EP3559176B1 - Utilisation de graisses lubrifiantes ayant un complexe de calcium et de graisses lubrifiantes ayant un complexe de sulfonate de calcium, pour la lubrification de câbles métalliques - Google Patents

Utilisation de graisses lubrifiantes ayant un complexe de calcium et de graisses lubrifiantes ayant un complexe de sulfonate de calcium, pour la lubrification de câbles métalliques Download PDF

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EP3559176B1
EP3559176B1 EP17842380.2A EP17842380A EP3559176B1 EP 3559176 B1 EP3559176 B1 EP 3559176B1 EP 17842380 A EP17842380 A EP 17842380A EP 3559176 B1 EP3559176 B1 EP 3559176B1
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Prior art keywords
calcium
lubricating grease
grease composition
acid
weight percent
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German (de)
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EP3559176A2 (fr
EP3559176B9 (fr
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Roman Müller
Stephan Müller
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Fuchs SE
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Fuchs Petrolub SE
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02—Mixtures of base-materials and thickeners
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/043—Sulfur; Selenenium; Tellurium
    • 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
    • C10M2201/0606—Metal compounds used as thickening agents
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • 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
    • C10M2201/087—Boron oxides, acids or salts
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal 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
    • 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
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • 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
    • C10M2219/046—Overbasedsulfonic acid salts
    • C10M2219/0466—Overbasedsulfonic acid salts used as thickening 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
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/68—Shear stability
    • 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

Definitions

  • the invention relates to the use of calcium complex grease compositions containing waxes (calcium complex hybrid greases) and/or calcium sulphonate complex grease compositions containing waxes (calcium sulphonate complex hybrid greases) as lubricants for wire ropes. Furthermore, the invention relates to a method for manufacturing the wire ropes and wire ropes provided with the grease composition.
  • a characteristic of a lubricating grease or a lubricating grease composition is that a liquid oil component is absorbed and held by a thickener component.
  • the pasty nature of a lubricating grease and its property of being spreadable and easily plastically deformable, together with the property of being adhesive, ensure that the lubricating grease wets the lubricating point and the lubricating effect develops permanently on the tribologically stressed surfaces.
  • the most important rheological properties of a lubricating grease include the consistency or its yield point, the avoidance of post-hardening and excessive oil separation under thermal and mechanical stress, and stable viscosity-temperature behavior.
  • a thixotropic (shear-thinning) and shear-unstable behavior of the lubricating grease is often advantageous.
  • a high level of practical experience is required.
  • Lubricating greases generally consist of a thickening agent that is homogeneously distributed in a base oil.
  • Various substances are known as base oils.
  • Organic and inorganic compounds are used as thickeners.
  • a variety of grease compositions are known. These also include calcium sulfonate complex greases and calcium complex greases.
  • the calcium sulfonate complex greases contain a base oil and a calcium sulfonate thickener which is obtained from a particulate amorphous calcium carbonate-containing overbased calcium sulfonate, the calcium carbonate converting at least partially, preferably predominantly by weight, to a calcitic structure during the course of the reaction.
  • calcite-containing overbased calcium sulfonate greases are detailed, for example, in US Pat EP 0613940 B1 described.
  • Calcium complex lubricating greases contain a base oil and a thickener made up of calcium hydroxide, fatty acid and a complexing agent.
  • Wire ropes sometimes also called steel ropes, are essential mechanical components that enable the transmission of tensile forces, especially in materials handling technology, in the fishing industry, in mining and in construction.
  • Wire ropes can fulfill static tasks, especially in the form of guy ropes, or are used to transmit power in dynamic applications, for example in cranes, elevators, cable cars or ski lifts.
  • Wire ropes for dynamic applications in particular are exposed to constant alternating loads, wear out after a certain period of use and therefore have to be replaced periodically. The wear of the wire ropes is due, among other things, to the individual elements rubbing against each other. Wire ropes that are used for dynamic applications are particularly affected by frictional wear, as they are subject to constant flexing when deflecting and/or winding and unwinding.
  • thixotropic lubricants based on solvent raffinates are used for wire ropes, but more rarely soap greases, here predominantly lithium soap greases.
  • CN102827678 discloses a rope lubricating composition for reducing rust and improving lubrication.
  • CN103484218 discloses a wire rope lubricant.
  • the task of the lubricating grease to be used according to the invention is to provide the following property profile as far as possible: excellent viscosity-temperature behavior, good pumpability, a low Fraass breaking point, excellent corrosion protection even with water absorption, good elastomer compatibility, a high Dropping point, excellent anti-wear properties, good EP (extreme pressure) behavior, low oil separation, good oxidation stability, good adhesion, good pH buffering capacity, low consistency loss through water absorption and excellent shear stability (compared to thixotropic lubricants) .
  • the grease should be non-bituminous and also be available in formulations with or without a low aromatic hydrocarbon content.
  • the invention also relates to wire ropes provided with the grease composition and the manufacture of wire ropes incorporating the grease composition.
  • Waxes are materials that are solid and kneadable at 20°C and higher, are translucent to opaque but not glassy, melt above 40°C without decomposition, and have relatively low viscosity above the melting point.
  • the lubricating grease composition is also referred to below as rope lubricant.
  • the wire ropes used according to the invention can have very different configurations. They always consist of several wires which, according to a preferred embodiment, are stranded and/or twisted so that several strands form a wire rope.
  • the wire rope can comprise a core made of steel or plastic, around which strands of 6 wires each are wound, with a further layer of wire with 12 strands, also each of 6 wires, being laid around this wire layer.
  • the individual elements can be provided with a common casing, for example made of a plastic.
  • inserts and snaffles can also be used.
  • Wire ropes can, for example, have a core wire or core strand as well as an insert (also called core).
  • Snaffles are fibers or solid polymers arranged to separate adjacent strands or wires in the same or superimposed layers, or to fill in the interstices of the rope.
  • insole materials There are essentially three types of insole materials: fiber inlays made from natural fibers or synthetic fibers and steel inlays.
  • Steel cores can be formed from one or more wire strands or as independently stranded wire rope.
  • Polymer inserts can be, inter alia, solid polymer in cylindrical form with and without grooves. Wire ropes within the meaning of the present invention therefore do not necessarily consist exclusively of steel, but can also additionally include synthetic or natural materials.
  • Grease Type I Calcium Sulphonate Complex Grease (Comparison Grease) and Calcium Sulphonate Complex Hybrid Grease
  • overbased calcium sulphonate is provided in a base oil.
  • Calcium carbonate can, but does not have to be added.
  • the activator(s) is/are added, in particular at from 40 to 100.degree.
  • gelation occurs with a time delay, depending on the temperature. This can also be done under a slight overpressure, which increases the reaction speed.
  • the activator/activators are heated above the boiling point in order to remove the activator mixture.
  • the consistency of the lubricating grease can be further thickened by additionally adding the above-mentioned further thickeners (see above under "optional components").
  • the soap is now heated to approx. 170-190 °C and the temperature is maintained for 30 to 60 minutes. After cooling to approx. 60 to 100 °C, additives to reduce wear, improve oxidation resistance, improve corrosion protection, etc. can be added.
  • the base oil (A) serves primarily as a dispersing medium, ie as a liquid carrier in which the solid particles are dispersed.
  • the base oil is typically organic liquids that are chemically essentially inert during manufacture or intended use.
  • the base oil preferably has a kinematic viscosity of 20 to 1000 mm 2 /s, preferably 100 to 500 mm 2 /s (in each case at 40° C.).
  • the base oil is usually an organic liquid that is non-volatile at room temperature, but which can also contain volatile components, which are usually largely separated after synthesis or refining. Volatile components are defined here as those components which boil at up to about 100° C. at atmospheric pressure, such as water or C1 to C4 alcohols.
  • the base oil preferably has a flash point greater than 180.degree. C., in particular greater than 200.degree.
  • Examples of corresponding organic liquids are alkanes and cycloalkanes, aromatics and cycloaromatics, which can also be alkyl- and/or alkenyl-substituted accordingly; ethers such as dialkyl ethers; alkyl aryl ethers; cycloalkyl ethers; alkyl cycloalkyl ethers; alkanols, alkylene glycols, polyalkylene glycols and esters of these glycols; alkyl ethers of alkylene glycols and polyalkylene glycols; silicate esters, glycerides, epoxidized glycerides, aliphatic and aromatic esters; and/or slack wax (unrefined paraffin-based petroleum fractions).
  • ethers such as dialkyl ethers; alkyl aryl ethers; cycloalkyl ethers; alkyl cycloalkyl ethers; alkanol
  • Low molecular weight liquid polymers which are generally referred to as oligomers, are also suitable as base oils. These include dimers, trimers, tetramers, pentamers, and the like. Specific examples of this large group of materials are poly-alpha-olefins defined as oligomers averaging 2 to 6 or more units of C8 to C13 alpha-olefins or independently having a viscosity of 2 to 100 mm 2 /s ( at 100°C). Another important group are polyisobutylenes from 200 to 4000 g/mol (number average).
  • Alkyl, cycloalkyl, and aryl and alkylaryl hydrocarbons represent the preferred class of base oils from the standpoint of availability, cost, and properties.
  • Liquid petroleum fractions represent another preferred class of base oils alkylated benzenes, naphthalenes and alkyl naphthalenes, cycloalkanes and alkylated cycloalkanes, cycloalkenes and alkylated cycloalkenes found in naphthenic-based petroleum fractions, and alkanes found in paraffin-based petroleum fractions.
  • Particularly preferred disperse systems are those which contain at least a certain proportion of mineral oil as a component of the disperse medium.
  • calcium sulfonate (B) as used herein in relation to the calcium sulfonate complex grease, generally refers to those sulfonates in which the sulfonic acid (without the metal counterion) has a molecular weight in the range of 200 to 1400 g/ mol, in particular 300 to 700 g/mol.
  • the calcium sulfonates are generally formed in situ from a mixture of calcium oxide and/or calcium hydroxide, particularly preferably calcium hydroxide, and the sulfonic acid, preferably in solution in a volatile organic solvent, such as the above activators, and a mineral oil.
  • the calcium sulfonate is said to be overbased because it contains an excess of calcium carbonate and/or calcium hydroxide.
  • the calcium hydroxide can also be provided as calcium oxide.
  • the actual stoichiometric excess of metal can vary considerably, for example from 0.1 to about 30 or more molar equivalents, in particular greater than 0.5, so that the following TBN (Total Base Number) is established.
  • the overbased calcium sulphonate preferably has a TBN of from 40 to 600, more preferably from 200 to 600 as measured according to ISO 3771.
  • the calcium carbonate is present as a colloidal particle.
  • the maximum particle size is below 5000 ⁇ .
  • the other sulfonic acids (C) can be oil-soluble and, in addition, possibly also water-soluble at the same time.
  • Preferred sulfonic acids have the following structure:
  • the sulfonate group is attached to a cyclic or aromatic moiety, which cyclic or aromatic moiety may further contain one or more linear or branched C1 to C30 hydrocarbyl moieties, preferably one or two C8 to C18 hydrocarbyl moieties remains.
  • alkyl benzene sulfonic acids such as dobanic acid (dodecyl benzene sulfonic acid).
  • sulfonic acids or sulfonates can be synthetic or natural sulfonates, the so-called “mahogany sulfonates”.
  • synthetic sulfonates refers to those sulfonates that result from the sulfonation of feedstocks that are synthetically produced.
  • the synthetic sulfonates include alkyl sulfonates and alkyl or di-alkylaryl sulfonates.
  • the aryl radical can be derived from benzene, toluene, phenylbenzene, diphenylbenzene, diphenylmethane, ethylbenzene, xylene isomers or naphthalene.
  • the cyclic radical can be, for example, cyclohexane or hexahydronaphthalene.
  • di-alkylaryl sulfonates are those with alkyl groups each having 8 to 18 carbon atoms. They are distinguished from the previous sulfonation feedstocks primarily in that they are straight chain and contain a large amount of disubstituted material.
  • sulfonates that can be used include, for example, lignin sulfonates, mono- and poly-wax substituted naphthalene sulfonates, dinonyl naphthalene sulfonates, naphthalene disulfide sulfonates, dicetyl thianthrene sulfonates, dilauryl beta-naphthol sulfonates, unsaturated paraffin wax sulfonates, hydroxy-substituted paraffin wax sulfonates, cycloaliphatic sulfonates such as lauryl cyclohexyl sulfonates, and mono- or poly-wax substituted cyclohexyl sulfonates.
  • Suitable alcohols are aliphatic, cycloaliphatic and arylaliphatic mono- or polyhydroxy alcohols. Alcohols having less than about 12 carbon atoms are particularly useful. For reasons of economy and to ensure expedient operation of the process, lower alkanols, for example alkanols having fewer than 8 carbon atoms, are preferred.
  • alkanols such as methanol, ethanol, isopropanol, n-propanol, isobutanol, tert-butanol, n-pentanol and the like; cycloalkyl alcohols such as cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 2-cyclohexylethanol and cyclopentylmethanol; phenylaliphatic alkanols such as benzyl alcohol, 2-phenylethanol and cinnamyl alcohol; Alkylene glycols with up to about 6 carbon atoms and their mono-, di- or tri-C1 to C6-alkyl ethers, such as ethylene glycol monomethyl ether, diethylene glycol, ethylene glycol, trimethylene glycol, hexamethylene glycol, triethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol
  • a particularly effective combination consists of a mixture of one or more activators and water in a weight ratio of activator(s) to water of from about 1:0.05: to 1:24, preferably from 1:2 to 1:6 at least one lower alkanol or glycol present in the alcohol component of these water-alkanol mixtures.
  • a volatile activator e.g. B. water or a water-soluble or slightly water-miscible or water-dispersible aliphatic C1 to C4 alcohol, preferably isopropanol, and / or a water-soluble or slightly water-miscible or easily water-dispersible alkoxyalkanol or glycols (especially mono-, di- or triglycols) , Each having 2 to 20 carbon atoms, including their mono-C1 to C4 alkyl ethers, and mixtures of one or more of these activators.
  • a volatile activator e.g. B. water or a water-soluble or slightly water-miscible or water-dispersible aliphatic C1 to C4 alcohol, preferably isopropanol, and / or a water-soluble or slightly water-miscible or easily water-dispersible alkoxyalkanol or glycols (especially mono-, di- or triglycols) , Each having 2 to
  • Type II grease Calcium complex hybrid grease
  • Calcium Complex Hybrid Greases are usually prepared by adding base oil, fatty acid (including hydroxy fatty acids) and/or triglyceride to a container and heating to about 80°C until all components have melted.
  • the base oil (a) can be specified as described above for base oil (A).
  • the calcium soap is a calcium salt of one or more saturated or unsaturated monocarboxylic acids having 10 to 36 carbon atoms, optionally substituted, in particular having 12 to 22 carbon atoms, particularly preferably corresponding hydroxycarboxylic acids.
  • suitable carboxylic acids are lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid, and preferably 12-hydroxystearic acid.
  • corresponding lower alcohol esters can also be used with saponification, e.g. B. corresponding triglycerides and the methyl, ethyl, propyl, isopropyl or sec-butyl esters of the acid / hydroxy acid to achieve better dispersion.
  • At least one of acetic acid, dicarboxylic acids or phosphoric acid is used as a complexing agent within the meaning of the invention.
  • other complexing agents can be used.
  • Further examples of complexing agents (c) are C1 to C6 carboxylic acids, C6 to C12 di- and/or tricarboxylic acids, benzoic acid, boric acids and their salts, phosphoric acids and their salts, especially calcium salts but also lithium, sodium or potassium salts . Mixtures of 2 or more of these components are also suitable. Particularly suitable complexing agents are explained below.
  • the lower aliphatic carboxylic acids are C1 to C6 carboxylic acids.
  • Examples of this class of acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, isobutyric acid, caprylic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and the like.
  • Formic acid, acetic acid and propionic acid are preferred, with acetic acid and propionic acid being particularly suitable.
  • the anhydrides of these acids are also suitable, so that according to the invention the term acid encompasses both the acid as such and its anhydride.
  • Hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid) or 4-hydroxy-4-methoxybenzoic acid are also suitable.
  • Particularly suitable dicarboxylic acids are adipic acid (C 6 H 10 O 4 ), sebacic acid (C 10 H 18 O 4 ), azelaic acid (C 9 H 16 O 4 ) and/or 3- tert -butyladipic acid (C 10 H 18 O 4 ).
  • Boric acid or boronic acids are also suitable complexing agents. These include boronic acids such as alkyl-B(OH) 2 ; or aryl-B(OH) 2 , boric acid (ie H 3 BO 3 ), tetraboric acid, metaboric acid and esters of these boric or boronic acids. Metaborate, diborate, tetraborate or orthoborate, such as calcium orthoborate or lithium tetraborate, for example, can be used as the borate.
  • the wax can be added during or after the soap(s) are made.
  • bentonites such as montmorillonite (the sodium ions of which may have been exchanged or partially exchanged for ammonium ions), aluminosilicates, alumina, silicic acid (eg Aerosil) or di- and polyureas can also be used as co-thickeners.
  • the bentonites, aluminosilicates, clays, silicic acid and/or oil-soluble polymers can be added to produce the base fat or, in particular, can be added later as an additive in the second step.
  • the di- and polyureas can be added as an additive.
  • the other components mentioned below can be added both to the calcium sulfonate complex hybrid lubricating grease and to the calcium complex hybrid lubricating grease.
  • C10 to C36 carboxylic acids and their hydroxycarboxylic acids and their esters can be used as further thickeners.
  • the rope lubricants for use according to the invention contain waxes. These are referred to herein as hybrid lubricants.
  • the waxes are in particular hydrocarbon waxes such as paraffin waxes, isoparaffin waxes (microwaxes), polyolefin waxes such as PE waxes or PP waxes, FT waxes, GTL waxes, etc., candeli-ila wax, ozokerite, or polyamide waxes.
  • Another group of waxes are ester-based waxes such as carnauba wax, candelilla wax, montan wax or alcohol-based waxes such as sonic acid wax.
  • the group of natural waxes includes ozokerite and montan wax (fossil wax), candelilla wax and carnauba wax (vegetable wax) or sonic acid wax (animal wax).
  • the group of synthetic waxes includes polyamide wax (polymer wax) or GTL or FT waxes.
  • the waxes have a solidification point of greater than 70°C, in particular greater than 110°C or alternatively greater than 140°C (measured e.g. according to DIN ISO 2207).
  • the waxes are contained in the lubricating grease composition at 10 to 50% by weight, in particular 20 to 35% by weight.
  • waxes one wax fraction having the solidification point described above and the other wax fraction having a solidification point which is at least 10° C., preferably at least 20° C., lower.
  • the dropping point of the lubricating grease is preferably greater than 325°C according to DIN ISO 2176.
  • compositions further contain lubricant additives as additives.
  • lubricant additives are antioxidants, antiwear agents, anticorrosive agents, detergents, dyes, lubricity improvers, viscosity additives, friction modifiers and extreme pressure additives and solid lubricants.
  • the grease compositions may contain conventional anti-corrosion, anti-oxidant, anti-metallic lubricant additives that act as chelate compounds, free-radical scavengers, UV protectants, reaction layer formers, and the like.
  • solid lubricants examples include polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth and zinc, salts of alkali and alkaline earth metals such as calcium carbonate, Sodium and calcium phosphates are used.
  • polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth and zinc
  • salts of alkali and alkaline earth metals such as calcium carbonate, Sodium and calcium phosphates are used.
  • Solid lubricants can be divided into the following groups: compounds with a layered lattice structure, such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride and some metal halides; oxidic and hydroxy compounds of transition and alkaline earth metals or their carbonates or phosphates; soft metals and/or plastics.
  • the desired advantageous lubricating properties can also be set through the use of lignin sulfonates without having to use solid lubricants. In many cases, these can be dispensed with entirely or they can at least be significantly minimized.
  • the rope lubricant based on calcium complex hybrid soaps contains at least the following components: Areas in wt% base oil 40 to 80 Ca complex soap 5 to 55, preferably 10 to 50 (Ca soap plus complexing agent) or 5 to 30, preferably 10 to 20 Additives (optional) 0 to 20, preferably 0.5 to 10 waxes 10 to 50, preferably 10 to 35, in particular 20 to 35
  • compositions contain at least acetic acid, dicarboxylic acid or phosphoric acid as complexing agent.
  • the numerical values each add up to 100% by weight.
  • the rope lubricant based on calcium sulphonate complex hybrid soaps includes at least the following components: Areas in wt% base oil 5 to 60, preferably 20 to 40 Ca sulphonate complex soap 10 to 80, preferably 20 to 70 or 10 to 33, preferably 20 to 30 (e.g. if other thickeners are used) Additives (optional) 0 to 20, preferably 0.5 to 10 waxes 10 to 50, preferably 10 to 35 ins particularly preferably 20 to 35 Activators (usually expelled or converted in the course of the reaction) at least greater than 1, preferably greater than 2, in particular 1 to 20 or 2 to 10. further thickeners (optional) eg single or complex soaps of Ca, Li or Al. 0 to 40, preferably 2 to 20
  • compositions contain at least acetic acid, dicarboxylic acid or phosphoric acid as complexing agent.
  • Typical methods for applying the rope lubricants to the wires are spraying (as an aerosol, airless or electrostatically), brushing, spraying, dip coating, flow coating, roller application, powder coating and the like.
  • the consistency of the composition can be adjusted for the particular application method.
  • the rope lubricant used according to the invention is preferably applied to the elements before the wires and/or strands are joined together.
  • the rope lubricant can also be used for relubrication.
  • the individual tensile elements are preferably moved past a stationary spraying device.
  • the tensile elements e.g. B. metal wires, for example, can be continuously unwound from a roll, past the stationary spraying device and then formed into a flexible and deflectable pulling element, which in turn is wound onto a take-up roll.
  • the rope lubricants can, if necessary after dilution or in diluted form or by heating, also be used to saturate the cores of the ropes, e.g. rope cores made of sisal rope and inserting them into the rope lubricant.
  • the wire core is then also used for relubrication from an internal reservoir.
  • Input materials wt% Overbased Ca Sulphonate* 54 base oil 19.7 tap water 5 butyl glycol 1.3 dobanic acid 5.3 Ca(OH) 2 2.8 12-Hydroxy Stearic Acid 3.65 Acetic acid (60% by weight) 0.6 Phosphoric acid (75% by weight) 2.75 CaCO 3 4.9 * Ca sulphonate with TBN 400, sales product: Calcinate ® OR from Chemtura
  • the base oil was initially introduced together with the Ca sulphonate and heated to 80.degree. Then the tap water and the butyl glycol were added with constant stirring; after thorough mixing, the dobanic acid was added with stirring (still at 80° C.). Gelation took place with a time delay. After about 1 hour, the temperature was increased to 105° C. and calcium hydroxide and then 12-hydroxystearic acid were added. After a waiting time of 15 minutes, the acetic acid was added in portions. The same was done with the phosphoric acid. It was then heated to 175-180° C. for 30 minutes and then cooled. The CaCO 3 was added at approx. 60°C. The lubricating grease was homogenized using a three-roll mill.
  • A.2 Rope lubricant based on a calcium sulfonate complex soap wax hybrid (Ca-Sul-X hybrid)
  • the base oil was introduced together with the mixed fatty acid and the beef tallow and heated to 80°C.
  • An aqueous suspension of Ca(OH) 2 was then added.
  • an aqueous solution of trisodium phosphate, sodium tetraborate decahydrate and calcium acetate was added.
  • the temperature was then gradually increased to 250°C with a residence time of approx. 30 minutes.
  • the lubricating grease (Ca-X) was homogenized using a three-roller mill.
  • rope lubricant based on a calcium sulphonate complex soap can be used to soak sisal cores.
  • Consistency class NLGI 000 can be used to soak sisal cores.
  • ANTICORIT ERC 7540 EU by FUCHS, Mannheim (ANTICORIT ERC 7540 EU is a base oil-wax-based product with additives to improve corrosion protection and reduce wear) ELASKON SK21-04 by Elaskon, Dresden (wax-based rope lubricant) ELASKON 20 BB 94 by Elaskon, Dresden (wax-based rope lubricant) NYROSTEN T55 from Nyrosten, Geldern (wax-based rope lubricant) RENOLIT LC-WP 2 from FUCHS, Mannheim, Li-/Ca-12-hydroxystearate with anti-corrosion additive RENOLIT CA-FG 50 from FUCHS, Mannheim Ca-12-hydroxystearate without anti-corrosion additive Elaskon SK-U by Elaskon, Dresden (wax-based rope lubricant) Elaskon SK-CE by Elaskon, Dresden (wax-based rope lubricant) Berucoat AK 376 von
  • the greases according to the invention show viscosity-temperature curves with the desired flat progression, cf Fig.1 .
  • the bubble-free and clear melted sample was poured into a test cylinder and cooled under prescribed conditions. At constant temperature, the sinking depth of a loaded and temperature-controlled test cone (total mass 150 g) was determined with a penetrometer during a test period of 5 s.
  • Ca-X-Hybrid Ca-Sul-X Hybrid and in particular Ca-Sul-X showed better consistency - temperature behavior compared to an oil-wax-based rope lubricant (Elaskon 21/04), as shown in Fig.2 evident.
  • the shear stability-temperature dependency was measured according to DIN 51580 ( Fig.3 ) and according to DIN ISO 2137 ( 2 and 3 ).
  • a layer of bitumen applied to a small sheet of metal was cooled by 1 °C per minute and bent in a defined manner every 1 minute.
  • the Fraass breaking point is the temperature in degrees °C at which the bitumen layer breaks or cracks when bent under specified test conditions.
  • breaking point [°C] Ca-Sul-X -62 ANTICORIT ERC 7540 EU -40 ELASKON SK 21/04 -38 ELASKON 20BB -36 NYROSTEN T55 -20
  • a cold-rolled steel test specimen measuring 15 cm x 10 cm was immersed in a solution of 30% rope lubricant and solvent and suspended from a non-metallic material (e.g. synthetic fibers, cotton threads or other insulating material) to allow the solvent to evaporate.
  • the fixtures for the samples were also made of durable non-metallic material. 4 samples were to be placed in 4 quadrants at an angle of 20° (+/- 5°) to the vertical in the chamber.
  • the test temperature was 35 °C
  • the spray volume was 1.5 (+/-0.5) ml/h
  • the concentration of the spray solution was 50 (+/-5) g/L NaCl
  • Corrosion protection behavior was comparable to that of conventional oil-wax-based rope lubricant formulations t ( h ) 30 50 125 150 220 290 310 370 460 rust ( % ) Ca-Sul-X 0 0 0 0 5 5 5 40 70 Ca-Sul-X hybrid 0 0 0 0 10 30 60 75 90 Ca-X hybrid 0 0 5 10 60 75 90 90 95 ANTICORIT ERC 7540 EU 0 0 5 10 15 30 40 50 60 Elaskon 20 BB 94 15 50 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 t ( h ) 490 550 620 650 rust ( % ) Ca-Sul-X 80 95 100 100 100 Ca-Sul-X hybrid 90 100 100 100 100 Ca-X hybrid 95 100 100 100 100 100 100 ANTICORIT ERC 7540 EU 70 90 100 100 100 Elaskon 20 BB 94 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Ca-Sul-X and Ca-Sul-X-hybrid did not contain any additional anti-corrosion additives.
  • the lubricating grease was tested with the addition of water in self-aligning ball bearings. After a specified cycle with a specific running time at a speed of 80 rpm without heating and loading and with a specific standstill time, the raceways of the test bearing outer rings were examined for corrosion.
  • test specimens installed in a test chamber of the oscillation test device and wetted with lubricant were mechanically stressed at a specified normal force with a specified test frequency and a specified vibration path.
  • the frictional forces were continuously measured.
  • Ca-Sul-X and Ca-X-Hybrid showed good anti-wear properties compared to commercially available rope lubricant compositions.
  • the rope lubricant sample is applied to a plate-plate rheometer using a template and heated to 80 °C. After the temperature had been reached, the excess amount of sample was smoothed off using a spatula. After cooling to 40°C, the template was removed and the top plate moved up to the re-solidified sample of lubricant until a preset distance was reached. Then, using a preset program, the upper plate was slowly immersed in the lubricant sample before it suddenly moved out of the sample again after a preset distance between the lower and upper plate had been reached. The force required to pull the top plate out of the lubricating composition was measured.
  • a rope loop, provided with the grease to be tested, is guided over a roller system and moved over the rollers in a pendulum motion. 1.2 million rollovers were carried out under the same load.
  • the rope is evaluated based on wire break counts, rusting and the White Paper test.
  • the white paper test refers to a piece of paper located under the test arrangement and describes the amount or number of particles thrown off the paper.
  • the rating scale for the White Paper Test and rusting is as follows: 0 none, 1 little, 2 little, 3 much, and 4 extremely much particulate matter or rust.
  • lubricant wire breaks rust formation
  • White paper test Ca-Sul-X 0 0 0 ANTICORIT ERC 7540 EU 1 1 0 Berucoat AK 376 113 3 3 Macromelt 145 4 4 Bio Grease MP 2 0 1 1 OKS 450 0 2 0

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)
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Claims (14)

  1. - Utilisation d'une composition de graisse lubrifiante comme lubrifiant pour câbles métalliques, ladite composition de graisse lubrifiante étant
    (i) une composition de graisse lubrifiante hybride complexe de sulfonate de calcium, contenant une huile de base, au moins un sel de calcium surbasifié d'un acide sulfonique organique, au moins un agent complexant et du carbonate de calcium dans une structure calcitique, ou
    (ii) une composition de graisse lubrifiante hybride complexe de calcium, contenant une huile de base, au moins un savon de calcium d'au moins un acide gras y compris un hydroxy-acide gras et au moins un agent complexant, ou
    (iii) un mélange de (i) et (ii),
    où, dans la composition de graisse lubrifiante selon (i), (ii) et (iii)
    - à chaque fois 10 à 50% en poids de cire sont contenus et la cire présente à chaque fois un point de solidification supérieur à 70°C, mesuré selon DIN ISO 2207, au moins l'acide acétique, les acides dicarboxyliques ou l'acide phosphorique étant utilisés comme agent complexant.
  2. - Utilisation selon la revendication 1, dans laquelle à chaque fois 20 à 35% en poids de cire ayant un point de solidification supérieur à 70°C, mesuré selon DIN ISO 2207, sont contenus.
  3. - Utilisation selon l'une des revendications 1 ou 2, dans laquelle la composition de graisse lubrifiante est introduite dans les câbles métalliques lors de la fabrication de ceux-ci, de préférence avant que plusieurs torons et/ou fils ne soient retordus pour former le câble métallique.
  4. - Utilisation selon l'une des revendications 1, 2 ou 3, dans laquelle la composition de graisse lubrifiante hybride complexe de sulfonate de calcium (i) contient :
    (a) 5 à 55 % en poids d'huile de base ;
    (b) 10 à 80 % en poids de sulfonate de calcium, dans lequel du carbonate de calcium est présent au moins partiellement dans une structure calcitique ;
    (c) un autre acide sulfonique ; et
    (d) 10 à 50% en poids, en particulier 20 à 35% en poids, de cire
    et la composition de graisse lubrifiante est surbasifiée.
  5. - Utilisation selon la revendication 3, dans laquelle la composition de graisse lubrifiante hybride complexe de sulfonate de calcium (i) contient un ou plusieurs des activateurs suivants ou ceux-ci ont été ajoutés à la composition de graisse lubrifiante hybride complexe de sulfonate de calcium (i) pendant sa fabrication :
    i) 1 à 20 % en poids d'eau avec des alcools en C1 à C4 ;
    ii) 1 à 20 % en poids d'alcools en C1 à C4, d'alcoxyalcanols et/ou de polyalcools tels que les glycols ;
    iii) 1 à 20 % en poids d'eau avec des acides hydroxycarboxyliques ;
    iv) 1 à 20% en poids de mélanges de i) et ii) ou ii) et iii) ou i), ii) et iii) ; et les activateurs sont présents dans la composition de graisse lubrifiante pendant la fabrication et, de préférence, sont éliminés au moins partiellement par traitement thermique.
  6. - Utilisation selon la revendication 4, dans laquelle le sel de calcium d'un acide sulfonique organique est utilisé comme sel de calcium surbasifié d'un acide sulfonique organique, contenant Ca(OH)2 et CaCO3, de préférence de manière prépondérante par rapport à la masse de CaCO3.
  7. - Utilisation selon l'une des revendications 1, 2 ou 3, dans laquelle la composition de graisse lubrifiante hybride complexe de calcium (ii) contient :
    (a) 40 à 80 % en poids d'huile de base ;
    (b) au moins un savon de calcium d'un acide gras y compris un hydroxy-acide gras ;
    (c) au moins un agent complexant ; et
    (d) 10 à 50 % en poids, en particulier 20 à 35 % en poids, de cire.
  8. - Utilisation selon au moins l'une des revendications précédentes, dans laquelle la composition de graisse lubrifiante contient en outre un ou plusieurs des composants suivants :
    - additifs pour graisses lubrifiantes ;
    - autres épaississants, en particulier
    autres savons métalliques d'acides carboxyliques en C12 à C36 ainsi que leurs acides hydroxycarboxyliques ;
    produits de réaction d'hydroxydes métalliques avec un acide phosphorique, l'acide acétique, l'acide borique ou un acide dicarboxylique et/ou leurs sels ; et/ou
    épaississants à base de polyurée.
  9. - Utilisation selon au moins l'une des revendications précédentes, dans laquelle la composition de graisse lubrifiante présente une valeur de pénétration de cône de 200 à 260, de préférence de 220 à 250 0,1 mm (à 25°C), mesurée selon DIN ISO 2137.
  10. - Utilisation selon au moins l'une des revendications précédentes, dans laquelle on introduit la composition de graisse lubrifiante hybride complexe de calcium (ii) et/ou la composition de graisse lubrifiante hybride de sulfonate de calcium (i) dans l'âme du câble, et la composition de graisse lubrifiante hybride complexe de calcium (i) et la composition de graisse lubrifiante hybride complexe de sulfonate de calcium (i) présentent à chaque fois une valeur de pénétration de cône de 400 à 475, de préférence de 420 à 460 0,1 mm (à 25°C), mesurée selon DIN ISO 2137.
  11. - Procédé d'application :
    (i) d'une composition de graisse lubrifiante hybride complexe de sulfonate de calcium contenant une huile de base, au moins un sel de calcium surbasifié d'un acide sulfonique organique, au moins un agent complexant et du carbonate de calcium dans une structure calcitique, ou
    (ii) d'une composition de graisse lubrifiante hybride complexe de calcium contenant une huile de base, au moins un savon de calcium d'au moins un acide gras y compris un hydroxy-acide gras et au moins un agent complexant, ou
    (iii) d'un mélange de (i) et (ii),
    où, dans la composition de graisse lubrifiante selon (i), (ii) et (iii)
    - à chaque fois 10 à 50% en poids de cire sont contenus et la cire présente un point de solidification supérieur à 70°C, mesuré selon DIN ISO 2207, au moins l'acide acétique, les acides dicarboxyliques ou l'acide phosphorique étant utilisés comme agent complexant,
    comme lubrifiant pour câbles métalliques par application sur les câbles par pulvérisation, au pinceau, par projection, par immersion, par ruissellement, par application au rouleau ou par revêtement de poudre.
  12. - Procédé selon la revendication 11, dans lequel la pulvérisation a lieu en tant qu'aérosol, par pulvérisation sans air ou par voie électrostatique.
  13. - Procédé selon la revendication 11, dans lequel le câble métallique comporte plusieurs fils et, avant un assemblage des fils et/ou des torons, la composition de graisse lubrifiante est appliquée sur les éléments du câble métallique.
  14. - Câble métallique pourvu :
    (i) d'une composition de graisse lubrifiante hybride complexe de sulfonate de calcium, contenant une huile de base, au moins un sel de calcium surbasifié d'un acide sulfonique organique, au moins un agent complexant et du carbonate de calcium dans une structure calcitique, ou
    (ii) d'une composition de graisse lubrifiante hybride complexe de calcium, contenant une huile de base, au moins un savon de calcium d'au moins un acide gras y compris un hydroxy-acide gras et au moins un agent complexant, ou
    (iii) d'un mélange de (i) et (ii),
    où, dans la composition de graisse lubrifiante selon (i), (ii) et (iii)
    - à chaque fois 10 à 50% en poids de cire sont contenus et la cire présente un point de solidification supérieur à 70°C, mesuré selon DIN ISO 2207, au moins l'acide acétique, les acides dicarboxyliques ou l'acide phosphorique étant utilisés comme agent complexant.
EP17842380.2A 2016-12-21 2017-12-21 Utilisation de graisses lubrifiantes ayant un complexe de calcium et de graisses lubrifiantes ayant un complexe de sulfonate de calcium, pour la lubrification de câbles métalliques Active EP3559176B9 (fr)

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DE102016125289.1A DE102016125289A1 (de) 2016-12-21 2016-12-21 Verwendung von Calcium-Komplex- und Calcium-Sulfonat-Komplex-Schmierfetten zur Schmierung von Drahtseilen
PCT/DE2017/101100 WO2018113850A2 (fr) 2016-12-21 2017-12-21 Utilisation de graisses lubrifiantes ayant un complexe de calcium et de graisses lubrifiantes ayant un complexe de sulfonate de calcium, pour la lubrification de câbles métalliques

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WO2018113850A3 (fr) 2018-10-11
WO2018113850A2 (fr) 2018-06-28
CA3047861C (fr) 2024-05-21
AU2017383702B2 (en) 2021-12-02
ZA201903798B (en) 2021-04-28
EP3559176B9 (fr) 2022-08-31
UA124742C2 (uk) 2021-11-10
RU2019121627A (ru) 2021-01-22
PL3559176T3 (pl) 2022-12-05
RU2753614C2 (ru) 2021-08-18
AU2017383702A1 (en) 2019-07-11
CN110234745B (zh) 2022-11-25
RU2019121627A3 (fr) 2021-01-28
US11505758B2 (en) 2022-11-22
MX2019007388A (es) 2019-08-16
JP7007383B2 (ja) 2022-02-10
PT3559176T (pt) 2022-08-17
CN110234745A (zh) 2019-09-13
KR20190100272A (ko) 2019-08-28
BR112019012914A2 (pt) 2019-12-31
KR102498915B1 (ko) 2023-02-13
HUE059663T2 (hu) 2022-12-28
US20190330556A1 (en) 2019-10-31
ES2924488T3 (es) 2022-10-07
DE102016125289A1 (de) 2018-06-21
JP2020514452A (ja) 2020-05-21
CA3047861A1 (fr) 2018-06-28

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