EP0652927B1 - Concentre de matiere lubrifiante et solution aqueuse de matiere lubrifiante a base d'amines grasses, leur procede de fabrication et leur utilisation - Google Patents

Concentre de matiere lubrifiante et solution aqueuse de matiere lubrifiante a base d'amines grasses, leur procede de fabrication et leur utilisation Download PDF

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Publication number
EP0652927B1
EP0652927B1 EP93917652A EP93917652A EP0652927B1 EP 0652927 B1 EP0652927 B1 EP 0652927B1 EP 93917652 A EP93917652 A EP 93917652A EP 93917652 A EP93917652 A EP 93917652A EP 0652927 B1 EP0652927 B1 EP 0652927B1
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EP
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Prior art keywords
lubricant
general formula
weight
water
lubricant concentrate
Prior art date
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Expired - Lifetime
Application number
EP93917652A
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German (de)
English (en)
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EP0652927A1 (fr
Inventor
Alfred Laufenberg
Wolfgang Preibsch
Karl-Heinz Schmitz
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Ecolab GmbH and Co oHG
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Henkel Ecolab GmbH and Co KG
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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary 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
    • 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
    • C10M2201/02—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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary 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
    • 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
    • C10M2215/26—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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • 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
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • 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
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to a lubricant concentrate and an aqueous lubricant solution based on fatty amines and optionally conventional diluents and / or auxiliaries or additives which contain at least one polyamine derivative of a fatty amine and / or a salt of such an amine.
  • the invention further relates to a method for producing the lubricant concentrate and the use of the lubricant concentrate and the aqueous lubricant solution as a chain lubricant in the food industry.
  • the lubricant concentrate according to the invention is used for the lubrication, cleaning and disinfection of automatic chain and belt lubrication systems which are used when filling foodstuffs, preferably beverages, in glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers and the like are used.
  • plate conveyor belts or other conveyor systems are usually used for the transport of the corresponding containers, which are lubricated with suitable aqueous lubricant preparations via immersion lubrication systems or more recently also via automatic belt lubrication systems and kept clean.
  • the chain lubricants previously used as lubricants are based on the one hand on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines in the form of their organic or inorganic salts.
  • DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage bottling plants, particularly in breweries, and for cleaning the belts using a liquid cleaning agent, which is characterized in that the chain-shaped bottle conveyor belts are used with belt lubricants based on neutralized primary Lubricates fatty amines, which preferably have 12 to 18 carbon atoms and contain an unsaturated fraction of more than 10%.
  • lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
  • these fatty amine-based lubricants show unsatisfactory foaming behavior.
  • the lubricants of EP-AO 327 628 tend to form too much foam, which makes subsequent cleaning of the goods transported on the belt necessary.
  • Lubricants according to DE-A-39 05 548 have a rather low foam formation, which leads to a rapid drainage of the applied lubricating film.
  • the main disadvantages of the above-mentioned lubricants are, on the one hand, the strong water dependency of the soap-based lubricants and, on the other hand, the regularly necessary system cleaning when using lubricants based on fatty amines, which is also caused by the water content.
  • the precipitates that occur in both prior art processes must be removed.
  • a simple acid-base reaction is used for removal.
  • complexing agent-containing cleaners are used for this, and organic or inorganic acids are used as technical equivalents for this purpose in products based on fatty amines as cleaners.
  • EP-A-0 044 458 describes lubricant preparations which are practically free from fatty acid soaps and which also contain a carboxylated nonionic surfactant and an acyl sarcosinate.
  • the pH of these products is 7 to 11 and is therefore preferably in the neutral to alkaline range.
  • DE-A-38 31 448 finally relates to aqueous, clear water-soluble, soap-free lubricant preparations, a process for their preparation and the use of these lubricant preparations, in particular as lubricants for plate conveyor belts which are used to transport glass bottles or polyethylene terephthalate bottles.
  • the essentially neutral aqueous lubricant preparations (pH in the range from 6 to 8) contain alkylbenzenesulfonates, alkoxylated alkanol phosphates and alkane carboxylic acids, if appropriate in addition to customary solubilizers, solvents, defoamers and disinfectants.
  • the present invention is therefore based on the object of providing a new lubricant preparation, in particular a chain lubricant, which does not have the disadvantages of the prior art.
  • Lubricants of this type should have a good coefficient of friction, that is to say an excellent lubricating effect, a metered foam behavior, good solubility in clear water, a good cleaning action and a good microbicidal action.
  • the term “clear water solubility” is coupled with the insensitivity of the lubricant constituents to anions contained in natural water, such as sulfate, bicarbonate and the like. If, for example, the clear water solubility of a lubricant formulation is not very pronounced, such formulations can react with the water constituents when the system is shut down for a longer period, for example over the course of a weekend. The resulting precipitations and cloudiness in the lubricant's application solutions lead to clogging of the filters and nozzles of the belt lubrication system in the short to medium term.
  • lubricants which contain at least one polyamine derivative of a fatty amine and / or a salt of such an amine have a significantly better solubility in clear water and have a more favorable foaming behavior in terms of application technology than lubricants based on unsubstituted and substituted fatty amines.
  • the lubricant concentrates according to the invention have excellent clear water solubility in their form diluted with water to the application concentration, for example in the form of aqueous solutions containing 0.02% by weight of the amines. With regard to their application properties, such aqueous lubricant solutions have a good coefficient of friction, a balanced foaming behavior, a good cleaning action and good microbicidal properties.
  • R is therefore suitable as substituents R in the abovementioned general formula (I): n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- Pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-uneicosyl and n-docosyl and the branched chain isomers of the alkyl radicals mentioned.
  • R can also mean the corresponding - mono- or poly-unsaturated alkyl radicals, which can also be linear or branched.
  • the anion X- can be an anion of any inorganic or organic acid. It is only important for the selection of this acid in the sense of the present invention that the acid or its anion in connection with the polyamines of the general formula (I) according to the invention does not lead to precipitations and thus impairs the clear water solubility of the lubricants according to the invention. In individual cases, the expert will make a suitable selection based on simple tests.
  • those acids are preferred whose anion X - is selected from the group amidosulfonate, nitrate, halide, hydrogen sulfate, sulfate, hydrogen carbonate, carbonate, phosphate or R 1 -COO-, the radical R 1 being hydrogen, is a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, the substituents being selected from one or more of the radicals hydroxyl, amino, imino and carboxy.
  • anion X - in addition to the inorganic anions already mentioned - anions of organic acids of the type R 1 -COO - are also suitable.
  • the radical R 1 here can be hydrogen or alkyl or alkenyl radicals; for the rest, the above explanations for R apply analogously.
  • Examples of organic anions X- of the type R 1 -COO - may be mentioned in particular: formate, acetate, glycolate, oleate, lactate, gluconate, citrate and glutamate.
  • Those amines in which k, 1 and m is 3 are particularly preferred.
  • Polyamines which correspond to the general formula (I) given above can be prepared by processes known from the literature and are also in some cases also offered as commercial products, for example from the company Berol Nobel, Sweden, under the name Amin 640, Amin 660, Amine 740, amine 760 and amine 780.
  • auxiliaries and / or additives are, in particular, solubilizers, for example alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butylglycol, butyldiglycol or ethylene glycol ether.
  • solubilizers for example alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butylglycol, butyldiglycol or ethylene glycol ether.
  • solubilizers for example alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butylglycol, butyldiglycol or ethylene glycol ether.
  • solubilizers for example alcohols, polyalcohols, ethers or polyethers, in particular isopropanol, butylglycol, butyldiglycol or ethylene glycol ether.
  • the amount of the solubilizer to be used depends in each case
  • Auxiliaries and / or additives according to the present invention are furthermore in particular nonionic and / or amphoteric surfactants, for example alkoxylated fatty amines, fatty alcohols and alkoxylated fatty alcohols. These surfactants can improve the wetting of the chains and plate conveyor belts, should this be necessary in individual cases. In general, surfactant additives in the range from 1 to 5% by weight, based on the total formulation, are sufficient for this.
  • the lubricant concentrates according to the invention preferably have a pH in the range from 4 to 11, in particular in the range from 5 to 8. If the pH of the lubricant concentrate is not already in this range, it can be adjusted to the desired value by adding an acid, preferably an acid with the anion X - defined above, for example with acetic acid or formic acid.
  • the lubricant concentrates have a dynamic viscosity of less than 300 mPa.s, in particular less than 150 mPa.s and particularly preferably in the range from 20 to 100 mPa.s - in each case at 20 ° C - to ensure their pumpability.
  • a separate adjustment of the viscosity to the values mentioned is generally not necessary or has been carried out optionally by adding suitable amounts of the diluent water or a solubilizer.
  • the invention also relates to a method for producing the lubricants according to the invention. These can be prepared by mixing the amine components, if appropriate with the addition of water and the auxiliaries or additives mentioned.
  • the present invention further relates to the use of lubricant concentrates of the type described above as chain lubricants in the food industry, in particular in automatic chain and belt lubrication systems.
  • the present invention relates to the use of the lubricant concentrates described above in the form of a 0.01 to 50% by weight, preferably 0.1 to 0.5% by weight, aqueous solution as chain lubricant for automatic chain and belt lubrication systems.
  • the invention also relates to an aqueous lubricant solution based on fatty amines and, if appropriate, customary diluents, characterized in that it contains at least one polyamine derivative of a fatty amine of the general formula (I).
  • this lubricant solution can be obtained from the lubricant concentrates according to the invention by dilution with a factor of 2 to 10,000, preferably by a factor of 300 to 500, with water.
  • Lubricant solutions which contain a content of 0.002 to 0.1% by weight, in particular 0.003 to 0.05% by weight, of a polyamine derivative of a fatty amine of the formula (I) and a pH between 5 and 8 are particularly preferred exhibit.
  • the present invention relates to the use of the aqueous lubricant solutions described above as chain lubricants in the food industry.
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • the lubricant solutions according to the invention can be used as chain lubricants for conveying or transporting containers or bottles made of glass, plastic-coated glass, plastics, in particular polyethylene terephthalate or polyvinyl chloride, tinplate or aluminum or lacquered or plastic-coated containers made of these metals.
  • the products according to the invention are clearly better soluble in clear water than the known fatty amine-based lubricants, and moreover have a metered foam behavior, a good microbicidal action and an excellent lubricating action.
  • the desired application properties of the lubricant concentrate or the aqueous lubricant solution can be specifically set by choosing the amine or the anion.
  • lubricant concentrates and solutions according to the invention can also advantageously be used as so-called cutting oils or cooling lubricants in metalworking.
  • the performance properties of the polyamine derivatives of fatty amines of the formula (I) were checked using their amine acetates.
  • 90 g of demineralized water heated to 50 to 60 ° C. were initially introduced and 10 g of the respective amine were stirred in in molten form.
  • the amine acetates were obtained by adding acetic acid until a pH of 6.5 was reached.
  • the lubricating effect of the amines is shown in Table II.
  • Table II E.g. Amine base Coefficient of friction Relubrication foam 1 Amine 1 * ⁇ ⁇ 0.1 7.5 min thin foam film 2nd Amine 2 * ⁇ ⁇ 0.1 8.5 min thin foam film 3rd Comparative experiment ** ⁇ ⁇ 0.1 7.5 min no foam * without surfactant ** Mixture of amine 6, amine 7, ester of dimer fatty acid (C 36 ) with polyethylene glycol (18 E0) and coconut amine with 12 E0 (10: 10: 5: 2).

Claims (14)

  1. Concentré d'agent lubrifiant à base d'amines grasses et le cas échéant d'agents de dilution usuels et/ou des substances auxiliaires ou d'additifs,
    caractérisé en ce que
    il contient au moins un dérivé de polyamine d'une amine grasse de formule générale (I)

            R-A-(CH2)k-NH-[(CH2)l-NH]y-(CH2)m-NH2 · (H+X-)n     (I)

    dans laquelle,
    R est un radical alcoyle linéaire ou ramifié, saturé ou non saturé une fois ou plusieurs fois, ayant de 8 à 22 atomes de carbone.
    A représente -NH-
    X- signifie un anion d'un acide minéral ou organique.
    K,l,m indépendamment les uns des autres est un nombre entier dans la zone de 1 à 6,
    y est 0,1,2 ou 3.
    n est un nombre entier de 0 à 6 et dans laquelle le concentré d'agent lubrifiant contient de 1 à 40 % en poids de dérivé de polyamine de formule générale (I) ainsi que de 99 à 60 % en poids d'eau et/ou de substances auxiliaires ou d'additifs à chaque fois rapporté à la formulation totale.
  2. Concentré d'agent lubrifiant selon la revendication 1, caractérisé en ce que l'anion X- est choisi dans le groupe des amidosulfonate, nitrate, halogénure, hydrogénosulfate, sulfate, hydrogéno-carbonate, carbonate, phosphate et R1-COO- dans lequel R1, représente de l'hydrogène, un radical alcoyle substitué ou non substitué, linéaire ou ramifié ayant de 1 à 20 atomes de carbone ou un radical alcényle ayant de 2 à 20 atomes de carbone, dans lesquels les substituants sont choisis parmi un ou plusieurs des radicaux hydroxy, amino, imino et carboxy.
  3. Concentré d'agent lubrifiant selon la revendication 1 ou 2,
    caractérisé en ce que
    il renferme un dérivé de polyamine de formule générale (I) dans laquelle A est -NH-, K,l,m indépendamment les uns des autres sont 3 ou 4 en particulier 3, y est 0 ou 1 ; et R, R1, X, n respectivement ont les significations indiquées dans les revendications 1 et 2 pour la formule générale (I).
  4. Concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 3,
    caractérisé en ce que
    dans la formule générale I, R représente un radical alcoyle linéaire ou ramifié, saturé ou une fois ou plusieurs fois non saturé, ayant de 12 à 18 atomes de carbone,
    A représente -NH- et,
    X- représente le radical R1COO- dans lequel R1 signifie de l'hydrogène, CH3, HO-CH2, ou CH3CH(OH).
  5. Concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 4,
    caractérisé en ce que
    il contient de 5 à 15 % en poids de dérivé de polyamine de formule générale (I) ainsi que 95 à 85 % en poids d'eau et/ou de substances auxiliaires ou d'additifs, à chaque fois rapporté à la formulation totale.
  6. Concentré d'agent lubrifiant selon la revendication 5, caractérisé en ce que
    il renferme comme substance auxiliaire ou comme additif un agent dissolvant et/ou un agent tensioactif non ionique et/ou un agent tensioactif amphotère.
  7. Concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 6,
    caractérisé en ce que
    il possède une valeur de pH dans la zone de 4 à 11, de préférence dans la zone de 5 à 8.
  8. Utilisation du concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 7 comme agent de glissement pour chaînes dans l'industrie alimentaire.
  9. Utilisation selon la revendication 8,
    caractérisée en ce que
    on utilise les concentrés d'agent lubrifiant dans les installations automatique à chaîne et à bande.
  10. Procédé d'obtention du concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 9,
    caractérisé en ce que
    on mélange le(s) composant(s) aminé(s) le cas échéant en ajoutant de l'eau, avec les substances auxiliaires ou les additifs.
  11. Solution aqueuse d'agent lubrifiant à base d'amines grasses et le cas échéant d'agents de dilution usuels,
    caractérisée en ce que
    elle contient au moins un dérivé de polyamine d'une amine grasse de formule générale (I) selon l'une ou plusieurs des revendications 1 à 4.
  12. Solution aqueuse d'agent lubrifiant selon la revendication 11,
    caractérisée en ce qu'elle est obtenue par dilution d'un concentré d'agent lubrifiant selon l'une ou plusieurs des revendications 1 à 7, avec de l'eau d'un facteur de 2 à 10.000 de préférence d'un facteur de 300 à 500.
  13. Solution aqueuse d'agent lubrifiant selon l'une des revendications 11 ou 12,
    caractérisée en ce que
    elle contient entre 0,002 et 0,1 % en poids, en particulier entre 0,003 et 0,05 % en poids d'un dérivé de polyamine d'une amine grasse de formule (I) et qu'elle possède un pH entre 5 et 8.
  14. Utilisation de la solution aqueuse d'agent lubrifiant selon l'une ou plusieurs des revendications 11 à 13 en tant qu'agent de glissement pour chaînes dans l'industrie alimentaire, pour favoriser ou pour le transport des fûts métalliques ou des bouteilles en verre, verre revêtu de matière plastique, matières plastiques, en particulier téréphtalate de polyéthylène ou chlorure de polyvinyle, fer blanc, ou aluminium ou de récipients laqués ou revêtus de matière plastique de ces métaux.
EP93917652A 1992-08-03 1993-07-26 Concentre de matiere lubrifiante et solution aqueuse de matiere lubrifiante a base d'amines grasses, leur procede de fabrication et leur utilisation Expired - Lifetime EP0652927B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4225254 1992-08-03
DE4225254 1992-08-03
PCT/EP1993/001984 WO1994003562A1 (fr) 1992-08-03 1993-07-26 Concentre de matiere lubrifiante et solution aqueuse de matiere lubrifiante a base d'amines grasses, leur procede de fabrication et leur utilisation

Publications (2)

Publication Number Publication Date
EP0652927A1 EP0652927A1 (fr) 1995-05-17
EP0652927B1 true EP0652927B1 (fr) 1996-12-18

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EP93917652A Expired - Lifetime EP0652927B1 (fr) 1992-08-03 1993-07-26 Concentre de matiere lubrifiante et solution aqueuse de matiere lubrifiante a base d'amines grasses, leur procede de fabrication et leur utilisation

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EP (1) EP0652927B1 (fr)
JP (1) JPH07509517A (fr)
KR (1) KR950702616A (fr)
AT (1) ATE146518T1 (fr)
AU (1) AU666038B2 (fr)
BR (1) BR9306831A (fr)
CA (1) CA2141811A1 (fr)
CZ (1) CZ26095A3 (fr)
DE (1) DE59304833D1 (fr)
DK (1) DK0652927T3 (fr)
ES (1) ES2096314T3 (fr)
FI (1) FI113784B (fr)
GR (1) GR3022255T3 (fr)
HU (1) HUT69076A (fr)
MX (1) MX9304645A (fr)
NO (1) NO312418B1 (fr)
NZ (1) NZ254769A (fr)
PL (1) PL307307A1 (fr)
SK (1) SK12695A3 (fr)
WO (1) WO1994003562A1 (fr)
ZA (1) ZA935573B (fr)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510045A (en) * 1988-07-14 1996-04-23 Diversey Corporation Alkaline diamine track lubricants
DE4315271A1 (de) * 1993-05-07 1994-11-10 Laporte Gmbh Schmiermittelzusammensetzungen
DE19642598A1 (de) * 1996-10-16 1998-04-23 Diversey Gmbh Schmiermittel für Förder- und Transportanlagen in der Lebensmittelindustrie
DE19721602A1 (de) * 1997-05-23 1998-11-26 Henkel Ecolab Gmbh & Co Ohg Pasten- oder gelförmiges Hochkonzentrat für aminhaltige Schmiermittellösungen in der Lebensmittelindustrie
US20040055965A1 (en) * 1997-06-13 2004-03-25 Hubig Stephan M. Recreational water treatment employing singlet oxygen
US20030194433A1 (en) * 2002-03-12 2003-10-16 Ecolab Antimicrobial compositions, methods and articles employing singlet oxygen- generating agent
DE19921709A1 (de) 1999-05-12 2000-11-16 Henkel Ecolab Gmbh & Co Ohg Verfahren und Anlage zur Schmierung und zur Reinigung von Abfüllanlagen für Getränke und Lebensmittel
DK1842898T3 (da) 1999-07-22 2012-08-13 Diversey Inc Anvendelse af en smøremiddelsammensætning til at smøre et transportbælte
US6495494B1 (en) 2000-06-16 2002-12-17 Ecolab Inc. Conveyor lubricant and method for transporting articles on a conveyor system
US6207622B1 (en) * 2000-06-16 2001-03-27 Ecolab Water-resistant conveyor lubricant and method for transporting articles on a conveyor system
DE19942536A1 (de) 1999-09-07 2001-03-08 Henkel Ecolab Gmbh & Co Ohg Verwendung von Schmiermitteln auf Polysiloxan-Basis
DE19942534A1 (de) 1999-09-07 2001-03-08 Henkel Ecolab Gmbh & Co Ohg Fluorhaltige Schmiermittel
DE19959315A1 (de) 1999-12-09 2001-06-21 Henkel Ecolab Gmbh & Co Ohg Verbesserung des Transports von Gebinden auf Transportanlagen
WO2001098441A1 (fr) * 2000-06-23 2001-12-27 Pentasol (Fb) Limited Lubrifiant pour transporteur
US6591970B2 (en) 2000-12-13 2003-07-15 Ecolab Inc. Water-activatable conveyor lubricant and method for transporting articles on a conveyor system
US6509302B2 (en) * 2000-12-20 2003-01-21 Ecolab Inc. Stable dispersion of liquid hydrophilic and oleophilic phases in a conveyor lubricant
DE10106954A1 (de) 2001-02-15 2002-09-05 Ecolab Gmbh & Co Ohg Schmiermittelkonzentrate auf alkoholischer Basis
EP1273653A1 (fr) * 2001-07-04 2003-01-08 Polygon Chemie AG Etherdiamines ou N-alkyle-diaminopropane ou leur melange comme lubrifiants
DE10146264A1 (de) 2001-09-20 2003-04-17 Ecolab Gmbh & Co Ohg Verwendung von O/W-Emulsionen zur Kettenschmierung
US20070020300A1 (en) * 2002-03-12 2007-01-25 Ecolab Inc. Recreational water treatment employing singlet oxygen
US20040235680A1 (en) * 2002-09-18 2004-11-25 Ecolab Inc. Conveyor lubricant with corrosion inhibition
US7148188B2 (en) * 2002-09-18 2006-12-12 Ecolab Inc. Bottlewash additive comprising an alkyl diphenylene oxide disulfonate
US20050119139A1 (en) * 2003-12-01 2005-06-02 Luigi Ciampi Composition of belt lubricant
US20050288191A1 (en) * 2004-06-24 2005-12-29 Ecolab Inc. Conveyor system lubricant
US20060046940A1 (en) * 2004-08-27 2006-03-02 Mohannad Almalki Aqueous conveyor and cutting lubricant
US7745381B2 (en) 2005-03-15 2010-06-29 Ecolab Inc. Lubricant for conveying containers
US7741257B2 (en) 2005-03-15 2010-06-22 Ecolab Inc. Dry lubricant for conveying containers
US7820603B2 (en) * 2005-03-15 2010-10-26 Ecolab Usa Inc. Low foaming conveyor lubricant composition and methods
DE102008009937A1 (de) 2008-02-20 2009-09-03 Calvatis Gmbh Reinigungsverfahren für Transportbänder
US8492572B2 (en) 2009-06-18 2013-07-23 Akzo Nobel Chemicals International B.V. Liquid fatty amine carboxylate salt composition
MX360111B (es) 2010-09-24 2018-10-23 Ecolab Usa Inc Lubricantes de transportador que incluyen emulsiones y metodos para emplear los mismos.
CA2904930C (fr) 2013-03-11 2021-12-14 Ecolab Usa Inc. Lubrification de plaques de transfert utilisant une huile ou des emulsions d'huile dans l'eau
FR3039835B1 (fr) * 2015-08-03 2019-07-05 Total Marketing Services Utilisation d'une amine grasse pour prevenir et/ou reduire les pertes metalliques des pieces dans un moteur
CN111171948B (zh) * 2020-01-17 2022-04-01 法尔胜泓昇集团有限公司 一种石墨烯改性润滑剂及其制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976179A (en) * 1954-08-23 1961-03-21 Exxon Research Engineering Co Rust preventives
US2990943A (en) * 1956-10-09 1961-07-04 Armour & Co Metal working process
US3634243A (en) * 1969-01-09 1972-01-11 Cincinnati Milling Machine Co Method of removing suspended matter from cutting fluids and cutting oils by addition of cationic surfactants
US3860521A (en) * 1972-03-20 1975-01-14 Basf Wyandotte Corp Soap based chain conveyor lubricant
GB1445993A (en) * 1973-06-27 1976-08-11 Exxon Research Engineering Co Lubricating oil compositions
US4374034A (en) * 1974-01-14 1983-02-15 The Lubrizol Corporation Polymeric compositions, method for their preparation, and lubricants containing them
DE3161426D1 (en) * 1980-07-18 1983-12-22 Unilever Nv Lubricant composition
US4505831A (en) * 1983-06-20 1985-03-19 Buckman Laboratories, Inc. Method of preservation of aqueous systems by addition to said systems of quaternary ammonium salts of hexamethylenetetramine
US4537694A (en) * 1983-09-23 1985-08-27 Mobil Oil Corporation Diamine carboxylates and lubricant compositions containing same
US4647389A (en) * 1985-08-19 1987-03-03 Texaco Inc. Anti-friction additives for lubricating oils
JPS62152245A (ja) * 1985-12-25 1987-07-07 Yamatake Honeywell Co Ltd 通信制御方式
DE3631953A1 (de) * 1986-09-19 1988-03-31 Akzo Gmbh Verfahren zum schmieren und reinigen von flaschentransportbaendern in der getraenkeindustrie
US5061797A (en) * 1988-03-29 1991-10-29 Buckman Laboratories International, Inc. 1-methyl-3,5,7-triaza-1-azoniatricyclodecane compounds
DE68928114T2 (de) * 1988-05-31 1998-01-22 Digital Equipment Corp Bitfolgenverarbeitungsgerät und -verfahren
DE3831448A1 (de) * 1988-09-16 1990-03-22 Henkel Kgaa Klarwasserloesliche seifenfreie schmiermittelzubereitung
EP0372628B2 (fr) * 1988-12-05 1996-10-30 Unilever N.V. Utilisation des solutions lubrifiantes aqueuses à base d'amines grasses alkylées
DE3905548A1 (de) * 1989-02-23 1990-09-06 Henkel Kgaa Schmiermittel und seine verwendung
JPH04180425A (ja) * 1990-11-15 1992-06-26 Toshiba Corp 通信システム
US5174914A (en) * 1991-01-16 1992-12-29 Ecolab Inc. Conveyor lubricant composition having superior compatibility with synthetic plastic containers

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Publication number Publication date
ZA935573B (en) 1994-02-03
US5474692A (en) 1995-12-12
BR9306831A (pt) 1998-12-08
DK0652927T3 (da) 1997-06-09
AU4702693A (en) 1994-03-03
FI950437A0 (fi) 1995-02-01
AU666038B2 (en) 1996-01-25
FI950437A (fi) 1995-02-01
ES2096314T3 (es) 1997-03-01
SK12695A3 (en) 1995-06-07
DE59304833D1 (de) 1997-01-30
CA2141811A1 (fr) 1994-02-17
CZ26095A3 (en) 1995-09-13
NO944100D0 (no) 1994-10-27
HU9500337D0 (en) 1995-03-28
EP0652927A1 (fr) 1995-05-17
JPH07509517A (ja) 1995-10-19
ATE146518T1 (de) 1997-01-15
WO1994003562A1 (fr) 1994-02-17
GR3022255T3 (en) 1997-04-30
FI113784B (fi) 2004-06-15
NO312418B1 (no) 2002-05-06
NO944100L (no) 1994-10-27
MX9304645A (es) 1994-02-28
PL307307A1 (en) 1995-05-15
NZ254769A (en) 1996-02-27
HUT69076A (en) 1995-08-28
KR950702616A (ko) 1995-07-29

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