EP3559176A2 - 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

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Publication number
EP3559176A2
EP3559176A2 EP17842380.2A EP17842380A EP3559176A2 EP 3559176 A2 EP3559176 A2 EP 3559176A2 EP 17842380 A EP17842380 A EP 17842380A EP 3559176 A2 EP3559176 A2 EP 3559176A2
Authority
EP
European Patent Office
Prior art keywords
calcium
grease composition
acid
wax
calcium sulfonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17842380.2A
Other languages
German (de)
English (en)
Other versions
EP3559176B9 (fr
EP3559176B1 (fr
Inventor
Roman Müller
Stephan Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuchs SE
Original Assignee
Fuchs Petrolub SE
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Filing date
Publication date
Application filed by Fuchs Petrolub SE filed Critical Fuchs Petrolub SE
Publication of EP3559176A2 publication Critical patent/EP3559176A2/fr
Application granted granted Critical
Publication of EP3559176B1 publication Critical patent/EP3559176B1/fr
Publication of EP3559176B9 publication Critical patent/EP3559176B9/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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—Overbased sulfonic acid salts
    • C10M2219/0466—Overbased sulfonic 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 comprising waxes (calcium complex hybrid greases) and calcium sulfonate complex grease compositions and / or calcium sulfonate complex grease compositions containing waxes (calcium sulfonate complex hybrid greases) as Lubricant for wire ropes. Furthermore, the invention relates to a method for producing the wire ropes and wire ropes provided with the grease composition.
  • Characteristic of a grease or a grease composition is that a liquid oil component is taken up and held by a thickener component.
  • Lubricating grease wets the lubrication point and the lubrication effect on the tri-biologically stressed surfaces unfolds permanently.
  • a grease Among the most important theological properties of a grease include the consistency or its yield point, the avoidance of post-curing and excessive oil separation under thermal and mechanical stress as well as a stable viscosity-temperature behavior. Frequently, a thixotropic (shear-thinning) and shear-unstable behavior of the lubricating grease is advantageous. In order to create a grease of high utility value depending on the lubrication and equipment requirements, a high degree of practical experience is required.
  • Greases generally consist of a thickening agent which is homogeneously distributed in a base oil.
  • Various substances are known as base oils.
  • the thickeners used are organic and inorganic compounds.
  • 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, wherein the calcium carbonate in the course of the reaction at least partially, preferably predominantly the weight fraction predominantly, into a calcite Structure passes over.
  • Such calcite-containing overbased calcium sulfonate lubricating greases are described in detail, for example, in EP 0613940 B1.
  • Calcium complex greases contain a base oil and a thickener formed from calcium hydroxide, fatty acid and a complexing agent.
  • Wire ropes sometimes also called steel ropes, are indispensable mechanical components, in particular in conveyor technology, in the fishing industry, in the mining industry and in construction, which permit the transmission of tensile forces.
  • Wire ropes can perform static tasks, in particular in the form of guy ropes or are used for power transmission in dynamic applications, for example in cranes, elevators, cable cars or ski lifts.
  • wire ropes for dynamic applications are subject to constant alternating load, wear out after a certain period of use and must therefore be replaced periodically.
  • the wear of the wire ropes is due among other things to the rubbing against each other individual elements.
  • Particularly affected by fretting are wire ropes, which are used for dynamic applications, as they are subjected to a constant flexing during deflection and / or rolling up and down.
  • the object of the grease to be used according to the invention is to provide the following property profile as far as possible: an excellent viscosity-temperature behavior, good conveyability, a low breaking point according to Fraigne, excellent corrosion protection even with water absorption, a good elastomer compatibility, a high Dropping point, excellent wear protection, good EP (extreme pressure), low oil separation, good oxidation stability, good adhesion, good pH buffering ability, low consistency loss through water absorption and excellent shear stability (compared to thixotropic lubricants). Also, the grease should be non-bituminous and also be available in low aromatics hydrocarbon compositions.
  • a calcium sulfonate complex grease composition containing calcium carbonate in calcite structure (calcium sulfonate complex) and optionally a wax having a solidification point greater than 70 ° C (calcium sulfonate complex hybrid) or (ii) a calcium complex grease composition further comprising at least one wax having a solidification point greater than 70 ° C (calcium complex hybrid), or
  • the wire ropes are preferably used for lifts, cable cars or ski lifts.
  • the lubricating grease composition used according to the invention in the wire ropes has at least the following components:
  • the calcium sulphonate complex grease contains:
  • (C) optionally a further sulfonic acid, preferably a C 12 -alkyl sulfonic acid, in each case in particular for the gelation process or the activation,
  • the activators are present in the grease composition during production and may be at least partially expelled by heat treatment if necessary, and
  • the Ca complex grease used according to the invention has at least the following components:
  • a base oil e.g. 40-90% by weight, especially 60-80% by weight;
  • Both grease types may include the following optional components:
  • Salts of phosphoric acid, acetic acid, boric acid and / or a dicarboxylic acid are salts of phosphoric acid, acetic acid, boric acid and / or a dicarboxylic acid; and or
  • the invention also relates to wire ropes provided with the grease composition and the manufacture of wire ropes incorporating the grease composition.
  • Waxes are substances which are firm and kneadable at 20 ° C and higher, are translucent to opaque, but are not glassy and melt above 40 ° C without decomposition and are relatively low viscous above the melting point.
  • the grease composition is also referred to below as a rope lubricant.
  • the wire ropes used in the invention can have very different configurations. They always consist of several wires, which are stranded and / or twisted into strands according to a preferred embodiment, so that several strands form a wire rope.
  • the wire rope may comprise a core made of steel or plastic, around which the strands are made of 6 wires in each case, wherein a further wire layer with 1 2 strands and 6 wires each is laid around this wire layer.
  • the individual elements can be provided with a common casing, for example made of a plastic.
  • the wires and strands also deposits and bridles can be used.
  • Wire ropes can e.g. Both a core wire or core strand and a deposit (also called soul) have.
  • Tethers are fibers or solid polymers arranged to separate adjacent strands or wires in the same or superimposed layers or to fill the interstices of the rope.
  • Steel inserts can be made of one or more wire strands or as independently stranded wire rope.
  • Polymer inserts can u.a. a solid polymer in cylindrical form with and without grooves.
  • Wire ropes in the sense of the present invention therefore do not necessarily consist exclusively of steel, but may additionally comprise synthetic or natural materials.
  • Grease Type I Calcium Sulphonate Complex Grease and Calcium Sulphonate Complex Hybrid Grease
  • the calcium sulphonate complex greases overbased calcium sulphonate is presented in a base oil.
  • Calcium carbonate may or may not be added.
  • the activator (s) is added in particular at 40 to 100 ° C.
  • the sulfonic acid occurs depending on the time delay gelation. This can also be done under slight overpressure, which increases the reaction rate.
  • the boiling point of the activator (s) is heated 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").
  • To optimize the soap structure is now heated to about 170-190 ° C and the temperature for 30 to 60 min. held. 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 usually consists of organic liquids which are chemically substantially inactive during manufacture or use as intended.
  • the base oil preferably has a kinematic viscosity of 20 to 1000 mm 2 / s, preferably 1 00 to 500 mm 2 / s (each at 40 ° C).
  • the base oil is i.d.R. a non-volatile organic liquid at room temperature, but which may also contain volatiles, which i.d.R. after the synthesis or refining are substantially separated. Volatile components are defined herein as those components which boil at up to about 100 ° C at normal pressure, such as water or C1 to C4 alcohols.
  • the base oil has a flash point greater than 180 ° C, especially greater than 200 ° C.
  • Examples of corresponding organic liquids are alkanes and cycloalkanes, aromatics and cycloaromatics, which may also be correspondingly alkyl- and / or alkenyl-substituted; Ethers, such as dialkyl ethers; alkyl aryl; Cycloalkyl ether; Alkylcycloalkylether; 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;
  • oligomers As base oils and low molecular weight liquid polymers, which are generally referred to as oligomers, are suitable. These include dimers, trimers, tetramers, pentamers and the like. Specific examples of this large group of materials are poly-alpha-olefins as oligomers of an average of 2 to 6 or more units of C8 to C13 alpha-olefins or independently defined over a viscosity of 2 to 100 mm 2 / s ( at 1 00 ° C). Another important group are polyisobutylenes of 200 to 4000 g / mol (number average).
  • Alkyl, cycloalkyl, aryl, and alkylaryl hydrocarbons are the preferred class of base oils from the standpoint of ease of accessibility, cost, and properties.
  • Liquid petroleum fractions are another preferred class of base oils. These preferred classes are included Benzenes and alkylated benzenes, naphthalenes and alkylnaphthalenes, cycloalkanes and alkylated cycloalkanes, cycloalkenes and alkylated cycloalkenes found in naphthene-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 the context of 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 used i.d.R. formed in situ from a mixture of calcium oxide and / or calcium hydroxide, more 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 called 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 metal excess 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) occurs.
  • the overbased calcium sulfonate preferably has a TBN of 40 to 600, in particular 200 to 600 measured according to ISO 3771.
  • the calcium carbonate is present as a colloidal particle.
  • the maximum particle size is preferably below 5000 A. Particularly preferred are mean particle sizes of less than 400 A, for example in the range from 20 to 300 A.
  • the other sulfonic acids (C) may be oil-soluble and, if appropriate, also water-soluble at the same time.
  • Preferred sulfonic acids have the following structure:
  • the sulfonate group is bonded to a cyclic or aromatic radical, wherein the cyclic or aromatic radical further comprises one or more linear or branched C1 to C30 hydrocarbyl radicals, preferably one or two C8 to C18 - Hydrocarbyl radicals, has.
  • alkylbenzenesulfonic acids such as dibasic acid (dodecylbenzenesulfonic acid).
  • sulfonic acids or sulfonates may be synthetic or natural sulfonates, the so-called “mahogany sulfonates.”
  • synthetic sulfonates refers to those sulfonates derived from the sulfonation of feeds 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 residue may e.g. Cyclohexane or hexahydronaphthalene.
  • di-alkylarylsulfonates are those having alkyl groups each having 8 to 18 carbon atoms. They are primarily distinguished from the previous sulfonation feeds in that they are straight-chain and contain a large amount of disubstituted material.
  • sulfonates that may be used include, for example, linolenic sulfonates, mono- and poly-wax-substituted naphthalenesulfonates, dinonylnaphthalenesulfonates, naphthalenedisulfide sulfonates, dicetylthianthrene sulfonates, dilauryl-beta-naphtholsulfonates, unsaturated paraffin wax sulfonates, hydroxy substituted paraffin wax sulfonates, cycloaliphatic sulfonates such as lauryl cyclohexyl sulfonates and mono- or poly-wax-substituted cyclohexylsulfonates.
  • Suitable alcohols are aliphatic, cycloaliphatic and arylaliphatic mono or polyhydroxy alcohols. Alcohols having less than about 12 carbon atoms are particularly suitable. For reasons of economy and to ensure an expedient process, lower alkanols, for example alkanols having less 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
  • 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.
  • activator s
  • 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 is present in the alcohol component of these water-alkanol mixtures.
  • a volatile activator e.g., water or a water-soluble or water-miscible or water-dispersible aliphatic C1 to C4 alcohol, preferably isopropanol, and / or a water-soluble or slightly water-miscible or slightly water-dispersible alkoxyalkanol or glycols (especially mono-, di or triglycols), each having 2 to 20 carbon atoms, including their mono-C 1 - to C 4 -alkyl ethers, and mixtures of one or more of these activators.
  • a volatile activator e.g.
  • water or a water-soluble or water-miscible or water-dispersible aliphatic C1 to C4 alcohol preferably isopropanol
  • a water-soluble or slightly water-miscible or slightly water-dispersible alkoxyalkanol or glycols especially mono-, di or triglycols
  • the preparation of the calcium complex hybrid greases is usually carried out so that base oil, fatty acid (including hydroxy fatty acids) and / or triglyceride placed in a container and heated to about 80 ° C until all components have melted. Subsequently, Ca (OH) 2 and optionally water are added. Furthermore, complexing agents are added. To start the reaction, the temperature is raised to 1 00 ° C. After expelling the reaction water, the reaction mixture is heated further, for example up to a maximum of 270 ° C. After cooling to about 60 to 1 00 ° C, the lubricant additives are added to reduce wear, improve the oxidation resistance, improve the corrosion protection, etc.
  • the base oil (a) can be specified as described above for base oil (A).
  • the Ca soap is a calcium salt of one or more saturated or unsaturated monocarboxylic acids having from 1 to 36 carbon atoms, optionally substituted, in particular having from 1 to 22 carbon atoms, particularly preferably corresponding hydroxycarboxylic acids.
  • Suitable carboxylic acids are e.g. Lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid and preferably 1 2 -hydroxystearic acid.
  • free acid group and corresponding lower alcohol esters can be used with saponification, z.
  • complexing agents (c) are C1- to C6-carboxylic acids, C6- to C1-di- and / or tricarboxylic acids, benzoic acid, boric acids and their salts, phosphoric acids and salts thereof, in particular 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 C 1 - to C 6 -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 includes 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 (gammarric acid) or 4-hydroxy-4 -methoxybenzoeklare.
  • dicarboxylic acids are adipic acid (C6Hio0 4 ), sebacic acid (Ci oHie0 4 ), azelaic acid (C9Hi60 4 ) and / or 3-Fe f-butyl-adipic acid (CioHie0 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 (i.e., H3BO3), tetraboric acid, metaboric acid, and esters of these boronic and boronic acids, respectively.
  • boric acid i.e., H3BO3
  • tetraboric acid metaboric acid
  • metaboric acid metaboric acid
  • metaborate diborate, tetraborate or orthoborate
  • calcium orthoborate or lithium tetraborate can be used.
  • Phosphoric acids and their salts are also suitable complexing agents. These include various alkyl and aryl phosphinic acids, phosphine acids, phosphonic acids and phosphonic acids.
  • Phosphoric acids obtained by reacting lower alkanols or unsaturated hydrocarbons, such as polyisobutenes, with phosphorus oxides and phosphorus sulfides, such as P2O5; and P2S5, are particularly suitable.
  • Suitable phosphates are alkali metal (preferably lithium) and alkaline earth metal (preferably calcium) dihydrogen phosphate, hydrogen phosphate or pyrophosphate.
  • Acetic acid or its salts e.g. Calcium acetate.
  • the wax may be added during or after preparation of the soap (s).
  • bentonites such as montmorillonite (whose sodium ions may have been exchanged or partially exchanged by ammonium ions), aluminosilicates, clays, silica (eg Aerosil) or else di- and polyureas, may additionally be used as co-thickeners.
  • the bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers may be added to make the base fat or, more particularly, added later as an additive in the second step.
  • the di- and polyureas can be added as an additive.
  • the other components mentioned below may be added to both the calcium sulfonate complex grease and the calcium complex hybrid grease.
  • Other thickeners which can be used are C 10 - to C 36 -carboxylic acids and their hydroxycarboxylic acids, and also esters thereof (such as, for example, with methanol or glycerol as mono-, di- or triglyceride).
  • the eye lubricants according to the invention contain waxes. These are referred to herein as hybrid lubricants.
  • the waxes are, in particular, hydrocarbon waxes, e.g. Paraffin waxes, isoparaffin waxes (microwaxes), polyolefin waxes such as PE waxes or PP wax, FT waxes, GTL waxes, etc., candelilla 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 sound-deadener waxes.
  • the group of natural waxes includes ozokerite and montan wax (fossil
  • Waxes candelilla wax and carnauba wax (plant waxes) or sound wax (animal wax).
  • the group of synthetic waxes includes polyamide wax (polymer wax) or GTL or FT waxes.
  • the waxes have a solidification point greater than 70 ° C., in particular greater than 110 ° C. or alternatively greater than 140 ° C. (measured, for example, according to DIN ISO 2207).
  • the waxes are 10 to 50 wt.%, In particular 20 to 35 wt.% Contained in the grease composition.
  • the dropping point of the grease is greater than 325 ° C according to DI N ISO 2176.
  • compositions according to the invention furthermore contain lubricant additives as additives.
  • lubricant additives in the context of the invention are antioxidants, anti-wear agents, corrosion inhibitors, detergents, dyes, lubricity improvers, viscosity additives, friction reducers and high-pressure additives and solid lubricants.
  • lubricant additives may be mentioned as:
  • Antioxidants such as amine compounds (e.g., alkylamines or 1-phenylaminonaphthalene), aromatic amines, e.g. Phenylnaphthylamines or diphenylamines, phenolic compounds (e.g., 2,6-di-tert-butyl-4-methylphenol), sulfur antioxidants;
  • amine compounds e.g., alkylamines or 1-phenylaminonaphthalene
  • aromatic amines e.g. Phenylnaphthylamines or diphenylamines
  • phenolic compounds e.g., 2,6-di-tert-butyl-4-methylphenol
  • High-pressure additives such as organic chlorine, sulfur and / or phosphorus
  • - adhesive active substances such as C2 to C6 polyols, polyglycols, fatty acids, fatty acid esters or animal or vegetable oils;
  • - anti-corrosion agents such as e.g. Petroleum sulfonate, dinonylnaphthalenesulfonate, sorbitan esters, sarcosines, succinimides, fatty acid derivatives or imidazolines,
  • Metal deactivators such as e.g. Benzotriazole and its derivatives, mercapto-thiadiazoles or sodium nitrite;
  • Viscosity improvers e.g. Polymethacrylate, polyisobutylene, poly-alpha-olefins such as oligo-dec-1-enes, oligocopolymers (ethylene and propylene copolymers) and polystyrenes;
  • metal such as zinc
  • ammonium dithiocarbamate metal (such as zinc) or ammonium dithiocarbamate
  • Metal such as zinc
  • Friction reducer e.g. functional polymers such as e.g. Oleylamides, polyether- and amide-based organic compounds, e.g. Alkylpolyethylene glycol tetradecylene glycol ethers, alkyl and / or aryl phosphoric esters, phosphonic acid esters and thiophosphoric acid esters;
  • functional polymers such as e.g. Oleylamides, polyether- and amide-based organic compounds, e.g. Alkylpolyethylene glycol tetradecylene glycol ethers, alkyl and / or aryl phosphoric esters, phosphonic acid esters and thiophosphoric acid esters;
  • the grease compositions of the present invention may contain conventional lubricant additives against corrosion, oxidation, and for protection against metal influences acting as chelate compounds, radical scavengers, UV protection, reaction layer formers, and the like.
  • Solid lubricants e.g. Polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such.
  • molybdenum disulfide tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth and zinc, salts of alkali and alkaline earth metals, such. Calcium carbonate, sodium and calcium phosphates, are used.
  • Solid lubricants can be divided into the following groups: layered structure compounds such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride, and some metal halides; oxidic and hydroxidic compounds of the transition and alkaline earth metals or their carbonates or phosphates; soft metals and / or plastics.
  • layered structure compounds such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride, and some metal halides
  • oxidic and hydroxidic compounds of the transition and alkaline earth metals or their carbonates or phosphates soft metals and / or plastics.
  • the desired advantageous lubrication properties can also be adjusted by the use of lignosulfonates, without having to use solid lubricants. In many cases, these can be dispensed with completely or at least can be significantly minimized.
  • the rope lubricant based on calcium complex hybrid soaps contains at least the following components:
  • the numerical values add up to 1 00% by weight.
  • the rope lubricant based on calcium sulphonate complex soaps or calcium sulphonate complex hybrid soaps comprises at least the following components:
  • the numerical values add up to 1 00% by weight.
  • a special feature of the rope lubricants used according to the invention is the bright appearance, since not necessarily bitumen or black solid lubricants must be used to achieve the required properties.
  • Typical methods for applying the rope lubricants to the wires are spraying (as aerosol, airless or electrostatically), brushing, spraying,
  • the rope lubricant used according to the invention is preferably applied to the elements before joining the wires and / or strands.
  • the rope lubricant can be used for relubrication.
  • the individual tensile elements are moved past a stationary spraying device. As a result, it is also possible to easily provide a heavy-grease composition for individual elements which are very long-lasting in a limited space.
  • metal wires can be unwound, for example, continuously with a take-off from a roll, past the stationary Aufsprühvorraum and then formed into a flexible and deflectable tension member, which in turn is wound on a take-up roll.
  • the rope lubricants according to the invention can, if appropriate after dilution or in diluted form or by heating, also be used for impregnating cores of the ropes, e.g. Cord made of sisal rope and inserted into the rope lubricant according to the invention.
  • the wire core is then used for relubrication from an inner reservoir.
  • rope lubricant based on a calcium sulfonate complex soap (consistency class NLGI 000) can be used to soak sisal souls.
  • ANTICORIT ERC 7540 EU from FUCHS, Mannheim (ANTICORIT ERC 7540 EU is a base oil wax-based product with additives to improve corrosion protection and reduce wear)
  • the fats according to the invention show viscosity-temperature curves with the desired flat profile, cf. FIG.
  • a Kaltbandstahlprüfenia with the dimensions 15 cm x 10 cm was immersed in a solution of 30% rope lubricant and solvent and stored to evaporate the solvent on a non-metallic material (eg. Synthetic fibers, cotton threads or other insulating material) hanging.
  • the holders for the samples were also made of durable non-metallic material.
  • Four 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 1, 5 (+/- 0.5) ml / h and the concentration of the spray solution 50 (+/- 5) g / L NaCl
  • Ca-Sul-X and Ca-Sul-X-hybrid did not contain any additional anticorrosive additives.
  • the grease was tested with the addition of water in self-aligning ball bearings. After a predetermined cycle with a certain running time at a speed of 80 min -1 without heating and load and with a certain downtime, the tracks of the test bearing outer rings were examined for corrosion.
  • a rope loop, equipped with the respective fat to be tested, is guided over a roller system and moved in a pendulum motion over the rollers. In each case 1.2 million overrolls were carried out under the same load.
  • the rope is evaluated after counted wire breaks, after rust formation and with the white paper test.
  • the white paper test refers to a paper under the test arrangement and indicates the amount or number of particles that have been removed on the paper.
  • the evaluation scale for the white paper test and the rust formation is as follows: 0 none, 1 hardly, 2 little, 3 lots and 4 extremely many particles or rust.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Ropes Or Cables (AREA)

Abstract

L'invention concerne l'utilisation de compositions de graisses lubrifiantes ayant un complexe de calcium et de compositions de graisses lubrifiantes ayant un complexe de sulfonate de calcium, en tant que lubrifiant de câbles métalliques. L'invention concerne également un procédé de fabrication des câbles métalliques et les câbles métalliques pourvus de la composition de graisse lubrifiante.
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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US11505758B2 (en) 2022-11-22
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WO2018113850A3 (fr) 2018-10-11
ZA201903798B (en) 2021-04-28
EP3559176B9 (fr) 2022-08-31
EP3559176B1 (fr) 2022-06-08
RU2753614C2 (ru) 2021-08-18
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