EP1444313B1 - Method for working or forming metals in the presence of aqueous lubricants based on methanesulphonic acid salts - Google Patents

Method for working or forming metals in the presence of aqueous lubricants based on methanesulphonic acid salts Download PDF

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Publication number
EP1444313B1
EP1444313B1 EP02803047A EP02803047A EP1444313B1 EP 1444313 B1 EP1444313 B1 EP 1444313B1 EP 02803047 A EP02803047 A EP 02803047A EP 02803047 A EP02803047 A EP 02803047A EP 1444313 B1 EP1444313 B1 EP 1444313B1
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EP
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Prior art keywords
water
soluble
ams
salt
aqueous
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Expired - Lifetime
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EP02803047A
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German (de)
French (fr)
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EP1444313A2 (en
Inventor
Gilles Darvaux-Hubert
Fabrice Domingues Dos Santos
François GUILLEMET
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Arkema France SA
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Arkema France SA
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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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • 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
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10N2040/20—Metal working
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49616—Structural member making

Definitions

  • the present invention relates to the field of lubricants and more particularly that of aqueous lubricants containing water-soluble extreme pressure additives, useful for working or shaping metals.
  • a lubricant to reduce workpiece to tool forces, remove chips and debris, cool and control the surface condition of the workpiece or worked sheet.
  • oil-based lubricants have been used. These are whole oils or emulsions to which lubricity agents, anti-wear additives (AU) and / or extreme pressure (EP) have optionally been added.
  • EP additives are generally sulfur-containing compounds. Under the high temperatures encountered at the contact between the metal parts during the metalworking operations, the sulfur compounds decompose. An iron sulphide layer is formed on the surface of the parts which prevents welding and adhesion phenomena.
  • aqueous fluids are growing more and more. They are either synthetic fluids that are aqueous solutions based on water-soluble additives, or semi-synthetic fluids that are oil-in-water microemulsions containing a large quantity of emulsifiers.
  • synthetic fluids that are aqueous solutions based on water-soluble additives
  • semi-synthetic fluids that are oil-in-water microemulsions containing a large quantity of emulsifiers.
  • the aqueous fluids are very good at evacuating heat and have improved resistance to bacterial growth, they are often limited to metalworking operations where the friction and wear conditions are not too severe.
  • the EP additives have been developed for oils, so that very few of these additives are soluble in water and are suitable for aqueous fluids.
  • dithiodiglycol is used in combination with a Polyoxyalkylene glycol derivative for improving the extreme pressure properties of aqueous lubricants.
  • the use of aminosulphonic acid derivatives as additives in aqueous lubricating systems has been the subject of the application WO 8602911. More recently, in the Japanese patent application JP 10 110 181, the water-soluble salts of the acid 3, 3'-dithiodipropionic have been associated with alkyl thioacids in aqueous drawing lubricants.
  • the application EP 915 183 also describes the use of tin methane sulphonate in a tinning process of copper pipes by chemical deposition of a thin layer of tin.
  • AMS methanesulfonic acid
  • AMS is stable in water and completely soluble in all proportions at room temperature. AMS is slightly corrosive; in aqueous solution, it does not release H 2 S. The AMS is easily biodegradable (100% decomposition in 28 days), which is favorable for the environment. The AMS provides lubricating formulations with particularly interesting extreme pressure properties.
  • the subject of the present invention is therefore a process for working or shaping metals in the presence of an aqueous lubricant containing an extreme water-soluble pressure additive, characterized in that this additive is a water-soluble salt of methanesulphonic acid (AMS). consisting of an alkali or alkaline earth metal salt, or a compound of the general formula: R 1 NR 2 R 3 in which the symbols R 1 , R 2 and R 3 , which are identical or different, each represent a hydrogen atom, an alkyl, alkenyl or alkylaryl radical having from 1 to 22 carbon atoms, or an oxyethylated radical of the form ( CH 2 -CH 2 -O) n H, n being between 1 and 20.
  • AMS methanesulphonic acid
  • the water-soluble salts of AMS according to the invention are obtained by neutralization of the AMS with a salifying agent.
  • alkaline salts those obtained by neutralization of AMS with sodium hydroxide or potassium hydroxide are preferred.
  • Nonlimiting examples of compounds R 1 NR 2 R 3 include alkanolamines, in particular monoethanolamine, diethanolamine or triethanolamine, and ethoxylated amines, for which R 1 is a radical having from 12 to 22 atoms carbon, R 2 and R 3 are oxyethyl radicals having between 1 to 10 ethylene oxide groups.
  • the salifying agent is added in a stoichiometric proportion with respect to the AMS, in excess of the AMS, or in defect with respect to the AMS, according to the desired pH for the final formulation. It is preferred that the molar ratio of AMS to salification agent be from 1: 1 to 1: 2.
  • the water-soluble salts of AMS according to the invention are perfectly stable in water at room temperature and make it possible to obtain concentrated or diluted aqueous lubricating formulations which are easily preserved without release. of H 2 S and possess particularly interesting extreme pressure properties.
  • AMS or water-soluble salts of AMS may be presented as a dilutable concentrate later in use, or as a dilute solution. They can be used alone, but in general, they are used in a mixture with other conventional additives of synthetic or semi-synthetic fluids for working or shaping metals. Among these additives, mention may be made of bactericidal agents, emulsifiers, lubricity agents, anti-wear additives, defoamers and corrosion inhibitors.
  • the concentrates contain between 10% and 50% by weight of AMS or water-soluble salt of AMS, preferably between 15% and 35%.
  • AMS or the water-soluble salts of AMS according to the invention can be incorporated into the aqueous lubricants usually used.
  • aqueous lubricants usually used.
  • synthetic fluids true solutions
  • semi-synthetic fluids microemulsions
  • the charge corresponding to the welding of the 4 balls corresponds to the extreme pressure power; it must be as high as possible, typically ⁇ 160 kg.
  • Table 2 summarizes the composition and the extreme pressure performance of the various formulations tested; they are dilute aqueous formulations of AMS or water-soluble 1: 1 salts of AMS. They contain 5% by weight of water-soluble additive.
  • the lubricating formulations based on AMS or a water-soluble salt of AMS make it possible to obtain a weld load ⁇ 160 kg, much higher than that measured with pure water taken as a control.
  • the incorporation of an additive based on AMS or a water-soluble salt of AMS according to the invention makes it possible to provide extreme pressure properties to the aqueous formulations used for working or shaping the metals.
  • AMS and Na and K salts of AMS provide the highest performance.
  • Table 3 shows the extreme pressure performance as well as the corrosion properties of 2 aqueous lubricants containing a water-soluble salt of AMS according to the invention.
  • These compositions are prepared by neutralizing the AMS with an excess of sodium hydroxide (NaOH) or monoethanolamine (MEA).
  • the water-soluble salt is at a concentration by weight of 5% in water; the compositions are clear, stable and without any particular odor.
  • AMS in moles
  • NaOH in moles
  • MEA in moles
  • Welding load in kg
  • Anti-corrosion rating 8 1 1.25 - 500 Well 9 1 - two 200 Well
  • compositions 8 and 9 according to the invention make it possible to obtain high solder loads during the 4-ball EP test. They have good properties vis-à-vis corrosion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A method for working or forming metals which consists in usings an aqueous lubricant containing as water-soluble extreme pressure additive, methanesulphonic acid or water-soluble methanesulphonic acid salt. The water-soluble methane sulphonic acid salt is an alkali or alkaline-earth, ammonium, alkanol amine or ethoxylated fatty amine salt. The inventive aqueous lubricants have good extreme pressure properties and good properties with respect to corrosion.

Description

La présente invention concerne le domaine des lubrifiants et plus particulièrement celui des lubrifiants aqueux contenant des additifs hydrosolubles extrême pression, utiles pour le travail ou la mise en forme des métaux.The present invention relates to the field of lubricants and more particularly that of aqueous lubricants containing water-soluble extreme pressure additives, useful for working or shaping metals.

Les opérations de travail ou de déformation des métaux nécessitent l'emploi d'un lubrifiant afin de réduire les efforts entre la pièce à travailler et l'outil, évacuer les copeaux et les débris, refroidir et contrôler l'état de surface de la pièce ou de la tôle travaillée. Traditionnellement, des lubrifiants à base d'huile ont été utilisés. Il s'agit d'huiles entières ou d'émulsions auxquelles des agents d'onctuosité, des additifs anti-usure (AU) et/ou extrême pression (EP) ont été éventuellement adjoints. Les additifs EP sont généralement des composés contenant du soufre. Sous les fortes températures rencontrées au niveau du contact entre les pièces de métal pendant les opérations de travail des métaux, les composés soufrés se décomposent. Une couche de sulfure de fer se forme en surface des pièces qui empêche les phénomènes de soudure et d'adhésion.Work or metal deformation operations require the use of a lubricant to reduce workpiece to tool forces, remove chips and debris, cool and control the surface condition of the workpiece or worked sheet. Traditionally, oil-based lubricants have been used. These are whole oils or emulsions to which lubricity agents, anti-wear additives (AU) and / or extreme pressure (EP) have optionally been added. EP additives are generally sulfur-containing compounds. Under the high temperatures encountered at the contact between the metal parts during the metalworking operations, the sulfur compounds decompose. An iron sulphide layer is formed on the surface of the parts which prevents welding and adhesion phenomena.

Les huiles entières possèdent d'excellentes propriétés lubrifiantes mais lorsque les cadences sont élevées, l'évacuation de la chaleur nécessite l'utilisation d'émulsions. Toutefois, l'emploi des émulsions tend aussi à être réduit car au cours du temps elles sont dégradées et engendrent de mauvaises odeurs.Whole oils have excellent lubricating properties but when rates are high, heat removal requires the use of emulsions. However, the use of emulsions also tends to be reduced because over time they are degraded and generate bad odors.

C'est pourquoi les fluides aqueux se développent de plus en plus. Il s'agit soit de fluides synthétiques qui sont des solutions aqueuses à base d'additifs solubles dans l'eau, soit de fluides semi-synthétiques qui sont des microémulsions huile dans eau contenant une quantité importante d'émulsifiants. Cependant, si les fluides aqueux évacuent très bien la chaleur et possèdent une résistance à la prolifération bactérienne améliorée, ils sont souvent limités à des opérations de travail des métaux où les conditions de frottement et d'usure ne sont pas trop sévères. En effet, les additifs EP ont été développés pour des huiles, si bien que très peu de ces additifs sont solubles dans l'eau et sont adaptés aux fluides aqueux.This is why aqueous fluids are growing more and more. They are either synthetic fluids that are aqueous solutions based on water-soluble additives, or semi-synthetic fluids that are oil-in-water microemulsions containing a large quantity of emulsifiers. However, if the aqueous fluids are very good at evacuating heat and have improved resistance to bacterial growth, they are often limited to metalworking operations where the friction and wear conditions are not too severe. Indeed, the EP additives have been developed for oils, so that very few of these additives are soluble in water and are suitable for aqueous fluids.

S'il existe nombre d'additifs EP solubles dans l'huile, le nombre d'additifs EP solubles dans l'eau est nettement plus restreint. Dans Lub. Eng. 1977, 3(6), 291-298, R. W. Mould et al ont fait état des propriétés EP de quelques additifs soufrés solubles dans l'eau tels que les sels de sodium des acides thiosalicylique , 2-mercaptopropionique, 2,2'-dithiodibenzoïque, 2,2'-dithiodipropionique et dithiodiglycolique. De même, l'utilisation de sels hydrosolubles de l'acide 3,3'-dithiodipropionique a fait l'objet des brevets EP 288 375 et JP 63 265 997. Dans le brevet EP 183 050, le dithiodiglycol est utilisé en association avec un dérivé de polyoxyalkylène glycol pour améliorer les propriétés extrême pression de lubrifiants aqueux. L'utilisation de dérivés d'acides aminosulfoniques comme additifs dans des systèmes aqueux lubrifiants a fait l'objet de la demande WO 8602911. Plus récemment, dans la demande de brevet japonais JP 10 110 181, les sels hydrosolubles de l'acide 3,3'-dithiodipropionique ont été associés à des alkyle thioacides dans des lubrifiants aqueux d'emboutissage.If there are many oil-soluble EP additives, the number of water-soluble EP additives is much smaller. In Lub. Eng. 1977, 3 (6), 291-298, RW Mold et al reported the EP properties of some water-soluble sulfur additives such as sodium salts of thiosalicylic acid, 2-mercaptopropionic, 2,2'-dithiodibenzoic acid. , 2,2'-dithiodipropionic and dithiodiglycolic. Similarly, the use of water-soluble salts of 3,3'-dithiodipropionic acid has been the subject of patents EP 288 375 and JP 63 265 997. In patent EP 183 050, dithiodiglycol is used in combination with a Polyoxyalkylene glycol derivative for improving the extreme pressure properties of aqueous lubricants. The use of aminosulphonic acid derivatives as additives in aqueous lubricating systems has been the subject of the application WO 8602911. More recently, in the Japanese patent application JP 10 110 181, the water-soluble salts of the acid 3, 3'-dithiodipropionic have been associated with alkyl thioacids in aqueous drawing lubricants.

Cependant, ces produits ne sont pas suffisamment stables dans l'eau. Ils favorisent le développement de bactéries et dégagent du sulfure d'hydrogène entraînant une forte odeur des fluides aqueux. Leur formulation nécessite ainsi l'utilisation d'une grande quantité d'agents bactéricides, incompatible avec les quantités généralement admises dans les lubrifiants aqueux. Par ailleurs, certains de ces additifs à effet extrême pression ne sont pas compatibles avec la plupart des autres additifs utilisés couramment dans les formulations synthétiques ou semi-synthétiques.However, these products are not sufficiently stable in water. They promote the development of bacteria and release hydrogen sulfide resulting in a strong odor of aqueous fluids. Their formulation thus requires the use of a large amount of bactericidal agents, incompatible with the amounts generally accepted in aqueous lubricants. On the other hand, some of these extreme pressure additives are not compatible with most other additives commonly used in synthetic or semi-synthetic formulations.

Récemment, des compositions lubrifiantes contenant des sels d'amines d'acide sulfamique à effet extrême pression ont fait l'objet de la demande de brevet WO 00/44848. Cependant, l'acide sulfamique est fortement corrosif. Par ailleurs, sa faible solubilité rend impossible la réalisation de concentrés liquides facilement utilisables dans les formulations. Enfin, afin de limiter l'impact sur l'environnement des formulations lubrifiantes utilisées dans le domaine du travail et de la mise en forme des métaux, il est particulièrement important de mettre en oeuvre des additifs facilement biodégradables.Recently, lubricating compositions containing salts of sulfamic acid amines with extreme pressure effect have been the subject of the patent application WO 00/44848. However, sulfamic acid is highly corrosive. Moreover, its low solubility makes it impossible to produce liquid concentrates that can be easily used in the formulations. Finally, in order to limit the environmental impact of lubricating formulations used in the field of working and shaping metals, it is particularly important to use readily biodegradable additives.

La demande EP 915 183 décrit par ailleurs l'utilisation de méthane sulfonate d'étain dans un procédé d'étamage de tuyaux en cuivre par déposition chimique d'une fine couche d'étain.The application EP 915 183 also describes the use of tin methane sulphonate in a tinning process of copper pipes by chemical deposition of a thin layer of tin.

Il a maintenant été trouvé que l'utilisation de sels d'acide méthanesulfonique (AMS) dans des formulations aqueuses de travail des métaux est particulièrement intéressante.It has now been found that the use of methanesulfonic acid (AMS) salts in aqueous metal working formulations is of particular interest.

L'AMS est stable dans l'eau et complètement soluble en toutes proportions à température ambiante. L'AMS est peu corrosif ; en solution aqueuse, il ne dégage pas d'H2S. L'AMS est facilement biodégradable (100 % de décomposition en 28 jours), ce qui est favorable pour l'environnement. L'AMS apporte aux formulations lubrifiantes des propriétés extrême pression particulièrement intéressantes.AMS is stable in water and completely soluble in all proportions at room temperature. AMS is slightly corrosive; in aqueous solution, it does not release H 2 S. The AMS is easily biodegradable (100% decomposition in 28 days), which is favorable for the environment. The AMS provides lubricating formulations with particularly interesting extreme pressure properties.

La présente invention a donc pour objet un procédé de travail ou de mise en forme des métaux en présence d'un lubrifiant aqueux contenant un additif extrême pression hydrosoluble, caractérisé en ce que cet additif est un sel hydrosoluble de l'acide méthanesulfonique (AMS) consistant en un sel de métal alcalin ou alcalinoterreux, ou d'un composé répondant à la formule générale :

        R1NR2R3

dans laquelle les symboles R1, R2 et R3, identiques ou différents, représentent chacun, un atome d'hydrogène, un radical alkyle, alcényle ou alkylaryle ayant de 1 à 22 atomes de carbone, ou un radical oxyéthylé de la forme (CH2-CH2-O)nH, n étant compris entre 1 et 20.The subject of the present invention is therefore a process for working or shaping metals in the presence of an aqueous lubricant containing an extreme water-soluble pressure additive, characterized in that this additive is a water-soluble salt of methanesulphonic acid (AMS). consisting of an alkali or alkaline earth metal salt, or a compound of the general formula:

R 1 NR 2 R 3

in which the symbols R 1 , R 2 and R 3 , which are identical or different, each represent a hydrogen atom, an alkyl, alkenyl or alkylaryl radical having from 1 to 22 carbon atoms, or an oxyethylated radical of the form ( CH 2 -CH 2 -O) n H, n being between 1 and 20.

Les sels hydrosolubles d'AMS selon l'invention sont obtenus par neutralisation de l'AMS avec un agent de salification.The water-soluble salts of AMS according to the invention are obtained by neutralization of the AMS with a salifying agent.

Parmi les sels alcalins, on préfère ceux obtenus par neutralisation de l'AMS avec de la soude ou de la potasse.Among the alkaline salts, those obtained by neutralization of AMS with sodium hydroxide or potassium hydroxide are preferred.

Comme exemples non limitatifs de composés R1NR2R3, on peut citer les alcanolamines, en particulier la monoéthanolamine, la diéthanolamine ou la triéthanolamine, les amines éthoxylées dont on préfère celles pour lesquelles R1 est un radical possédant de 12 à 22 atomes de carbone, R2 et R3 sont des radicaux oxyéthylés comportant entre 1 à 10 groupements d'oxyde d'éthylène.Nonlimiting examples of compounds R 1 NR 2 R 3 include alkanolamines, in particular monoethanolamine, diethanolamine or triethanolamine, and ethoxylated amines, for which R 1 is a radical having from 12 to 22 atoms carbon, R 2 and R 3 are oxyethyl radicals having between 1 to 10 ethylene oxide groups.

L'agent de salification est ajouté en proportion stoechiométrique par rapport à l'AMS, en excès par rapport à l'AMS, ou en défaut par rapport à l'AMS, selon le pH désiré pour la formulation finale. On préfère que le rapport molaire entre l'AMS et l'agent de salification soit compris entre 1:1 et 1:2.The salifying agent is added in a stoichiometric proportion with respect to the AMS, in excess of the AMS, or in defect with respect to the AMS, according to the desired pH for the final formulation. It is preferred that the molar ratio of AMS to salification agent be from 1: 1 to 1: 2.

Les sels hydrosolubles d'AMS selon l'invention sont parfaitement stables dans l'eau à température ambiante et permettent d'obtenir des formulations lubrifiantes aqueuses concentrées ou diluées qui se conservent aisément sans dégagement d'H2S et possèdent des propriétés extrême pression particulièrement intéressantes.The water-soluble salts of AMS according to the invention are perfectly stable in water at room temperature and make it possible to obtain concentrated or diluted aqueous lubricating formulations which are easily preserved without release. of H 2 S and possess particularly interesting extreme pressure properties.

De plus, ces formulations ne sont pas corrosives.In addition, these formulations are not corrosive.

L'AMS ou les sels hydrosolubles d'AMS peuvent être présentés sous forme de concentré diluable ultérieurement lors de l'utilisation, ou sous forme de solution diluée. Ils peuvent être utilisés seuls, mais en général, on les utilise en mélange avec d'autres additifs usuels des fluides synthétiques ou semi-synthétiques pour travail ou mise en forme des métaux. Parmi ces additifs, on peut mentionner les agents bactéricides, les émulsifiants, les agents d'onctuosité, les additifs à effet anti-usure, les antimousses, les inhibiteurs de corrosion.AMS or water-soluble salts of AMS may be presented as a dilutable concentrate later in use, or as a dilute solution. They can be used alone, but in general, they are used in a mixture with other conventional additives of synthetic or semi-synthetic fluids for working or shaping metals. Among these additives, mention may be made of bactericidal agents, emulsifiers, lubricity agents, anti-wear additives, defoamers and corrosion inhibitors.

Les concentrés renferment entre 10 % et 50 % en poids d'AMS ou de sel hydrosoluble d'AMS, de préférence entre 15 % et 35 %.The concentrates contain between 10% and 50% by weight of AMS or water-soluble salt of AMS, preferably between 15% and 35%.

L'AMS ou les sels hydrosolubles d'AMS selon l'invention, les concentrés contenant ceux-ci et d'autres additifs classiquement rencontrés dans les lubrifiants aqueux de travail ou de mise en forme des métaux, peuvent être incorporés aux lubrifiants aqueux usuellement employés pour le travail ou la mise en forme des métaux, plus particulièrement aux fluides synthétiques (solutions vraies) ou semi-synthétiques (microémulsions), en concentration pondérale allant de 0,01 % à 20 %, et de préférence entre 0,1 % et 10 %.The AMS or the water-soluble salts of AMS according to the invention, the concentrates containing these and other additives conventionally found in aqueous lubricants for working or shaping metals, can be incorporated into the aqueous lubricants usually used. for working or shaping metals, more particularly synthetic fluids (true solutions) or semi-synthetic fluids (microemulsions), in a weight concentration ranging from 0.01% to 20%, and preferably between 0.1% and 10%.

L'efficacité des additifs extrême pression selon l'invention est évaluée par des essais sur machine à 4 billes par le test 4-billes extrême pression selon la norme ASTM D-2783 : ce test consiste à évaluer le pouvoir extrême pression d'un fluide par la valeur de la charge à partir de laquelle 4 billes sont soudées entre elles en empêchant la rotation de la bille supérieure sur les 3 autres maintenues dans le fluide à tester, selon le protocole de mesure suivant :

  • Billes en acier 100C6 de 12,7 mm de diamètre
  • Vitesse de rotation de la bille supérieure : 1500 tours par minute
  • Durée de l'essai : 10 secondes
  • Charges croissantes
The effectiveness of the extreme pressure additives according to the invention is evaluated by 4-ball machine tests using the 4-ball extreme pressure test according to ASTM D-2783: this test consists of evaluating the extreme pressure power of a fluid. by the value of the charge from which 4 balls are welded together by preventing the rotation of the upper ball on the other 3 maintained in the test fluid, according to the following measurement protocol:
  • 100C6 steel balls of 12.7 mm diameter
  • Rotation speed of the upper ball: 1500 rpm
  • Duration of the test: 10 seconds
  • Increasing loads

La charge correspondant à la soudure des 4 billes correspond au pouvoir extrême pression ; elle doit être la plus élevée possible, typiquement ≥160 kg.The charge corresponding to the welding of the 4 balls corresponds to the extreme pressure power; it must be as high as possible, typically ≥160 kg.

Le pouvoir anti-corrosion des additifs extrême pression selon l'invention est évalué en mettant en contact des copeaux de fonte avec le lubrifiant aqueux à tester selon le protocole suivant :

  • 2 g de copeaux de fonte normalisés (ASTM D-4627) sont recouverts de 5 ml de lubrifiant aqueux à tester dans une boite de pétri comportant sur le fond un papier filtre.
  • Durée du contact : 2 heures à température ambiante
The anti-corrosion power of the extreme pressure additives according to the invention is evaluated by bringing molten chips into contact with the aqueous lubricant to be tested according to the following protocol:
  • 2 g of standardized melt chips (ASTM D-4627) are coated with 5 ml of aqueous lubricant to be tested in a petri dish with a filter paper on the bottom.
  • Duration of contact: 2 hours at room temperature

L'apparition de rouille sur le papier filtre est l'indicateur du pouvoir anti-corrosion ; la notation est résumée dans le tableau 1 : Tableau 1 Observation sur le papier filtre Pouvoir anti-corrosion Pas de trace de rouille Bon Quelques traces de rouille Moyen Traces de rouille Mauvais The appearance of rust on the filter paper is the indicator of the anti-corrosion power; the notation is summarized in Table 1: <b><u> Table 1 </ u></b> Observation on filter paper Anti-corrosion power No trace of rust Well Some traces of rust Way Traces of rust Bad

Les exemples suivants illustrent l'invention sans la limiter. Les pourcentages indiqués sont exprimés en poids.The following examples illustrate the invention without limiting it. The percentages indicated are expressed by weight.

EXEMPLE 1EXAMPLE 1

Le tableau 2 résume la composition et les performances extrême pression des différentes formulations testées ; il s'agit de formulations aqueuses diluées d'AMS ou de sels hydrosolubles 1 :1 d'AMS. Elles contiennent 5 % en poids d'additif hydrosoluble.Table 2 summarizes the composition and the extreme pressure performance of the various formulations tested; they are dilute aqueous formulations of AMS or water-soluble 1: 1 salts of AMS. They contain 5% by weight of water-soluble additive.

Ces formulations sont obtenues à température ambiante dans un bécher de 300 ml contenant 200 ml d'eau bi-permutée. La quantité adéquate d'AMS pur est lentement ajoutée sous agitation magnétique modérée. La soude (NaOH), la potasse (KOH), la monoéthanolamine (MEA), la triéthanolamine (TEA) ou l'amine grasse éthoxylée (NORAMOX® C2 : mono amine sur base coprah éthoxylée avec 2 moles d'oxyde d'éthylène ou NORAMOX® O2 : mono amine sur base oléïque éthoxylée avec 2 moles d'oxyde d'éthylène , de la société CECA) est ensuite ajoutée dans les proportions stoechiométriques pour obtenir un sel 1:1 à 5 % en poids de matière active. Les solutions sont toutes limpides, stables et sans odeur particulière. Chacune des compositions a fait l'objet du test 4-billes avec détermination de la charge de soudure. Tableau 2 Composition Charge de Formulation Eau (en %) Additif (en %) soudure (en kg) Témoin 100 aucun 80 1 95 AMS 5 400 2 95 AMS 3,53 400 NaOH 1,47 3 95 AMS 3,16 400 KOH 1,84 4 95 AMS 3,06 250 MEA 1,94 5 95 AMS 1,96 200 TEA 3,04 6 95 AMS 1,19 160 Noramox C2 3,81 7 95 AMS 1,04 160 Noramox O2 3,96 These formulations are obtained at room temperature in a 300 ml beaker containing 200 ml of bi-permutated water. The proper amount of pure AMS is slowly added with moderate magnetic stirring. Soda (NaOH), potassium hydroxide (KOH), monoethanolamine (MEA), triethanolamine (TEA) or ethoxylated fatty amine (NORAMOX® C2: monoamine on a coconut basis ethoxylated with 2 moles of ethylene oxide or NORAMOX® O2: monoamine on oleic base ethoxylated with 2 moles of ethylene oxide, CECA) is then added in stoichiometric proportions to obtain a salt 1: 1 to 5% by weight of active ingredient. The solutions are all clear, stable and without any particular smell. Each of the compositions was the subject of the 4-ball test with determination of the welding load. <b><u> Table 2 </ u></b> Composition In charge of Formulation Water (in%) Additive (in%) welding (in kg) Witness 100 no 80 1 95 AMS 5 400 two 95 AMS 3.53 400 NaOH 1.47 3 95 AMS 3.16 400 KOH 1.84 4 95 AMS 3.06 250 MEA 1.94 5 95 AMS 1.96 200 TEA 3.04 6 95 AMS 1.19 160 Noramox C2 3.81 7 95 AMS 1.04 160 Noramox O2 3.96

A l'examen des résultats concernant le test 4-billes, on constate que les formulations lubrifiantes à base d'AMS ou d'un sel hydrosoluble d'AMS, conformes à l'invention, permettent d'obtenir une charge de soudure ≥ 160 kg, bien supérieure à celle mesurée avec de l'eau pure prise pour témoin. L'incorporation d'un additif à base d'AMS ou d'un sel hydrosoluble d'AMS selon l'invention permet d'apporter des propriétés extrême pression aux formulations aqueuses mises en oeuvre pour le travail ou la mise en forme des métaux. L'AMS et les sels de Na et K de l'AMS permettent d'obtenir les performances les plus élevées.On examining the results concerning the 4-bead test, it can be seen that the lubricating formulations based on AMS or a water-soluble salt of AMS, in accordance with the invention, make it possible to obtain a weld load ≥ 160 kg, much higher than that measured with pure water taken as a control. The incorporation of an additive based on AMS or a water-soluble salt of AMS according to the invention makes it possible to provide extreme pressure properties to the aqueous formulations used for working or shaping the metals. AMS and Na and K salts of AMS provide the highest performance.

EXEMPLE 2EXAMPLE 2

Le tableau 3 montre les performances extrême pression ainsi que les propriétés vis à vis de la corrosion de 2 lubrifiants aqueux contenant un sel hydrosoluble d'AMS conformes à l'invention. Ces compositions sont préparées en neutralisant l'AMS avec un excès de soude (NaOH) ou de monoéthanolamine (MEA). Le sel hydrosoluble est à une concentration pondérale de 5 % dans l'eau ; les compositions sont limpides, stables et sans odeur particulière. Tableau 3 Formulation AMS (en moles) NaOH (en moles) MEA (en moles) Charge de soudure (en kg) Cotation anti-corrosion 8 1 1,25 - 500 Bon 9 1 - 2 200 Bon Table 3 shows the extreme pressure performance as well as the corrosion properties of 2 aqueous lubricants containing a water-soluble salt of AMS according to the invention. These compositions are prepared by neutralizing the AMS with an excess of sodium hydroxide (NaOH) or monoethanolamine (MEA). The water-soluble salt is at a concentration by weight of 5% in water; the compositions are clear, stable and without any particular odor. <b><u> Table 3 </ u></b> Formulation AMS (in moles) NaOH (in moles) MEA (in moles) Welding load (in kg) Anti-corrosion rating 8 1 1.25 - 500 Well 9 1 - two 200 Well

Les compositions 8 et 9 selon l'invention permettent d'obtenir des charges de soudure élevées lors du test 4-billes EP. Elles ont de bonnes propriétés vis-à-vis de la corrosion.The compositions 8 and 9 according to the invention make it possible to obtain high solder loads during the 4-ball EP test. They have good properties vis-à-vis corrosion.

Claims (6)

  1. A method for working or forming metals in the presence of an aqueous lubricant containing a water-soluble extreme pressure additive, characterized in that said additive is a water-soluble salt of methanesulfonic acid consisting of a salt of an alkali or alkaline-earth metal, or of a compound with the formula:

            R1NR2R3

    where the symbols R1, R2 and R3, identical or different, each represent a hydrogen atom, an alkyl, alkenyl or alkylaryl radical with 1 to 22 carbon atoms, or an oxyethylated radical of the form (CH2-CH2-O)nH, where n is between 1 and 20.
  2. The method as claimed in claim 1, characterized in that the water-soluble MSA salt is the sodium or potassium salt.
  3. The method as claimed in claim 1, characterized in that the compound R1NR2R3 is an alkanolamine, in particular monoethanolamine, diethanolamine or triethanolamine.
  4. The method as claimed in claim 1, characterized in that the compound R1NR2R3 is an ethoxylated amine in which R1 is a radical with 12 to 22 carbon atoms and the radicals R2 and R3 are oxyethylated radicals with n between 1 and 10.
  5. The method as claimed in one of claims 1 to 4, characterized in that the water-soluble MSA salt is obtained with a molar ratio of 1:1 to 1:2 between the MSA and the salifying agent.
  6. The method as claimed in one of claims 1 to 5, characterized in that the concentration of MSA or of water-soluble MSA salt in the aqueous lubricant is between 0.01% and 20% by weight, and preferably between 0.1% and 10% by weight.
EP02803047A 2001-11-15 2002-11-08 Method for working or forming metals in the presence of aqueous lubricants based on methanesulphonic acid salts Expired - Lifetime EP1444313B1 (en)

Applications Claiming Priority (3)

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FR0114787A FR2832160B1 (en) 2001-11-15 2001-11-15 PROCESS FOR WORKING OR FORMING METALS IN THE PRESENCE OF AQUEOUS LUBRICANTS BASED ON METHANESULFONIC ACID (AMS) OR AMS WATER SOLUBLE SALT
FR0114787 2001-11-15
PCT/FR2002/003847 WO2003042342A2 (en) 2001-11-15 2002-11-08 Method for working or forming metals in the presence of aqueous lubricants based on methanesulphonic acid

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EP1444313B1 true EP1444313B1 (en) 2006-08-23

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