam turbines, but can also be a desired component of the respective liquid media. In all such cases, protecting the metal surfaces coming into contact with the liquid media against corrosion poses a significant problem. Iron or iron-containing alloys in particular are corroded by water or moisture in the process liquids. The result in the ongoing process is a reduction in the service life of the respective system or, in the case of further processing of the metal surfaces, the need for complex cleaning of the metal surfaces in preparation for subsequent process steps, for example by phosphating, electroplating, painting, etc.
  • a corrosion inhibitor is added to the process, cleaning or cooling liquids in such cases, which should inhibit, if not completely suppress, the corrosion.
  • DE-B-11 49 843 and EP-B-0 002 780 describe amine salts of amic acids which are obtained by reacting succinic or maleic anhydride with primary alkylamines, and alkanolamine salts of maleic acids as corrosion inhibitors for fuel and lubricating oils or also called water-containing systems.
  • such compounds have the disadvantage that they tend to foam very strongly or - with a low tendency to foam - lose a large part of their corrosion-inhibiting effect.
  • DE-B-12 98 672 also discloses alkali or amine salts of sulfonaminocarboxylic acids, which likewise have a good corrosion protection effect in known metalworking fluids or oil-containing oil emulsions.
  • a disadvantage of these compounds is that they are to be regarded as relatively toxic and their use is therefore subject to severe restrictions.
  • DE-A-29 43 963 also discloses alkanolamine salts of certain alkenylsuccinic acids which, in aqueous systems without foam formation, show good corrosion protection on metal surfaces made of iron or iron-containing alloys.
  • EP-A-0 127 132 also discloses alkenylsuccinic acid halamides as corrosion inhibitors, which are also used in aqueous process fluids for drilling, cutting or rolling metals. In aqueous media in particular, however, hydrolysis of the succinic acid derivatives mentioned is observed, which drastically reduces the corrosion-inhibiting effect of such compounds.
  • the invention relates to the use of alkoxyhydroxy fatty acids and their salts of the general formula (I) in R 1 for unbranched alkyl radicals or alkenyl radicals with 6 to 8 C atoms, R 2 for unbranched or branched alkyl radicals with 1 to 18 C atoms or for unbranched or branched alkenyl radicals with 2 to 18 C atoms, M for hydrogen or organic Ammonium radicals with one or more alkyl radicals or hydroxyalkyl radicals on the nitrogen atom and m represent integers in the range from 3 to 13, in quantities of 0.01 to 10% by weight, based on oil, as corrosion inhibitors in oils and oil-containing emulsions.
  • R 1 for unbranched alkyl radicals or alkenyl radicals with 6 to 8 C atoms
  • R 2 for unbranched or branched alkyl radicals with 1 to 18 C atoms or for unbranched or branched alkenyl radicals with 2 to 18 C atoms
  • the compounds of the general formula (1) which are used according to the invention for corrosion inhibition are known as such.
  • the process for their preparation is described in the relevant literature, for example in DE-A-33 18 596 (EP-A-0 127 810).
  • Alkoxyhydroxy fatty acids and their salts of the general formula (I) are then formed, for example, by the fact that fatty acids or their esters of the general formula (11) in which R 1 and m have the meanings given above and M can stand for hydrogen or an alkyl group, preferably alcohols occurring in natural fats or oils, can be exposed by methods known per se.
  • Such an epoxidation reaction can be carried out, for example, by reacting the fatty acids or their esters of the general formula (II) with organic peroxo acids under suitable conditions.
  • the epoxides obtained in this way which carry the oxirane ring at the position in the molecule at which the olefinic double bond was found in the starting materials, are then, according to processes which are also known per se, by acid-catalyzed ring opening with alcohols of the general formula in which R 2 can have the meanings given above, converted into the corresponding alkoxyhydroxyfatty acid derivatives in which the alkoxy group R 2 0 and the hydroxyl group are each attached to the two carbon atoms connected in the starting material by the olefinic double bond.
  • the terminal ester grouping of the epoxides can also be transesterified.
  • esters resulting from this reaction sequence are then saponified by alkaline methods which are also known per se, giving the salts of the general formula (I) in which M represents organic ammonium radicals having one or more alkyl or hydroxyalkyl radicals on the nitrogen atom. If appropriate, the corresponding salts can be converted into the corresponding acids (I) in which M represents hydrogen by adjusting an acidic pH in the reaction medium.
  • Naturally occurring fats and oils of the general formula (11) are preferably used, which are inexpensively available in large quantities from native sources.
  • Soybean oil which has a high content of oleic acid and linoleic acid, sunflower oil, sesame oil, corn oil, cottonseed oil, palm oil or coconut oil are preferred.
  • Such natural fats and oils contain high proportions of esters of unsaturated fatty acids of the general formula (I), in which R 'represents unbranched alyl radicals or alkenyl radicals, for example with 8 carbon atoms.
  • esters of different chain lengths can also be found in such oils of native origin, for example, in soybean oil, mixtures of fatty acid esters of the general formula (11) are found in which R 'represents alkyl and alkenyl radicals with 8 C atoms, the saturated and Unsaturated portions are in a weight ratio of 1: 2.
  • R ' represents alkyl and alkenyl radicals with 8 C atoms
  • Unsaturated portions are in a weight ratio of 1: 2.
  • Such compounds are to be regarded as preferably usable in the sense of the present invention.
  • the alcohols of the general formula (III) used for the alcoholysis of the oxirane ring contain unbranched or branched allyl residues with 1 to 18 carbon atoms or unbranched or branched alkenyl residues with 2 to 18 carbon atoms.
  • Unbranched alkyl radicals or alkenyl radicals with 8 to 18 carbon atoms are to be regarded as preferred, which can also be provided inexpensively in large quantities from native sources.
  • alcohol mixtures of natural origin are used which have unbranched alkyl radicals with 16 carbon atoms and alkenyl radicals with 18 carbon atoms.
  • salt (1) in which M stands for a diethanolammonium radical is particularly preferably used.
  • the alkoxyhydroxy fatty acids mentioned and their salts of the general formula (I) given are used as corrosion inhibitors in lubricating oils, lubricating greases, power transmission oils and metalworking emulsions based on mineral oils. They are used in a wide range of quantities in oils or oil-containing emulsions. The amounts can vary in the range from 0.01 to 10% by weight, based on the oil base, and are preferably from 0.05 to 0.5%. Oils and oil-containing emulsions which contain alkoxyhydroxy fatty acids or their salts of the general formula (I) in these amounts show a corrosion protection on iron and iron-containing metal surfaces which is at least equivalent to that of the compounds known hitherto.
  • the alkoxyhydroxy fatty acids mentioned or their salts are superior to the previously known compounds in that they can be made inexpensively accessible in large quantities from natural raw materials.
  • test specimens were stored in solutions without inhibitor (see FIG. 1) or in the corresponding mixtures which contained a commercially available alkenylsuccinic acid half-ester, the concentration of which corresponded to the concentration of the alkoxyhydroxy fatty acids used according to the invention (see FIG. 2).
  • concentration of which corresponded to the concentration of the alkoxyhydroxy fatty acids used according to the invention see FIG. 2.
  • Tables 2 and 3 The results are also shown in Tables 2 and 3 below.
  • gray cast iron chips were wetted on a round filter with an oil emulsion in water contaminated with chloride or hardness, which were produced using alkoxyhydroxy fatty acids or their salts of the general formula (I) according to the invention. After an exposure time of 2 h at room temperature, the corrosion marks on the filter paper were assessed visually according to the method specified in the standard.
  • the emulsions were prepared from the corresponding concentrates by customary methods using water with a total hardness of 3.58 mmol CaCl 2 .6H 2 O and MgSO 4 .7H 2 O.
  • the emulsions were prepared by stirring 8 to 25% by weight of the stated concentrates (formulations 1 and 2) in water with the stated total hardness. This corresponds to DIN 51360 / Part 2.
  • Example 2 Analogously to Example 2, an emulsion was used which did not contain an inhibitor of the general formula (I). In this comparison emulsion, the ratio of naphthenic mineral oil: emulsifier (adduct of 6.5 EO with nonylphenol) was 4: 1.
  • the corrosion protection S was then calculated in% according to the following equation from the comparison of the results with the averaged removals in the case of a blank sample made from inhibitor-free emulsion:
  • steel sheets (quality ST 1405, degreased and sanded, dimensions: 25 x 50 mm) were immersed in mineral oil emulsions which had been produced using the substances used according to the invention. Different amounts of inhibitor were used in the mineral oil emulsions. After a certain draining and drying time, the sheets were stored in a humidity chamber at 100% relative atmospheric humidity. After the test period (1 to 7 days), the steel sheets were checked for signs of corrosion. The evaluation was carried out on the evaluation scale given in Example 1 from 0 to 4.
  • Example 4 identical steel sheets of the same size were stored in mineral oil emulsions which did not contain an inhibitor.
  • the comparison emulsions contained naphthenic mineral oil and emulsifier (adduct of 6.5 EO with nonylphenol) in a weight ratio of 4: 1.

Abstract

Acid cleaning/pickling compositions for metal surfaces containing (A) at least one protein-derived polymer, sugar-derived polymer, sorbitol, tannin, or vinyl-based polymer, (B) at least one iodine or iodine-affording compound; acids solutions prepared therefrom; and methods for their use.

Description

In technischen Prozessen der mechanischen Bearbeitung und Reinigung von Metalloberflächen wie auch in technischen kühlprozessen kommen mitunter bei hohen Temperaturen Öle und ölhaltige Emulsionen mit Metalloberflächen in Kontakt, wobei die flüssigen Medien mehr oder weniger große Wassermengen enthalten. Diese resultieren zum Teil aus dem jeweils ablaufenden Prozeß, wie dies beispielsweise bei Dampfturbinen der Fall ist, können jedoch auch erwünschter Bestandteil der jeweiligen flüssigen Medien sein. In allen derartigen Fällen wirft der Schutz der mit den flüssigen Medien in Kontakt kommenden Metalloberflächen gegen Korrosion ein erhebliches Problem auf. Insbesondere Eisen oder eisenhaltige Legierungen werden durch Wasser bzw. Feuchtigkeit in den Prozeßflüssigkeiten korrodiert. Die Folge sind im laufenden Prozeß eine Reduzierung der Lebensdauer der jeweiligen Anlage bzw. bei Weiterverarbeitung der Metalloberflächen das Erfordernis einer aufwendigen Reinigung der Metalloberflächen zur Vorbereitung für nachfolgende Prozeßschritte, beispielsweise durch Phosphatierung, galvanische Beschichtung, Lackierung usw.In technical processes for mechanical processing and cleaning of metal surfaces as well as in technical cooling processes, oils and oil-containing emulsions come into contact with metal surfaces at high temperatures, the liquid media containing more or less large amounts of water. These result in part from the particular process taking place, as is the case, for example, with steam turbines, but can also be a desired component of the respective liquid media. In all such cases, protecting the metal surfaces coming into contact with the liquid media against corrosion poses a significant problem. Iron or iron-containing alloys in particular are corroded by water or moisture in the process liquids. The result in the ongoing process is a reduction in the service life of the respective system or, in the case of further processing of the metal surfaces, the need for complex cleaning of the metal surfaces in preparation for subsequent process steps, for example by phosphating, electroplating, painting, etc.

Zur Inhibierung der Korrosion wird in solchen Fällen den Prozeß-, Reinigungs- oder Kühlflüssigkeiten ein Korrosionsinhibitor zugesetzt, der die Korrosion inhibieren, wenn nicht sogar vollständig unterdrücken soll.To inhibit corrosion, a corrosion inhibitor is added to the process, cleaning or cooling liquids in such cases, which should inhibit, if not completely suppress, the corrosion.

In der DE-B-11 49 843 sowie der EP-B-0 002 780 werden Aminsalze von Amidsäuren, die man durch Umsetzung von Bernstein- oder Maleinsäureanhydrid mit primären Alkylaminen erhält, sowie Alkanolaminsalze von Maleinamidsäuren als Korrosionsinhibitoren für Brennstoff-und Schmieröle bzw. auch Wasser enthaltende Systeme genannt. Derartige Verbindungen weisen jedoch den Nachteil auf, daß sie ausgesprochen stark zur Schaumbildung neigen oder - bei geringer Neigung zur Schaumbildung - einen großen Teil ihrer korrosionsinhibierenden Wirkung einbüßen.DE-B-11 49 843 and EP-B-0 002 780 describe amine salts of amic acids which are obtained by reacting succinic or maleic anhydride with primary alkylamines, and alkanolamine salts of maleic acids as corrosion inhibitors for fuel and lubricating oils or also called water-containing systems. However, such compounds have the disadvantage that they tend to foam very strongly or - with a low tendency to foam - lose a large part of their corrosion-inhibiting effect.

In der DE-B-12 98 672 werden zudem Alkali- bzw. Aminsalze von Sulfonaminocarbonsäuren offenbart, die ebenfalls eine gute Korrosionsschutzwirkung in bekannten Metallbearbeitungsflüssigkeiten oder Wasser enthaltenden Ölemulsionen zeigen. Nachteilig an diesen Verbindungen ist jedoch, daß sie als relativ toxisch anzusehen sind und ihre Verwendung daher starken Beschränkungen unterworfen ist.DE-B-12 98 672 also discloses alkali or amine salts of sulfonaminocarboxylic acids, which likewise have a good corrosion protection effect in known metalworking fluids or oil-containing oil emulsions. However, a disadvantage of these compounds is that they are to be regarded as relatively toxic and their use is therefore subject to severe restrictions.

Aus der DE-A-29 43 963 sind zudem Alkanolaminsalze bestimmter Alkenylbernsteinsäuren bekannt, die in wässrigen Systemen ohne Schaumbildung einen guten Korrosionsschutz auf Metalloberflächen aus Eisen oder eisenhaltigen Legierungen zeigen. Aus der EP-A-0 127 132 sind außerdem Alkenylbernsteinsäurehalbamide als Korrosionsschutzmittel bekannt, die ebenfalls in wässrigen Prozeßflüssigkeiten zum Bohren, Schneiden bzw. Walzen von Metallen eingesetzt werden. Gerade in wässrigen Medien wird jedoch mitunter eine Hydrolyse der genannten Bernsteinsäurederivate beobachtet, die die korrosionsinhibierende Wirkung derartiger Verbindungen drastisch herabsetzt. Außerdem stehen die zur Herstellung derartiger Verbindungen notwendigen Ausgangsstoffe erst nach zum Teil aufwendigen Synthesen zur Verfügung, so daß es erforderlich schien, neue korrosionsschützende Wirkstoffe zu finden, die nicht nur universell anwendbar sind, sondern auch die hiergeschilderten Nachteile, wie Neigung zur Schaumbildung, Hydrolyseinstabilität, Toxizität, Unverträglichkeit mit hartem Prozeßwasser usw. nicht aufweisen.DE-A-29 43 963 also discloses alkanolamine salts of certain alkenylsuccinic acids which, in aqueous systems without foam formation, show good corrosion protection on metal surfaces made of iron or iron-containing alloys. EP-A-0 127 132 also discloses alkenylsuccinic acid halamides as corrosion inhibitors, which are also used in aqueous process fluids for drilling, cutting or rolling metals. In aqueous media in particular, however, hydrolysis of the succinic acid derivatives mentioned is observed, which drastically reduces the corrosion-inhibiting effect of such compounds. In addition, the starting materials required for the preparation of such compounds are only available after in some cases complex syntheses, so that it seemed necessary to find new anticorrosive active ingredients which are not only universally applicable, but also the disadvantages described here, such as tendency to foam formation, hydrolysis instability, Do not display toxicity, incompatibility with hard process water etc.

Es wurde nun überraschend gefunden, daß Ringöffnungsprodukte von Epoxyfettsäuren mit unverzweigten oder verzweigten Alkoholen sowie deren Salze als Korrosionshibitoren in Mineralölen und mineralölhaltigen Emusionen vorzüglich geeignet sind. Die Erfindung betrifft die Verwendung von Alkoxyhydroxyfettsäuren und deren Salzen der allgemeinen Formel (I)

Figure imgb0001
in der R1 für unverzweigte Alkylreste oder Alkenylreste mit 6 bis 8 C-Atomen, R2 für unverzweigte oder verzweigte Alkylreste mit 1 bis 18 C-Atomen oder für unverzweigte oder verzweigte Alkenylreste mit 2 bis 18 C-Atomen, M für Wasserstoff oder organische Ammoniumreste mit einem oder mehreren Alkylresten oder Hydroxyalkylresten am Stickstoffatom und m für ganze Zahlen im Bereich von 3 bis 13 stehen, in Mengen von 0,01 bis 10 Gew.-%, bezogen auf Ölbasis, als Korrosionsinhibitoren in Ölen und ölhatigen Emulsionen.It has now surprisingly been found that ring opening products of epoxy fatty acids with unbranched or branched alcohols and their salts are particularly suitable as corrosion inhibitors in mineral oils and emulsions containing mineral oils. The invention relates to the use of alkoxyhydroxy fatty acids and their salts of the general formula (I)
Figure imgb0001
 in R 1 for unbranched alkyl radicals or alkenyl radicals with 6 to 8 C atoms, R 2 for unbranched or branched alkyl radicals with 1 to 18 C atoms or for unbranched or branched alkenyl radicals with 2 to 18 C atoms, M for hydrogen or organic Ammonium radicals with one or more alkyl radicals or hydroxyalkyl radicals on the nitrogen atom and m represent integers in the range from 3 to 13, in quantities of 0.01 to 10% by weight, based on oil, as corrosion inhibitors in oils and oil-containing emulsions.

Die Verbindungen der allgemeinen Formel (1), die erfindungsgemäß zur Korrosionsinhibierung verwendet werden, sind als solche bekannt. Das Verfahren zu ihrer Herstellung ist im einschlägigen Schrifttum, beispielsweise in der DE-A-33 18 596 (EP-A-0 127 810), beschrieben. Alkoxyhydroxyfettsäuren und deren Salze der allgemeinen Formel (I) entstehen danach beispielsweise dadurch, daß Fettßsäuren oder deren Ester der allgemeinen Formel (11)

Figure imgb0002
in der R1 und m die oben angegebenen Bedeutungen haben und M für Wasserstoff oder eine Alkylgruppe, bevorzugt von in natürlichen Fetten oder Ölen verestert vorkommenden Alkoholen stehen kann, nach an sich bekannten Verfahren expodiert werden. Eine derartige Epoxidationsreaktion kann beispielsweise durch Umsetzung der Fettsäuren oder deren Estern der allgemeinen Formel (II) mit organischen Peroxosäuren unter geeigneten Bedingungen erfolgen. Die auf diesem Wege erhaltenen Epoxide, die den Oxiranring an der Position im Molekül tragen, an der in den Edukten die olefinische Doppelbindung zu finden war, werden dann nach ebenfalls an sich bekannten Verfahren durch sauerkatalysierte Ringöffnung mit Alkoholen der allgemeinen Formel
Figure imgb0003
in der R2 die oben angegebenen Bedeutungen haben kann, in die entsprechenden Alkoxyhydroxyfettsäurederivate überführt, in denen die Alkoxygruppe R20 und die Hydroxygruppe je an den beiden im Edukt durch die olefinische Doppelbindung verbundenen Kohlenstoffatomen angebunden sind. Je nach Einsatzmenge an Alkohol kann dabei auch die endständige Estergruppierung der Epoxide umgeestert werden.The compounds of the general formula (1) which are used according to the invention for corrosion inhibition are known as such. The process for their preparation is described in the relevant literature, for example in DE-A-33 18 596 (EP-A-0 127 810). Alkoxyhydroxy fatty acids and their salts of the general formula (I) are then formed, for example, by the fact that fatty acids or their esters of the general formula (11)
Figure imgb0002
 in which R 1 and m have the meanings given above and M can stand for hydrogen or an alkyl group, preferably alcohols occurring in natural fats or oils, can be exposed by methods known per se. Such an epoxidation reaction can be carried out, for example, by reacting the fatty acids or their esters of the general formula (II) with organic peroxo acids under suitable conditions. The epoxides obtained in this way, which carry the oxirane ring at the position in the molecule at which the olefinic double bond was found in the starting materials, are then, according to processes which are also known per se, by acid-catalyzed ring opening with alcohols of the general formula
Figure imgb0003
 in which R 2 can have the meanings given above, converted into the corresponding alkoxyhydroxyfatty acid derivatives in which the alkoxy group R 2 0 and the hydroxyl group are each attached to the two carbon atoms connected in the starting material by the olefinic double bond. Depending on the amount of alcohol used, the terminal ester grouping of the epoxides can also be transesterified.

Die aus dieser Reaktionsfolge resultierenden Ester werden dann nach ebenfalls an sich bekannten Methoden alkalische verseift, wobei die Salze der allgemeinen Formel (I) entstehen, in denen M für organische Ammoniumreste mit einem oder mehreren Alkyl- oder Hydroxyalkylresten am Stickstoffatom steht. Gegebenenfalls können die entsprechenden Salze durch Einstellen eines sauren pH-Wertes im Reaktionsmedium in die entsprechenden Säuren (I) überführt werden, in denen M für Wasserstoff steht.The esters resulting from this reaction sequence are then saponified by alkaline methods which are also known per se, giving the salts of the general formula (I) in which M represents organic ammonium radicals having one or more alkyl or hydroxyalkyl radicals on the nitrogen atom. If appropriate, the corresponding salts can be converted into the corresponding acids (I) in which M represents hydrogen by adjusting an acidic pH in the reaction medium.

Für derartige Reaktionsfolgen werden bevorzugt natürlich vorkommende Fette und Öle der allgemeinen Formel (11) eingesetzt, die aus nativen Quellen in großen mengen preisgünstig zugängliche sind. Bevorzugt werden dabei Sojabohnenöl, das einen hohen Gehalt an Ölsäure und Linolsäure aufweist, Sonenblumenöl, Sesamöl, Maisöl, Baumwollsamenöl, Palmöl oder Kokosnußöl. Derartige natürliche Fette und Öle enthalten hohe Anteile an Estern ungesättigter Fettsäuren der allgemeinen Formel (I), in denen R' für unverzweigte Alylreste oder Alkenylreste, beispielsweise mit 8 C-Atomen, steht. Mitunter sind in derartigen Ölen nativer Herkunft auch Gemische von Estern unterschiedlicher Kettenlänge anzutreffen, beispiellsweise findet man in Sojaöl Mischungen von Fettsäureestern der allgemeinen Formel (11), in denen R' für Alkyl- und Alkenylreste mit 8 C-Atomen steht, wobei die gesättigten und ungesättigten Anteile zueinander im Gewichtsverhältnis von 1:2 stehen. Derartige Verbindungen sind als im Sinne der vorliegenden Erfindung bevorzugt verwendbar anzusehen.For such reaction sequences, naturally occurring fats and oils of the general formula (11) are preferably used, which are inexpensively available in large quantities from native sources. Soybean oil which has a high content of oleic acid and linoleic acid, sunflower oil, sesame oil, corn oil, cottonseed oil, palm oil or coconut oil are preferred. Such natural fats and oils contain high proportions of esters of unsaturated fatty acids of the general formula (I), in which R 'represents unbranched alyl radicals or alkenyl radicals, for example with 8 carbon atoms. Mixtures of esters of different chain lengths can also be found in such oils of native origin, for example, in soybean oil, mixtures of fatty acid esters of the general formula (11) are found in which R 'represents alkyl and alkenyl radicals with 8 C atoms, the saturated and Unsaturated portions are in a weight ratio of 1: 2. Such compounds are to be regarded as preferably usable in the sense of the present invention.

Die für die Alkoholyse des Oxiranrings verwendeten Alkohole der allgemeinen Formel (111) enthalten unverzweigte oder verzweigte Alylreste mit 1 bis 18 C-Atomen oder unverzweigte oder verzweigte Alkenylreste mit 2 bis 18 C-Atomen. Als bevorzugt sind dabei unverzweigte Alkylreste oder Alkenylreste mit 8 bis 18 C-Atomen anzusehen, die ebenfalls aus nativen Quellen in großen Mengen preiswert zur Verfügung gestellt werden können. Dabei greift man insbesondere auf Alkoholgemische natürlicher Herkunft zurück, die unverzweigte Alkylreste mit 16 C-Atomen und Alkenylreste mit 18 C-Atomen aufweisen. Als solche sind beispielsweise Gemische aus Cetylalkohol und Oleylalkohol anzusehen; Umsetzungsprodukte dieser Alkoholgemische mit expoxidierten Fettsäuren nativer Herkunft führen zu Alkoxyhydroxyfettsäuren, die als besonders bevorzugt im Sinne der vorliegenden Erfindung verwendet werden können.The alcohols of the general formula (III) used for the alcoholysis of the oxirane ring contain unbranched or branched allyl residues with 1 to 18 carbon atoms or unbranched or branched alkenyl residues with 2 to 18 carbon atoms. Unbranched alkyl radicals or alkenyl radicals with 8 to 18 carbon atoms are to be regarded as preferred, which can also be provided inexpensively in large quantities from native sources. In particular, alcohol mixtures of natural origin are used which have unbranched alkyl radicals with 16 carbon atoms and alkenyl radicals with 18 carbon atoms. Mixtures of cetyl alcohol and oleyl alcohol are to be regarded as such; Reaction products of these alcohol mixtures with epoxidized fatty acids of native origin lead to alkoxyhydroxy fatty acids, which can be used as particularly preferred in the sense of the present invention.

Erfindungsgemäß sind als Korrosionsinhibitoren nicht nur die freien Alkoxyhydroxyfettsäuren (I) verwendbar, in denen M für Wasserstoff steht, sondern auch deren öllösliche Salze (I), in denen M für organische Ammoniumreste mit einem oder mehreren Alkylresten oder Hydroxyalkylresten am Stickstoffatom steht. Als bevorzugte Kationen derartiger Salze werden Ammoniumkationen angesehen, die zwei oder drei Alkylreste oder Hydroxyalkylreste am Stickstoffatom tragen. Von diesen besonders bevorzugt verwendet wird das Salz (1), in dem M für einen Diethanolammoniumreste steht.According to the invention, not only the free alkoxyhydroxy fatty acids (I) in which M represents hydrogen, but also their oil-soluble salts (I) in which M represents organic ammonium radicals with one or more alkyl radicals or hydroxyalkyl radicals on the nitrogen atom can be used as corrosion inhibitors. Preferred cations of such salts are ammonium cations which carry two or three alkyl radicals or hydroxyalkyl radicals on the nitrogen atom. Of these, salt (1) in which M stands for a diethanolammonium radical is particularly preferably used.

Die genannten Alkoxyhydroxyfettsäuren und deren Salze der angegebenen allgemeinen Formel (I) werden in Schmierölen, Schmierfetten, Kraftübertragungsölen und Metallbearbeitungsemulsionen auf Mineralölbasis als Korrosionsinhibitoren eingesetzt. Sie werden dabei in weiten Mengenbereichen in Ölen oder ölhaltigen Emulsionen verwendet. Die Mengen können im Bereich von 0,01 bis 10 Gew.-%, bezogen auf die Ölbasis, schwanken und liegen vorzugsweise bei 0,05 bis 0,5%. Öle und ölhatige Emulsionen, die Alkoxyhydroxyfettsäuren oder deren Salze der allgemeinen Formel (I) in diesen Mengen enthalten, zeigen einen den bisher bekannten Verbindungen zumindest gleichwertigen Korrosionsschutz auf Eisen und eisenhaltigen Metalloberflächen. Die genannten Alkoxyhydroxyfettsäuren oder deren Salze sind den bisher bekannten Verbindungen dadurch überlegen, daß sie aus natürlichen Rohstoffen in großen Mengen preiswert zugänglich gemacht werden können.The alkoxyhydroxy fatty acids mentioned and their salts of the general formula (I) given are used as corrosion inhibitors in lubricating oils, lubricating greases, power transmission oils and metalworking emulsions based on mineral oils. They are used in a wide range of quantities in oils or oil-containing emulsions. The amounts can vary in the range from 0.01 to 10% by weight, based on the oil base, and are preferably from 0.05 to 0.5%. Oils and oil-containing emulsions which contain alkoxyhydroxy fatty acids or their salts of the general formula (I) in these amounts show a corrosion protection on iron and iron-containing metal surfaces which is at least equivalent to that of the compounds known hitherto. The alkoxyhydroxy fatty acids mentioned or their salts are superior to the previously known compounds in that they can be made inexpensively accessible in large quantities from natural raw materials.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.

Zur erfindungsgemäßen Verwendung wurden nach dem oben beschreibenen Weg die Verbindungen der nachfolgenden Tabelle 1 hergestellt, deren Löslichkeit in Ölen unterschiedlichen Charakters ebenfalls in Tabelle 1 angegeben wird.

Figure imgb0004
For the use according to the invention, the compounds of Table 1 below were prepared according to the route described above, and their solubility in oils of different characters is also given in Table 1.
Figure imgb0004

Beispiel 1example 1

Entfettete und geschmirgelte Stahlstäbe (Material: CK15 nach DIN 17 210) wurden 24 h in gerührten Mischungen aus Mineralöl und destilliertem Wasser im Verhältnis 10:1 (Verfarhen A) bzw. Mineralöl und künstlichem Meerwasser (Verhältnis 10:1) (Verfahren B) nach DIN 51585 bei 60°C gelagert. Nach Ablauf der vorgeschreibenen Prüfdauer wurden die Prüfkörper auf Korrosionserscheinungen beurteilt. Die Bewertung folgte folgender Bewewrtungksskala:

  • 0: keine Korrosion,
  • 1: Spuren von Korrosion,
  • 2: leichte Korrosion (korrodierte Fläche 5%),
  • 3: Mäßige Korrosion (korrodierte Fläche im Bereicht von 5 bis 20%), und
  • 4: starke Korrosion (korrodierte Fläche 20%).
  • Die Ergebnisse sind den nachfolgenden Tabellen 2 und 3 zu entnehmen.
Degreased and sanded steel rods (material: CK15 according to DIN 17 210) were subsequently mixed for 24 hours in stirred mixtures of mineral oil and distilled water in a ratio of 10: 1 (procedure A) or mineral oil and artificial sea water (ratio 10: 1) (procedure B) DIN 51585 stored at 60 ° C. After the prescribed test period, the test specimens were assessed for signs of corrosion. The evaluation followed the following evaluation scale:
  • 0: no corrosion,
  • 1: traces of corrosion,
  • 2: slight corrosion (corroded area 5%),
  • 3: moderate corrosion (corroded area in the range of 5 to 20%), and
  • 4: severe corrosion (corroded area 20%).
  • The results are shown in Tables 2 and 3 below.

Vergleichsbeispiele 1 und 2Comparative Examples 1 and 2

Zum Vergleich wurden unter den Beispiel 1 angegebenen Bedingungen identische Prüfkörper in Lösungen ohne Inhibitor (Vgl. 1) bzw. in den entsprechenden Mischungen gelagert, die einen handelsüblichen Alkenylbernsteinsäurehalbester enthielten, dessen Konzentration der Konzentration der erfindungsgemäß verwendeten Alkoxyhydroxyfettsäuren entsprach (Vgl. 2). Die Ergebnisse sind ebenfalls den nachfolgenden Tabellen 2 und 3 zu entnehmen.

Figure imgb0005
Figure imgb0006
 For comparison, identical test specimens were stored in solutions without inhibitor (see FIG. 1) or in the corresponding mixtures which contained a commercially available alkenylsuccinic acid half-ester, the concentration of which corresponded to the concentration of the alkoxyhydroxy fatty acids used according to the invention (see FIG. 2). The results are also shown in Tables 2 and 3 below.
Figure imgb0005
Figure imgb0006

Beispiel 2Example 2

Grauguß-Filterpapiertest nach DIN 51360/Teil 2.Gray cast iron filter paper test according to DIN 51360 / Part 2.

In diesem Prüfverfahren wurden Graugußspäne auf einem Rundfilter mit einer Ölemulsion in chloridbelastetem bzw. härtebelastetem Wasser benetzt, die unter erfindungsgemäßer Verwendung von Alkoxyhydroxyfettsäuren bzw. deren Salzen der allgemeinen Formel (I) hergestellt waren. Nach einer Einwirkungsdauer von 2 h bei Raumtemperatur wurden die Korrosionabzeichnungen auf dem Filterpapier nach dem in der Norm angegebenen Verfahren visuell beurteilt.In this test method, gray cast iron chips were wetted on a round filter with an oil emulsion in water contaminated with chloride or hardness, which were produced using alkoxyhydroxy fatty acids or their salts of the general formula (I) according to the invention. After an exposure time of 2 h at room temperature, the corrosion marks on the filter paper were assessed visually according to the method specified in the standard.

Die Emulsionen wurden aus den entsprechenden Konzentraten nach üblichen Methoden unter Einsatz von Wasser mit einer Gesamthärte von 3,58 mmol CaCl2·6H2O und MgSO4·7H2O hergestellt.The emulsions were prepared from the corresponding concentrates by customary methods using water with a total hardness of 3.58 mmol CaCl 2 .6H 2 O and MgSO 4 .7H 2 O.

Die verwendeten Rezepturen wurden unter Verwendung folgender Konzentrate hergestellt:

Figure imgb0007
Figure imgb0008
 The recipes used were made using the following concentrates:
Figure imgb0007
Figure imgb0008

Alle Prozentangaben sind Gewichtsprozente.All percentages are percentages by weight.

Die Emulsionen wurden dadurch hergestellt, daß 8 bis 25 Gew.-% der angegebenen Konzentrate (Rezepturen 1 bzw. 2) in Wasser mit der angegebenen Gesamthärte eingerührt wurden. Dies entspricht DIN 51360/Teil 2.The emulsions were prepared by stirring 8 to 25% by weight of the stated concentrates (formulations 1 and 2) in water with the stated total hardness. This corresponds to DIN 51360 / Part 2.

Die Ergebnisse sind der nachfolgenden Tabelle 4 zu entnehmen.The results are shown in Table 4 below.

Der Korrosionograd wurde dabei wie folgt bewertet:

  • 0: keine Korrosion,
  • 1: Spuren von Korrosion, 10
  • 2: leichte Korrosion (korrodierte Fläche 1%),
  • 3: mäßige Korrosion (korrodierte Fläche im Bereich von 1 bis 5%), und
  • 4: starke Korrosion (korrodierte Fläche 5%).
The degree of corrosion was assessed as follows:
  • 0: no corrosion,
  • 1: traces of corrosion, 1 0
  • 2: slight corrosion (corroded area 1%),
  • 3: moderate corrosion (corroded area in the range of 1 to 5%), and
  • 4: severe corrosion (corroded area 5%).

Vergleichsbeispiel 3Comparative Example 3

In Analogie zu Beispiel 2 wurde eine Emulsion verwendet, die keinen Inhibitor der allgemeinen Formel (I) enthielt. In dieser Vergleichsemulsion betrug das Verhältnis naphthenisches Mineralöl:Emulgator (Addukt von 6,5 EO an Nonylphenol) 4:1.Analogously to Example 2, an emulsion was used which did not contain an inhibitor of the general formula (I). In this comparison emulsion, the ratio of naphthenic mineral oil: emulsifier (adduct of 6.5 EO with nonylphenol) was 4: 1.

Die Ergebenisse sind ebenfalls der nachfolgenden Tabelle 4 zu entnehmen (Vgl. 3).

Figure imgb0009
The results are also shown in Table 4 below (see Fig. 3).
Figure imgb0009

Beispiel 3Example 3

Es wurde ein weiterer Korrosionsschutztest durchgeführt, in dem geschmirgelte Stahlbleche (ST 1405), Maße: 25 x 50 mm in gerührten Mineralölemulsionen bei erhöhter Temperatur gehalten wurden. Es wurden zwei jeweils rotierende Stahlbleche gleicher Zusammensetzung, Große und Oberflächengüte bei 50°C über drei Tage der Einwirkung einer chlorid- und härtebelasteten Mineralölemulsion ausgesetzt und nach Ablauf der Prüfdauer bei beiden Blechen gravimetrisch die Massenverluste bestimmt und gemittelt.Another corrosion protection test was carried out in which sanded steel sheets (ST 1405), dimensions: 25 x 50 mm, were kept in stirred mineral oil emulsions at elevated temperature. Two rotating steel sheets of the same composition, size and surface quality were exposed to a chloride and hardness-stressed mineral oil emulsion at 50 ° C for three days and after the test period the mass losses of both sheets were determined and averaged gravimetrically.

Aus dem Vergleich der Ergebnisse mit den gemittelten Abträgen bei einer Blindprobe aus inhibitorfreier Emulsion wurde danach der Korrosionsschutz S in % gemäß folgender Gleichung errechnet:

Figure imgb0010
The corrosion protection S was then calculated in% according to the following equation from the comparison of the results with the averaged removals in the case of a blank sample made from inhibitor-free emulsion:
Figure imgb0010

In der Gleichung bedeuten:

  • Go: Gewichtsdifferenz des Prüfblechs vor und nach der Lagerung in inhibitorfreier Emulsion, und
  • G,: Gewichtsdifferenz des Prüfblechs vor und nach der Lagerung in inhibitorhaltiger Emulsion.
In the equation:
  • G o : weight difference of the test sheet before and after storage in an inhibitor-free emulsion, and
  • G ,: Weight difference of the test sheet before and after storage in an inhibitor-containing emulsion.

Die Ergebnisse sind der nachfolgenden Tabelle 5 zu entnehmen.The results are shown in Table 5 below.

Vergleichsbeispiel 4Comparative Example 4

In Analogie zu Beispiel 3 wurden Stahlbleche unter gleichen Reaktionsbedingungen in einer Mineralölemulsion gehalten, die keinen Inhibitor enthielt. In dieser Emulsion betrug das Gewichtsverhältnis Mineralöl:Emulgator 4:1.In analogy to Example 3, steel sheets were kept under the same reaction conditions in a mineral oil emulsion which contained no inhibitor. The mineral oil: emulsifier weight ratio in this emulsion was 4: 1.

Die Ergebnisse sind ebenfalls Tabelle 5 zu entnehmen (Vgl. 4).

Figure imgb0011
The results are also shown in Table 5 (cf. 4).
Figure imgb0011

Beispiel 4Example 4

In einem weiteren Korrosionstest wurden Stahlbleche (Qualität ST 1405, entfettet und geschmirgelt, Maße: 25 x 50 mm) in Mineralölemulsionen getaucht, die unter Einsatz der erfindungsgemäß verwendeten Substanzen hergestellt worden waren. In den Mineralölemulsionen wurden unterschiedliche Inhibitormengen verwendet. Die Bleche wurden nach einer bestimmten Abtropf- und Trockendauer bei 100% relativer Luftfeuchtigkeit in einer Feuchtigkeitskammer gelagert. Nach Ablauf der Prüfdauer (1 bis 7 Tage) wurden die Stahlbleche auf Korrosionserscheinungen überprüft. Die Bewertung wurde nach der in Beispiel 1 angegebenen Bewertungsskala von 0 bis 4 vorgenommen.In a further corrosion test, steel sheets (quality ST 1405, degreased and sanded, dimensions: 25 x 50 mm) were immersed in mineral oil emulsions which had been produced using the substances used according to the invention. Different amounts of inhibitor were used in the mineral oil emulsions. After a certain draining and drying time, the sheets were stored in a humidity chamber at 100% relative atmospheric humidity. After the test period (1 to 7 days), the steel sheets were checked for signs of corrosion. The evaluation was carried out on the evaluation scale given in Example 1 from 0 to 4.

Die Ergebnisse sind der nachfolgenden Tabelle 6 zu entnehmen.The results are shown in Table 6 below.

Vergleichsbeispiel 5Comparative Example 5

Entsprechend den in Beispiel 4 angegebenen Bedingungen wurden identische Stahlbleche gleicher Größe in Mineralölemulsionen gelagert, die keinen Inhibitor enthielten. Die Vergleichsemulsionen enthielten naphthenisches Mineralöl und Emulgator (Addukt von 6,5 EO an Nonylphenol) im Gewichtsverhältnis 4:1.According to the conditions given in Example 4, identical steel sheets of the same size were stored in mineral oil emulsions which did not contain an inhibitor. The comparison emulsions contained naphthenic mineral oil and emulsifier (adduct of 6.5 EO with nonylphenol) in a weight ratio of 4: 1.

Die Ergebenisse der vergleichenden Versuche sind ebenfalls der nachfolgenden Tabelle 6 zu entnehmen (Vgl. 5).

Figure imgb0012
The results of the comparative tests can also be found in Table 6 below (see FIG. 5).
Figure imgb0012

Claims (10)

1. The use of alkoxyhydroxy fatty acids corresponding to general formula (I)
Figure imgb0015
in which R' represents unbranched alkyl or alkenyl radicals containing 6 to 8 C atoms, R2 represents unbranched or branched alkyl radicals containing 1 to 18 C atoms or unbranched or branched alkenyl radicals containing 2 to 18 C atoms, M represents hydrogen or organic ammonium residues containing one or more alkyl groups or hydroxyalkyl groups at the nitrogen atom and m is an integer of 3 to 13, or salts thereof in quantities of 0.01 to 10% by weight, based on oil, as corrosion inhibitors in oils and oil-containing emulisons.
2. The use claimed in claim 1, characterized in that, in the compounds of general formula (I), R' is an alkyl radical or alkenyl radical containing 8 C atoms.
3. The use claimed in claims 1 and 2, characterized in that, in the compounds of general formula (I), R1 represents alkyl radicals and alkenyl radicals containing 8 C atoms in a ratio of 1:2.
4. The use claimed in claims 1 to 3, characterized in that, in the compounds corresponding to general formula (I), m is an integer of 7 to 11.
5. The use claimed in claims 1 to 4, characterized in that, in the compounds corresponding to general formula (I), R2 represents unbranched alkyl radical or alkenyl radicals containing 8 to 18 C atoms.
6. The use claimed in claims 1 to 5, characterized in that, in the compounds corresponding to general formula (I), R2 represents art unbranched alkyl radical containing 16 C atoms and an unbranched alkenyl radical containing 18 C atoms.
7. The use claimed in claims 1 to 6, characterized in that, in the compounds corresponding to general formula (I), M represents hydrogen.
8. The use claimed in claims 1 to 6, characterized in that, in the compounds corresponding to general formula (I), M represents a group NH2(C2H40H)2.
9. The use claimed in claims 1 to 8, characterized in that the compounds of general formula (I) are used in quantities of 0.05 to 0.5% by weight, based on oil.
10. The use of alkoxyhydroxy fatty acids corresponding to formula (I) and salts thereof as corrosion inhibitors in lubricating oils, lubricating greases, power transmission oils and metal-working emulsions based on mineral oils.
EP86115325A 1985-11-13 1986-11-05 Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil Expired - Lifetime EP0222311B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86115325T ATE60083T1 (en) 1985-11-13 1986-11-05 USE OF ALKOXYHYDROXYFATTY ACIDS AS CORROSION INHIBITORS IN OILS AND OIL CONTAINING EMULSIONS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3540246 1985-11-13
DE19853540246 DE3540246A1 (en) 1985-11-13 1985-11-13 USE OF ALKOXYHYDROXY FATTY ACIDS AS CORROSION INHIBITORS IN OILS AND OIL-BASED EMULSIONS

Publications (3)

Publication Number Publication Date
EP0222311A2 EP0222311A2 (en) 1987-05-20
EP0222311A3 EP0222311A3 (en) 1989-05-03
EP0222311B1 true EP0222311B1 (en) 1991-01-16

Family

ID=6285879

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115325A Expired - Lifetime EP0222311B1 (en) 1985-11-13 1986-11-05 Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil

Country Status (8)

Country Link
US (2) US4957641A (en)
EP (1) EP0222311B1 (en)
JP (1) JPS62115093A (en)
AT (1) ATE60083T1 (en)
AU (1) AU577715B2 (en)
DE (2) DE3540246A1 (en)
ES (1) ES2003505A6 (en)
ZA (1) ZA868592B (en)

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8711534D0 (en) * 1987-05-15 1987-06-17 Ciba Geigy Ag Corrosion inhibiting composition
ES2032596T3 (en) * 1987-07-14 1993-02-16 Ciba-Geigy Ag CORROSION INHIBITOR COMPOSITIONS.
GB8727323D0 (en) * 1987-11-21 1987-12-23 Ciba Geigy Ag Corrosion inhibitor
DK653488D0 (en) * 1988-11-23 1988-11-23 Esti Kemi Aps based lubricant
DE3933137A1 (en) * 1989-10-04 1991-04-18 Henkel Kgaa METHOD FOR PRODUCING STABILIZED, LOW VISCOUS O / W ANTI-VIRUSULUS EMULSIONS
US5049299A (en) * 1989-10-26 1991-09-17 Kiwi Brands Incorporated Liquid lavatory cleansing and sanitizing composition
DE4244386A1 (en) * 1992-12-29 1994-06-30 Basf Ag Vinylpyrrolidone and vinylimidazole copolymers, processes for their preparation and their use in detergents
US5411677A (en) * 1993-04-26 1995-05-02 The Penn State Research Foundation Method and composition for preventing copper corrosion
US5492629A (en) * 1993-10-12 1996-02-20 H.E.R.C. Products Incorporated Method of cleaning scale and stains in water systems and related equipment
US5634979A (en) * 1994-12-22 1997-06-03 Henkel Corporation Composition and method for degreasing metal surfaces
US5525252A (en) * 1995-01-17 1996-06-11 Levin; Scott Aqueous, non-corrosive, composition with detergent for rust and stain removal
US5607911A (en) * 1995-01-17 1997-03-04 Levin; Scott Aqueous compositions with detergent for rust and stain removal
WO1997045510A1 (en) * 1996-05-30 1997-12-04 Salient Science, Inc. Foaming acidic detergent/cleansing gel
US5707955A (en) * 1996-07-15 1998-01-13 Colgate-Palmolive Co. High foaming nonionic surfactant based liquid detergent
WO1998033857A1 (en) * 1997-01-31 1998-08-06 Elisha Technologies Co. L.L.C. Corrosion protective coatings
US5895763A (en) * 1997-04-16 1999-04-20 H.E.R.C. Products Incorporated Controlled carbonate removal from water conduit systems
US5873944A (en) * 1997-05-13 1999-02-23 H.E.R.C. Products Incorporated Vacuum waste pipe cleaning
US6197451B1 (en) 1998-04-07 2001-03-06 Henkel Corporation Corrosion inhibiting electrolytic solutions
ZA991306B (en) * 1998-07-23 1999-08-20 Magdelena Christiana Cor Stols "A cleaning composition".
DE19842054A1 (en) * 1998-09-15 2000-03-16 Bayer Ag Use of water-soluble polymeric polycarboxylates in cleaning formulations with an abrasive effect
US6165952A (en) * 1999-04-05 2000-12-26 King Industries, Inc. Ashless rust inhibitor lubricant compositions
US6346217B1 (en) * 1999-06-02 2002-02-12 Water Whole International, Inc. Composition and method for cleaning drink water tanks
DE10005113A1 (en) * 2000-02-07 2001-08-09 Henkel Kgaa Corrosion inhibitor and corrosion protection method for metal surfaces
DK1274883T3 (en) 2000-04-13 2006-10-23 Baker Hughes Inc Corrosion inhibitor
US6964275B2 (en) * 2001-12-26 2005-11-15 H.E.R.C. Products Incorporated Countermeasure washdown system cleaning
US20040235680A1 (en) * 2002-09-18 2004-11-25 Ecolab Inc. Conveyor lubricant with corrosion inhibition
US20040074847A1 (en) * 2002-10-16 2004-04-22 Jaquess Percy A. Stable N-bromo-2-pyrrolidone and methods to make the same
US7964044B1 (en) * 2003-10-29 2011-06-21 Birchwood Laboratories, Inc. Ferrous metal magnetite coating processes and reagents
US20060180795A1 (en) * 2005-02-17 2006-08-17 Mccormick David R Stable acid inhibitor formulations with improved performance, lower toxicity and minimal environmental issues
US7828908B1 (en) 2010-03-31 2010-11-09 Ecolab USA, Inc. Acid cleaning and corrosion inhibiting compositions comprising gluconic acid
JP5518269B2 (en) * 2010-12-21 2014-06-11 ザ ルブリゾル コーポレイション Lubricating composition containing antiwear agent
US8795589B1 (en) 2011-04-29 2014-08-05 Cortec Corporation Bio-based volatile corrosion inhibitors
NL2011852C2 (en) 2013-11-28 2015-06-01 Univ Delft Tech Biobased membrane.
US9567554B2 (en) 2014-01-10 2017-02-14 General Electric Company Apparatus, method, and solvent for cleaning turbine components
CN115323385A (en) * 2022-08-30 2022-11-11 重庆广仁铁塔制造有限公司 Preparation method of efficient environment-friendly galvanized pickling corrosion inhibitor, corrosion inhibitor and application of corrosion inhibitor
CN115433945B (en) * 2022-10-19 2023-09-05 中国大唐集团科学技术研究院有限公司中南电力试验研究院 Quaternary composite corrosion inhibitor for chemical cleaning of coal-fired boiler and application

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2564422A (en) * 1947-04-28 1951-08-14 Shell Dev Corrosion preventive composition
US2708184A (en) * 1952-03-03 1955-05-10 Karl F Hager Tincture of iodine as acid pickling inhibitor
US3087853A (en) * 1956-07-02 1963-04-30 Gen Aniline & Film Corp Water soluble compositions consisting essentially of iodine and a water soluble oxygen containing polymer
US2956067A (en) * 1956-07-05 1960-10-11 Petrolite Corp Certain surfactants and method of making same
US2977315A (en) * 1956-09-12 1961-03-28 Lazarus Lab Inc Water soluble iodine-phosphoric-acidsynthetic detergent composition
BE568954A (en) * 1958-01-07
US3249547A (en) * 1958-05-19 1966-05-03 Monsanto Co Inhibition of acidic corrosion by use of a combination of a sugar and an iodide or bromide salt
US3029183A (en) * 1959-05-18 1962-04-10 West Laboratories Inc Germicidal iodine compositions
US3066159A (en) * 1960-11-29 1962-11-27 Petrolite Corp Reaction product of polyols and epoxidized fatty compounds
US3136755A (en) * 1960-12-01 1964-06-09 Gen Aniline & Film Corp Insoluble polymeric-iodine complexes
US3161598A (en) * 1961-12-11 1964-12-15 Geld Isidore Method and composition for chemical rust removal
US3119848A (en) * 1962-01-11 1964-01-28 Arthur N Wrigley Oxyethylated diols, nitriles and soaps
GB1052771A (en) * 1963-03-05
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3296149A (en) * 1964-09-25 1967-01-03 Hooker Chemical Corp Corrosion-inhibiting composition of mixture of molasses, potassium iodide and metal salt of a fatty acid
US3505184A (en) * 1966-02-07 1970-04-07 Enthone Acid zinc electrodepositing
US3349037A (en) * 1966-12-14 1967-10-24 Joseph C Peterson Additive for stainless steel pickling baths
US3539520A (en) * 1967-07-12 1970-11-10 West Laboratories Inc Compositions comprising quaternary ammonium germicides and nonionic surfactants
DE1298672B (en) * 1967-07-15 1969-07-03 Hoechst Ag Corrosion-preventing metalworking agent
US3687855A (en) * 1969-05-05 1972-08-29 Synergistics Inc Solid iodophor cleansing compositions
US3728267A (en) * 1970-01-14 1973-04-17 Mitsubishi Heavy Ind Ltd Peeling type pickling compositions
US3696048A (en) * 1970-04-06 1972-10-03 Universal Oil Prod Co Corrosion inhibiting composition and use thereof
US3773465A (en) * 1970-10-28 1973-11-20 Halliburton Co Inhibited treating acid
US3686129A (en) * 1971-01-08 1972-08-22 Minnesota Mining & Mfg Hydrogen embrittlement prevention
US3728449A (en) * 1972-05-01 1973-04-17 West Laboratories Inc Germicidal iodine compositions for application to skin tissue including teats of milk animals
JPS4935244A (en) * 1972-08-04 1974-04-01
US3816322A (en) * 1972-10-02 1974-06-11 Dow Chemical Co Corrosion inhibitor
DE2256908C2 (en) * 1972-11-20 1982-06-09 Henkel KGaA, 4000 Düsseldorf Process for the production of higher molecular weight di- and polyhydroxycarboxylic acids
US3911107A (en) * 1972-12-18 1975-10-07 Flow Pharma Inc Iodine composition and dissipating solution
US4017407A (en) * 1973-05-14 1977-04-12 West Laboratories, Inc. Methods for preparing solid iodine carrier mixtures and solid formulations of iodine with iodine carriers
US3898326A (en) * 1973-05-14 1975-08-05 West Laboratories Inc Polyvinylpyrrolidone-iodide compositions and polyvinylpyrrolidone-iodide-iodine complexes prepared therefrom
US4094967A (en) * 1976-10-22 1978-06-13 Allor Foundation Iodine-polyvinylpyrrolidone solid product and method of preparation
US4088597A (en) * 1977-06-13 1978-05-09 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Iodophor solution
US4275194A (en) * 1977-11-26 1981-06-23 Nihon Tennen Gas Kogyo Co., Ltd. Chitosan-iodine adduct
DE2758123A1 (en) * 1977-12-24 1979-07-05 Basf Ag CORROSION PROTECTION AGENTS IN Aqueous SYSTEMS
US4214059A (en) * 1978-06-12 1980-07-22 The Purdue Frederick Company Method for the production of iodophor powders
DE2927686A1 (en) * 1979-07-09 1981-02-05 Henkel Kgaa NEW LITHIUM SOAPS AND THEIR USE AS A THICKENING AGENT IN LUBRICANTS OR. GREASES
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)
US4518519A (en) * 1981-08-03 1985-05-21 Lott Peter F Acid based variable viscosity compositions such as corrosion and grease removers and polishes
DE3137339A1 (en) * 1981-09-19 1983-04-07 Henkel KGaA, 4000 Düsseldorf IODINE DISINFECTANT
DE3318596A1 (en) * 1983-05-21 1984-11-22 Henkel KGaA, 4000 Düsseldorf NEW HYDROXYALCOXYCARBONIC ACIDS AND THEIR SALTS, THEIR PRODUCTION AND USE
DE3319183A1 (en) * 1983-05-27 1984-11-29 Hoechst Ag, 6230 Frankfurt USE OF ALKENYLSBERSTALIC ACID HALBAMIDES AS AN ANTI-CORROSIVE AGENT
US4595517A (en) * 1983-08-24 1986-06-17 Khodabandeh Abadi Composition for removing scale from a surface comprising alpha-hydroxy carboxylic acid and thickener
US4576818A (en) * 1984-08-07 1986-03-18 Euroceltique, S.A. Iodophor composition
DE3609401A1 (en) * 1986-03-20 1987-09-24 Henkel Kgaa WATER-SOLUBLE MIXTURES OF FATTY ACID-AMMONIUM SALTS AND POLYOL FATTY ACIDS OR THEIR ALKALI OR AMMONIUM SALTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS CORROSION INHIBITORS IN AQUEOUS SYSTEMS

Also Published As

Publication number Publication date
DE3540246A1 (en) 1987-05-14
US4851149A (en) 1989-07-25
AU6506486A (en) 1987-05-21
EP0222311A2 (en) 1987-05-20
DE3676950D1 (en) 1991-02-21
AU577715B2 (en) 1988-09-29
ES2003505A6 (en) 1988-11-01
ZA868592B (en) 1987-06-24
ATE60083T1 (en) 1991-02-15
EP0222311A3 (en) 1989-05-03
JPS62115093A (en) 1987-05-26
US4957641A (en) 1990-09-18

Similar Documents

Publication Publication Date Title
EP0222311B1 (en) Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil
EP0237959B1 (en) Water soluble mixtures of ammonium salts from fatty acids and polyol-fatty acids, or of their alcali or ammonium salts, process for their production and their use as corrosion inhibitors in aqueous systems
DE10353603B4 (en) Use of ether carboxylic acids based on alkoxylated mono-, di- and / or tri (1-phenylethyl) phenols in cooling lubricants
DE3617550A1 (en) USE OF SALTS FROM ESTER LONG CHAIN FATTY ALCOHOLS WITH (ALPHA) SULFOURIC ACIDS
EP2828419B1 (en) Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate
EP0584711B1 (en) Alkenyl succinic acid derivatives as metal working agents
EP0566956B1 (en) Corrosion inhibitor
EP0060455B1 (en) Inhibitors against corrosion by carbon dioxide and hydrogen sulfide in water-in-oil emulsions
DE10123210C1 (en) New ether carboxylic acids and salts derived from alkoxylated mercaptobenzothiazoles are used as corrosion inhibitors in metal working and petroleum and natural gas recovery and processing
EP0231524B1 (en) Application of alkylbenzoylacrylic acids as corrosion inhibitors
EP0191952B1 (en) Salts of alkenylsuccinamic acids, process for their preparation and their use as corrosion inhibitors
EP0216280B1 (en) Use of alkenylsuccinic monoamides as corrosion inhibitors
EP2111440A1 (en) Cooling lubricant with high dispersing properties for the wet machining of light alloys
EP0726335B1 (en) Lactobionamide containing corrosion inhibiting composition
DE3830068A1 (en) AMIDOAMINE SALTS OF ALKENYLSBERSTEINSEUR DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS CORROSION INHIBITORS
DE19747895A1 (en) Metal treatment liquid for the neutral pH range
DE19959588A1 (en) Metal treatment liquid for the neutral pH range
DE10043040A1 (en) Use of N-alkyl-beta-alanine derivatives for the production of cleaning anti-corrosion agents
WO2008089857A1 (en) Cooling lubricant for the wet machining of aluminium alloyed magnesium
EP0109549B1 (en) Corrosion inhibitors for aqueous solutions for the treatment of metals, and process for their preparation
EP2796447B1 (en) New compounds containing sulfide bridges, method for their manufacture and use thereof
EP0464473B1 (en) Alkenylsuccinic monoamide salts and their use as corrosion inhibitors and emulsifiers for metal working oils
AT390055B (en) Process for the preparation of novel esters
DE3031636A1 (en) Alkali acyl cyanamide salt soln. - used as corrosion-protective agent in aq. metal-processing fluid or metal-cleansing soln.
CH496795A (en) Stabilizer for heating oils containing corrosion inhibitors

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE FR GB IT NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19890426

17Q First examination report despatched

Effective date: 19900130

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE FR GB IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19910116

Ref country code: GB

Effective date: 19910116

Ref country code: NL

Effective date: 19910116

Ref country code: SE

Effective date: 19910116

REF Corresponds to:

Ref document number: 60083

Country of ref document: AT

Date of ref document: 19910215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3676950

Country of ref document: DE

Date of ref document: 19910221

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19911105

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19911130

26N No opposition filed
BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19911130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST