WO2001007545A1 - Composition de lubrifiant contenant du soufre elementaire pour l'usinage de metaux - Google Patents

Composition de lubrifiant contenant du soufre elementaire pour l'usinage de metaux Download PDF

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Publication number
WO2001007545A1
WO2001007545A1 PCT/EP2000/006650 EP0006650W WO0107545A1 WO 2001007545 A1 WO2001007545 A1 WO 2001007545A1 EP 0006650 W EP0006650 W EP 0006650W WO 0107545 A1 WO0107545 A1 WO 0107545A1
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Prior art keywords
oil
sulfur
cooling lubricant
water
acid
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PCT/EP2000/006650
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German (de)
English (en)
Inventor
Ilona Lange
Jürgen Geke
Jürgen Föll
Henry Rossmaier
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU61588/00A priority Critical patent/AU6158800A/en
Publication of WO2001007545A1 publication Critical patent/WO2001007545A1/fr

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    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
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    • 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
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2201/02—Water
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/043—Sulfur; Selenenium; Tellurium
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/18—Ammonia
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • 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
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    • C10M2207/28—Esters
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    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2207/286—Esters of polymerised unsaturated acids
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
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    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/241—Manufacturing joint-less pipes
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Definitions

  • the invention is in the field of metal machining. It concerns cooling lubricants and cooling lubricant concentrates that are used in these work steps.
  • metal cutting examples include cutting, drilling, turning, milling, grinding, honing or lapping.
  • Liquid aids so-called cooling lubricants, are required for these processes. These essentially have the task of reducing the friction between the tool and the workpiece, dissipating the heat generated and removing metal debris or chips. Furthermore, they must prevent discoloration and / or corrosion of the machined workpieces.
  • oils Today paraffin or mineral oils are preferably used as oil components. There are also so-called synthetic lubricants (“synthetic oils”) such as polyolefins. Further examples of oil components are ester oils, which can be based on vegetable or animal oils, acetals or dialkyl ethers. By selecting the oils and their mixtures according to properties such as polarity or viscosity, metalworking agents can be formulated that meet the technical requirements for a wide variety of applications.
  • the cooling lubricants In order to develop a sufficient lubricating effect, the cooling lubricants must contain lubricating components. With water-soluble cooling lubricants that do not contain an oil phase, polyglycols are often used as the lubricating component. Such aqueous cooling lubricants cause good heat dissipation, but their lubricating effect is limited. On the other hand, essentially water-free oils can be used as cooling lubricants. These have a very good lubricating effect and, due to their hydrophobicity, also an anti-corrosion effect, but the cooling effect is limited due to the low heat capacity of the oils.
  • cooling lubricants in the form of oil-in-water emulsions. These generally contain about 0.05 to about 5% by weight of an oil phase, which is in the form of emulsifiers of droplets in the submicrometer and micrometer range is dispersed in the water phase.
  • a further essential component of such cooling lubricant emulsions are corrosion inhibitors.
  • EP additives are often added to improve the lubricating effect of purely oily cooling lubricants (which are also referred to as cutting oils) or of oil-containing cooling lubricant emulsions. These can be selected from phosphorus, sulfur or, in the case of reduced environmental protection requirements, chlorine-containing organic compounds. In particular, organic sulfur compounds are frequently used as EP additives. Due to its chemical properties, sulfur is particularly well suited in principle to increase the lubricating performance in lubricants by forming the required sulfide layers. Due to its poor solubility, sulfur can only be dissolved up to approx. 1% in mineral oils.
  • sulfur compounds also have an unsatisfactory skin tolerance and an unpleasant smell, which in practice leads to annoyance and a health hazard to people.
  • dialkyl oligosulfides such as e.g. B. diisononyl pentasulfide in use, which, however, like the other EP additives of the prior art, frequently do not show a satisfactory effect.
  • the price-performance ratio of the known EP additives is in many cases unsatisfactory or the solubility or dispersibility in the base oils is insufficient.
  • the object of the invention is to provide improved cooling lubricants and their concentrates for metal cutting which contain elemental sulfur to improve the lubricating effect.
  • the invention relates to a cooling lubricant for metal cutting, containing 0.01 to 0.5% by weight, preferably 0.02 to 0.2% by weight, based on the total amount of the cooling lubricant ready for use, with elemental sulfur an average particle size in the range from 10 to 1500 nm.
  • the elemental sulfur preferably has an average particle size in the range from 25 to 800 nm.
  • the particle diameter of commercially available sulfur bloom was determined to be 29 ⁇ m (Fraunhofer diffraction with Sympatec Helos device).
  • a high-performance ultrafine granulometer can be used.
  • the average particle size is usually expressed as a so-called X50 value. This value means that 50% of all particles have a size that is less than or equal to this value.
  • “medium Particle size” understood these X50 values with regard to the diameter in the direction of the greatest longitudinal expansion of the particles.
  • the sizes of the individual particles follow a more or less broad distribution curve.
  • the nanoparticulate sulfur contained in the cooling lubricants according to the invention can be produced by different processes.
  • the preparation is preferably carried out in such a way that an aqueous sulfur dispersion —also referred to as “colloidal sulfur” - is first prepared by one of the processes known from the prior art. Such processes are described, for example, in Gmelins Handbuch der inorganic Chemie, Volume 9 [A], 8th edition, Verlag Chemie, Weinheim 1953, p. 485 f.
  • the aqueous dispersion can be used as such for use in water-containing lubricant preparations. If desired, a certain concentration of the dispersion can be adjusted by adding or removing water.
  • the aqueous sulfur dispersion is freed from the water, which can preferably be done by freeze-drying.
  • the aqueous sulfur dispersion is prepared by reacting the following components: a) hydrogen sulfide or an alkali metal salt of hydrogen sulfide and b) sulfur dioxide, sulfurous acid or an alkali metal salt of sulfurous acid.
  • a Bronsted acid preferably a mineral acid
  • a Bronsted acid is also to be added in order to set the acidic pH of below 7 required for the reaction.
  • the aqueous sulfur dispersion is prepared in the presence of one or more surface modifiers, the order in which they are added to the other reaction partners is generally not critical.
  • the nanoparticulate sulfur particles can therefore be encased by at least one surface modifier.
  • This coating improves the chemical stability against oxidative and photochemical changes during the storage of the particles and increases their stability against agglomeration. Furthermore, by suitable coating of the particles, their redispersibility can be improved and these different dispersing agents can be adapted.
  • Surface modification agents are understood to mean substances which physically adhere to the surface of the finely divided particles, but do not react chemically with them.
  • the individual molecules of the surface modification agents adsorbed on the surface are essentially free of intermolecular bonds with one another.
  • Surface modifiers are to be understood in particular as dispersants. Dispersants are also known to the person skilled in the art, for example, under the terms emulsifiers, protective colloids, wetting agents and detergents.
  • Suitable surface modifiers are emulsifiers of the nonionic surfactant type from at least one of the following groups:
  • alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs; (5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
  • polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;
  • partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside Lauryl glucoside) and polyglucosides (eg cellulose);
  • the adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters, and sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • C ⁇ / i ⁇ alkyl mono- and oligoglycosides their preparation and their use are known from the prior art. They are manufactured in particular by Reaction of glucose or oligosaccharides with primary alcohols with 8 to
  • glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • anionic emulsifiers are droxymischethersulfate soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, ⁇ - methyl ester sulfonates, sulfofatty acids, alkyl sulfates, alkyl ether sulfates, such as fatty alcohol ether sulfates, Glycerol ether, hybrid, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example that
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a Cs / i ⁇ -alkyl or - acyl group, contain at least one free amino group and at least one - COOH or -SO ß H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with approximately 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci 2 / i ⁇ -acylsarcosine.
  • quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • thiols of the general formula HSR 1 where R 1 is an acyclic or cyclic aliphatic, araliphatic, alkylaromatic or aromatic radical having 5 to 30 carbon atoms, which additionally has one or more substituents selected from the group ONO 2 , NO 2 , Cl, Br, CN, SO 3 M or OSO 3 M can be substituted, where M is hydrogen or an alkali metal.
  • thioethers of the general formula R 1 -S x -R 2 where R 1 and R 2 each have the same meaning as described for R 1 under a) and can be the same or different, and x is an integer between 1 and 12 means.
  • Protective colloids suitable as surface modifiers are, for example, natural water-soluble polymers such as, for. B. gelatin, casein, gum arabic, alginic acid, sodium alginate, lysalbic acid, starch, albumin, water-soluble derivatives of water-insoluble polymeric natural substances such.
  • B. cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or modified Carboxymethyl cellulose, hydroxyethyl starch or hydroxypropyl guar
  • synthetic water-soluble polymers such as.
  • the sulfur and the surface modification agent or agents are used in a weight ratio of 1:50 to 50: 1, preferably 1:25 to 25: 1 and in particular 1:10 to 10: 1.
  • the nanoparticulate sulfur contained in the lubricants according to the invention can be produced by condensing vaporous sulfur in water, which optionally contains one or more surface modifiers, and then freeing the suspension obtained from the water, for example by freeze-drying.
  • Another manufacturing possibility is that one
  • Solvent comes to precipitation of the nanoparticulate particles, the organic solvent preferably evaporating. Instead of an aqueous one
  • O / W emulsions or O / W microemulsions can also be used.
  • the surface modification agents already explained at the beginning can be used as surface-active compounds.
  • GAS process Gas Anti Solvent Recrystallization
  • the process uses a highly compressed gas or supercritical fluid (e.g. carbon dioxide) as a non-solvent for the crystallization of solutes.
  • the compressed gas phase is introduced into the primary solution of the starting material and absorbed there, which increases the volume of the liquid, the solubility decreases and fine particles are separated out.
  • the PCA method Precipitation with a Compressed Fluid Anti-Solvent
  • the primary solution of the starting material is introduced into a supercritical fluid, whereby finely divided droplets form in which diffusion processes take place, so that the finest particles are precipitated.
  • the starting material is melted by injecting gas (e.g. carbon dioxide or propane). Pressure and temperature reach near or supercritical conditions. The gas phase dissolves in the solid and causes a lowering of the melting temperature, the viscosity and the surface tension. When expanding through a nozzle, cooling effects lead to the formation of very fine particles.
  • gas e.g. carbon dioxide or propane
  • the cooling lubricant can be in the form of an oil-free water phase in which the elemental sulfur is dispersed.
  • the cooling lubricant is in the form of an oil in which the elemental sulfur is dispersed.
  • the cooling lubricant is in the form of an oil-in-water emulsion, in the water phase of which the elemental sulfur is dispersed.
  • the elemental sulfur is dispersed in the oil phase of the oil-in-water emulsion.
  • one or the other embodiment can be achieved.
  • Dispersion in the water phase is achieved by using an aqueous sulfur sol to produce the oil-in-water emulsion or by adding powdered sulfur of the specified particle size to the emulsion after its production, which can be obtained, for example, by freeze-drying a sulfur sol , Dispersion in the oil phase can be achieved if the elemental sulfur of the particle size mentioned is incorporated into the oil phase before the emulsion is prepared.
  • oil or “oil phase”
  • oil means liquid substances at the application temperature which cannot be mixed with water in any ratio and which are preferably essentially insoluble in water and which are higher Have viscosity as water.
  • the oil can be selected from paraffinic or naphthenic mineral oils, polyolefins, ester oils, acetals or dialkyl ethers.
  • Ester oils are understood to mean esters of carboxylic acids having 10 to 24 carbon atoms, which are preferably of animal or vegetable origin, with mono- or polyhydric alcohols.
  • ester oils examples include so-called triglycerides, glycerol fatty acid esters, which are preferably of vegetable or animal origin, that is to say preferably so-called “native oils”. represent.
  • the ester oils can also be chemical conversion products, for example transesterification products of such native oils.
  • acetals or dialkyl ethers which contain such a number of C-
  • the cooling lubricants according to the invention in the form of oil-in-water emulsions can contain further components which are mentioned in the prior art for this area of application. Examples are emulsifiers, corrosion inhibitors and / or biocides.
  • a side aspect of the invention is that, in some cases, the biostatic properties of elemental sulfur make it possible to dispense with biocides.
  • Suitable corrosion inhibitors are salts of carboxylic acids of the formula (I)
  • Ph-COCH CH group, where R is a linear or branched alkyl radical having 8 to 18 carbon atoms and Ph is a phenyl group. R 3 can furthermore represent an aromatic radical.
  • Typical examples are the fatty acids caproic acid, caprylic acid, capric acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, and eradic acidic acid, and eradic acidic acid, and eradic acidic acid, and eradic acid, and eradic acid, theiridic acid, herodic acid, and eradic acid, herodic acid, herodic acid, and eradic acid, theiridic acid, and eradic acid, theiridic acid, and its acidic acid, gadoleic acid, and its acidic acid technical mixtures, such as those used in the pressure splitting of natural fats and oils occur.
  • substituted carboxylic acids are included in the group of alkylbenzoylacrylic acids.
  • the use of 3- (p-dodecylbenzoyl) acrylic acid is particularly preferred.
  • the acids mentioned can be used in particular as alkali, alkaline earth, ammonium, alkylammonium and / or zinc salts.
  • Anionic surfactants of the petroleum sulfonate type can be considered as a further group of corrosion inhibitors. These are sulfoxidation products of paraffin fractions with an average of 6 to 30, in particular 10 to 20, carbon atoms.
  • the petroleum sulfonates can also be regarded as secondary alkane sulfonates, with alkali or alkaline earth metals, ammonium or alkylammonium being suitable as counterions.
  • the petroleum sulfonates are preferably used in the form of their sodium or calcium salts.
  • a further group of corrosion inhibitors are sulfonation products of unsaturated fatty acid glyceride esters of the formula (II), so-called “sulfotriglycerides” or “sulfoils”.
  • R 6 CO and R 'CO independently of one another represent acyl radicals having 6 to 24 carbon atoms and 0 or 1 to 5 double bonds.
  • Sulfotriglycerides are known substances which can be obtained, for example, by adding sulfur trioxide or chlorosulfonic acid to unsaturated triglycerides, in particular rapeseed oil or sunflower oil.
  • unsaturated triglycerides in particular rapeseed oil or sunflower oil.
  • rapeseed oil in particular rapeseed oil or sunflower oil.
  • sulfonated rapeseed oil is preferably used in the form of the sodium, calcium, ammonium or alkylammonium salt.
  • corrosion inhibitors are - individually or in combination - alkanolamines and their salts, in particular carboxylic acid salts, sulfonates, organic boron compounds, in particular boric acid esters, fatty acid amides, aminodicarboxylic acids, dimer fatty acids, phosphoric acid esters, thiophenic acid esters, dialkyldithiophosphates, mono- and dialkylobutylsulfonobenzylsulfonobenzylsulfonates, some of which also have emulsifying properties.
  • alkanolamines and their salts in particular carboxylic acid salts, sulfonates, organic boron compounds, in particular boric acid esters, fatty acid amides, aminodicarboxylic acids, dimer fatty acids, phosphoric acid esters, thiophenic acid esters, dialkyldithiophosphates, mono- and dialkylobutylsulfonobenzyls
  • Addition products of ethylene and / or propylene oxide onto compounds with acidic hydrogen atoms or fatty acid esters come as emulsifiers into consideration. These include, for example, alkoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid methyl esters and sorbitan esters, which can be obtained by the known processes of the prior art.
  • Typical examples are addition products of an average of 1 to 20, preferably 2 to 10, moles of ethylene oxide and 0 or 1 to 5 moles of propylene oxide onto fatty alcohols with 6 to 22 carbon atoms, alkylphenols with 4 to 12 carbon atoms in the alkyl radical, and fatty acids, fatty amines and fatty acid esters, each with 6 to 22 carbon atoms in the fat residue.
  • Addition products of 2 to 10 moles of ethylene oxide with lauryl or "21-4 ⁇ are particularly preferred
  • coconut fatty alcohol (conventional or restricted homolog distribution), on octylphenol, lauric or C- j 2 / i4 coconut fatty acid, laurylamine, coconut fatty acid methyl ester and / or sorbitan monolaurate.
  • anionic surfactants such as soaps, sulfonates and alkyl phosphates are also suitable.
  • Typical examples of this group of compounds are alkali soaps of fatty acids, naphthen soaps, alkylarylsulfonates, alkanesulfonates,
  • the ready-to-use cooling lubricant emulsion according to the invention preferably contains the basic components mentioned in addition to the elemental sulfur in the following amounts:
  • the cooling lubricants according to the invention can be they purely aqueous cooling lubricants, cutting oils or the preferred cooling lubricant emulsions, can be produced by mixing the individual components together at the point of use.
  • users of cooling lubricants generally refrain from this. Rather, they prefer to purchase either ready-to-use cutting oils or concentrates for aqueous cooling lubricants or water-mixed cooling lubricant emulsions, the ready-to-use cooling lubricant being produced from these concentrates by mixing with the appropriate amount of water.
  • the invention therefore relates in a further aspect to a concentrate for the
  • This concentrate preferably contains the following components:
  • ready-to-use cooling lubricants in the form of oil-in-water dispersions in which the elemental sulfur is dispersed in the water phase
  • concentrates for cooling lubricant emulsions as are currently customary in the art, are suitable.
  • the ready-to-use cooling lubricant according to the invention is produced from this by mixing 0.5 to 10 parts by weight of concentrate with 99.5 to 90 parts by weight of an aqueous sulfur sol which contains sulfur in the particle size range mentioned.
  • an aqueous sulfur sol which contains sulfur in the particle size range mentioned.
  • One can also proceed in such a way that instead of an aqueous sulfur sol which already contains the amount of sulfur to be used according to the invention, a more highly concentrated sol is used together with water.
  • the oil-containing concentrate can be mixed in the stated proportions with water and with sulfur powder or a sulfur paste which contain sulfur in the particle size range mentioned.
  • a sulfur powder can be obtained, for example, by freeze-drying a sulfur sol, as occurs in the production of elemental sulfur in the particle size range mentioned below.
  • a sulfur paste can be obtained, for example, by mixing the sulfur sol obtained in the production with a water-miscible solvent with a boiling point higher than water and preferably by removing water under reduced pressure until the desired paste has formed.
  • Suitable solvents are, for example, monohydric or polyhydric alcohols with a higher boiling point than water, glycols, glycol ethers or alcohol ethoxylates.
  • the cooling lubricants according to the invention can be used in processes for machining metals.
  • the invention therefore relates to such working methods in a further aspect.
  • this is equivalent to the use of cooling lubricants which contain 0.01 to 0.5% by weight of elemental sulfur with an average particle size in the range from 10 to 1500 nm, preferably in the range from 25 to 800 nm, for which machining of metals. Examples of such working methods were initially listed. It is recommended that the composition of the cooling lubricant is matched to the properties of the metal to be processed. This applies in particular to the choice of corrosion inhibitors.
  • Cooling lubricants that contain anions of carboxylic acids with 6 to 12 carbon atoms as corrosion inhibitors are particularly suitable for machining steel and other iron-containing alloys.
  • cooling lubricants are preferably selected which contain alkylphosphonic acids with 4 to 18, preferably 6 to 12, carbon atoms in the alkyl group as corrosion inhibitors.
  • alkylphosphonic acids with 4 to 18, preferably 6 to 12, carbon atoms in the alkyl group as corrosion inhibitors.
  • octylphosphonic acid can be used.
  • Cooling lubricants containing so-called non-ferrous metal inhibitors are preferably used to process non-ferrous metals such as copper, bronze or brass. These can be selected, for example, from the group of triazoles, in particular from benzotriazoles and tolyltriazoles.
  • 4.5 ml of solution a) were added to solution b) using a pipette.
  • sulfuric acid the solution turns yellow
  • the resulting mixture was a mixture of the remaining 145.5 ml of solution a) and 16.5 g of conc. Sulfuric acid added. This produced a yellowish-white precipitate.
  • the mixture obtained was left to stand in an Erlenmeyer flask covered with a watch glass for 1 h, during which a sediment formed.
  • the particle size was determined using an ultra-compact, high-performance ultra-fine granulometer (UPA).
  • UPA ultra-compact, high-performance ultra-fine granulometer
  • the X50 value means that 50% of all particles have a size that is less than or equal to this value.
  • Nanoparticulate sulfur was produced analogously to Example 1, with the difference that the peptization of the sulfur gel on the filter was distilled with 900 ml. Water was carried out, to which 4.32 g of a 25% by weight aqueous solution of cetyltrimethylammonium chloride (Dehyquart R A from Henkel KGaA) had been added.
  • Composition concentrate A (parts by weight, occasionally with and without EP additive.
  • sample samples each contain: 1.5 g of concentrate A without EP additive, different amounts of S-sol and water.
  • Comp. 1a 1.5 g of concentrate A without EP additive and 28.5 g of water.
  • Comp. 2a 1.5 g of concentrate A with EP additive and 28.5 g of water.
  • sample samples each contain: 1.5 g of concentrate A without EP additive, various amounts of solid S-sol which contains 2.5% Optigel SH.
  • Comp. 1b 1.5 g of concentrate A without EP additive and 28.5 g of water.
  • Comp. 2b 1.5 g of concentrate A with EP additive and 28.5 g of water.
  • Composition concentrate B (parts by weight, occasionally with and without EP additive.
  • sample samples each contain: 1.5 g of concentrate B without EP additive, different amounts of S-sol and water.
  • Comp. 1a 1.5 g of concentrate B without EP additive and 28.5 g of water.
  • Comp. 2a 1.5 g of concentrate B with EP additive and 28.5 g of water.
  • sample samples each contain: 1.5 g of concentrate B without EP additive, various amounts of solid S-sol which contains 2.5% Optigel SH.
  • Comp. 1b 1.5 g concentrate B without EP additive and 28.5 g water.
  • Comp. 2b 1.5 g of concentrate B with EP additive and 28.5 g of water.

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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)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un lubrifiant pour l'usinage de métaux par enlèvement de copeaux, qui contient 0,01 à 0,5 % en poids, par rapport à la quantité totale dudit lubrifiant prêt à être utilisé, de soufre élémentaire présentant une taille moyenne de particule comprise dans la plage 10-1500 nm, ainsi que des concentrés d'un tel lubrifiant.
PCT/EP2000/006650 1999-07-21 2000-07-12 Composition de lubrifiant contenant du soufre elementaire pour l'usinage de metaux WO2001007545A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61588/00A AU6158800A (en) 1999-07-21 2000-07-12 Lubricating composition containing elemental sulphur for machining metals

Applications Claiming Priority (2)

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DE19934170.2 1999-07-21
DE19934170A DE19934170A1 (de) 1999-07-21 1999-07-21 Kühlschmierstoff und Kühlschmierstoffkonzentrat enthaltend feinteiligen elementaren Schwefel

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002064713A1 (fr) * 2001-02-15 2002-08-22 Ecolab Inc Lubrifiants concentres a base d'alcool
CN102517133A (zh) * 2011-12-07 2012-06-27 石家庄金刚内燃机零部件集团有限公司 水基珩磨液及利用水基珩磨液的珩磨方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005014764A1 (fr) * 2003-07-24 2005-02-17 Ecolab Inc. Lubrifiants de chaine
EP3991919A1 (fr) * 2020-10-28 2022-05-04 Hilti Aktiengesellschaft Machine-outil mobile comprenant un lubrifiant à base d'eau ainsi qu'utilisation de la machine-outil mobile
EP4011561B1 (fr) * 2020-12-11 2024-04-10 Hilti Aktiengesellschaft Machine-outil mobile et procédé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR640880A (fr) * 1927-02-24 1928-07-24 Perfectionnements aux lubrifiants
GB424578A (en) * 1932-08-24 1935-02-25 Aeg Improvements relating to lubricants
DE695766C (de) * 1932-08-25 1940-09-02 Hugo Farwick Verfahren zur Herstellung einer Schwefel in feinster Verteilung enthaltenden Paste fuer Schneide- und Bohroele
GB588283A (en) * 1945-02-07 1947-05-19 Bertram Leonard Philip Anthony Improvements in or relating to sulphur-containing lubricants
DE937784C (de) * 1954-03-14 1956-01-12 Fritz Dr Singer Verfahren zur Kaltformgebung von Metallen
GB993836A (en) * 1963-03-26 1965-06-02 Shell Int Research Cutting oils
US4416788A (en) * 1981-10-13 1983-11-22 Atlantic Richfield Company Metal cutting oil and method for using same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR640880A (fr) * 1927-02-24 1928-07-24 Perfectionnements aux lubrifiants
GB424578A (en) * 1932-08-24 1935-02-25 Aeg Improvements relating to lubricants
DE695766C (de) * 1932-08-25 1940-09-02 Hugo Farwick Verfahren zur Herstellung einer Schwefel in feinster Verteilung enthaltenden Paste fuer Schneide- und Bohroele
GB588283A (en) * 1945-02-07 1947-05-19 Bertram Leonard Philip Anthony Improvements in or relating to sulphur-containing lubricants
DE937784C (de) * 1954-03-14 1956-01-12 Fritz Dr Singer Verfahren zur Kaltformgebung von Metallen
GB993836A (en) * 1963-03-26 1965-06-02 Shell Int Research Cutting oils
US4416788A (en) * 1981-10-13 1983-11-22 Atlantic Richfield Company Metal cutting oil and method for using same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002064713A1 (fr) * 2001-02-15 2002-08-22 Ecolab Inc Lubrifiants concentres a base d'alcool
US7462584B2 (en) 2001-02-15 2008-12-09 Ecolab Inc. Lubricant concentrate based on alcohols
CN102517133A (zh) * 2011-12-07 2012-06-27 石家庄金刚内燃机零部件集团有限公司 水基珩磨液及利用水基珩磨液的珩磨方法

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DE19934170A1 (de) 2001-01-25

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