EP3820978A1 - Graisse lubrifiante écologique destinée à des câbles en acier - Google Patents

Graisse lubrifiante écologique destinée à des câbles en acier

Info

Publication number
EP3820978A1
EP3820978A1 EP19740328.0A EP19740328A EP3820978A1 EP 3820978 A1 EP3820978 A1 EP 3820978A1 EP 19740328 A EP19740328 A EP 19740328A EP 3820978 A1 EP3820978 A1 EP 3820978A1
Authority
EP
European Patent Office
Prior art keywords
weight
grease
biodegradable
mixtures
din
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
EP19740328.0A
Other languages
German (de)
English (en)
Other versions
EP3820978B1 (fr
Inventor
Brigitte Mayrhofer
Maximilian ERHARD
Patrick WITTMEYER
Stefan Seemeyer
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.)
Klueber Lubrication Muenchen GmbH and Co KG
Original Assignee
Klueber Lubrication Muenchen SE and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Klueber Lubrication Muenchen SE and Co KG filed Critical Klueber Lubrication Muenchen SE and Co KG
Publication of EP3820978A1 publication Critical patent/EP3820978A1/fr
Application granted granted Critical
Publication of EP3820978B1 publication Critical patent/EP3820978B1/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
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • 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
    • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
    • C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C10M125/30—Clay
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
    • 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
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
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    • 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
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • C10M2201/1036—Clays; Mica; Zeolites used as thickening agents
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/105—Silica
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • 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
    • C10M2207/126—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 monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M2207/127—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 polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M2207/1285—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 used as thickening agents
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • C10M2209/1023—Polyesters used as base material
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
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    • 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
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    • 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
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • C10N2020/01—Physico-chemical properties
    • C10N2020/081—Biodegradable compounds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the invention relates to an environmentally compatible grease for steel cables, in particular galvanized steel cables.
  • the invention further relates to a method for producing the grease and its use.
  • Lubricants for steel cables are used to separate the individual rope strands from each other by a lubricating film, i. H. to lubricate and thereby reduce wear, as well as to protect the steel cable as a whole against corrosion.
  • a lubricating film i. H. to lubricate and thereby reduce wear, as well as to protect the steel cable as a whole against corrosion.
  • the lubricants In the field of application, the lubricants must also perform various additional tasks. For example, in the marine industry and in the oil and gas industry, it is necessary that the lubricants not only have a good lubricating effect, but can also be used in a wide temperature range and in the presence of water. Are galvanized
  • Environmentally compatible lubricants must be biodegradable and must have minimal toxicity and no bioaccumulation.
  • the CH 540331 A describes a lubricant for steel cables, which as
  • main component contains a saturated or unsaturated fatty acid having 5-30 carbon atoms or an ester of such an acid or a mixture thereof.
  • EP 0108536 A1 describes a corrosion protection composition comprising a corrosion inhibitor, a thickener and a thixotropic gel.
  • the anti-corrosion composition can be used to treat multi-wire electrical conductors, wire ropes or cables.
  • esters contains specific synthetic esters, namely polyol esters, trimellitate esters and polymeric fatty acid esters and a mixture of polyisobutylene polymers with different molecular weights.
  • Lubricant composition can also be used to treat wire ropes, among other things.
  • US 4486319 A describes a microporous lubricating composition containing an ionomer polymer and a liquid lubricant.
  • the ionomer polymer can be combined with other polymers and the composition may contain various additives to modify the performance and properties of the composition formed.
  • Composition can be used to lubricate mechanical components including wire ropes and bearings, such as B. plain bearings can be used.
  • CA 2364200 describes a lubricating composition for lubricating wire ropes comprising: (a) between 50 and 95 percent by volume of one
  • Base fluid (b) between 1 and 8 volume percent of a low acid lubricant; (c) between 0.2 and 5.0 volume percent of one
  • volume percent of an extreme pressure medium (e) between 0.1 and 10
  • US6329073 B1 describes a steel article treated with a corrosion-inhibiting and adhesion-resistant composition, the composition comprising: A) an oily or waxy carrier as a carrier of active components and B) active components, comprising: B1) a corrosion inhibitor in the form of a sulfonate of group IIA ; B2) a co-corrosion inhibitor selected from the group consisting of: (a) one or more fatty acids having 6 to 24 carbon atoms, aromatic acids and naphthenic acids, the acids having the free acid form or the salt form (b) one or more imidazoline derivatives with a C6-24 alkyl unit; and (c) one or more of C6-24 alkyl succinic anhydride compounds; and (d) mixtures of one or more of the compounds defined under (a), (b) and (c) or mixtures of multiple forms of the compounds defined under (a), (b) and (c); and C) optionally a compound selected from the group consisting of: C1) one
  • C2 a synthetic ester derived from a C1-10 alcohol with 1-12 hydroxyl groups and C6-24 fatty acids; and C3) a C6-18 alcohol; and C4) a mixture of one or more the compounds defined under C1), C2) and C3) or mixtures of several forms of the compounds defined under C1), C2) and C3); the elongated steel object being a hard-drawn steel wire.
  • a gel composition comprising a combination of: at least one base oil from about 45 to about 90 percent by weight; at least one polymer from about 10 to about 20% by weight at least partially miscible with the at least one base oil; and about 1 to about 50% by weight of at least one silicate thickener which comprises at least one compound selected from the group consisting of aluminum silicate, magnesium silicate,
  • CN 102102047 A describes a protective grease composition for a high-temperature resistant steel wire rope and a manufacturing process therefor.
  • the grease composition is made up of base oil (highly viscous mineral oil or synthetic oil), a thickener, an additive and a covering agent.
  • the grease for the steel wire rope is through
  • Thicken the base oil with a solid hydrocarbon thickener Thicken the base oil with a solid hydrocarbon thickener.
  • the thickener is bentonite.
  • a high molecular tackifier and a grease are used as a solid filler to make the
  • the protective grease for the steel wire rope is specially designed to protect steel wire ropes in an extreme
  • CN 102618371 A describes steel cable grease with a high dropping point and a preparation method for the steel cable grease.
  • the steel cable grease consists of the following components (in percentages by weight): 65% -85% base oil, 5% -20% Thickener, 2% -15% adhesive, 1% -6% rust inhibitor, 0-5%
  • Antioxidant 0-5% polar additive and 0.5% -6% solid lubricant.
  • CN 102827678 A describes a wire rope grease composition which, in addition to lubrication, also offers corrosion protection.
  • the composition consists of the following components: 51.0% to 72.5% calcium sulfonate composite fat No. 2, 25.0 to 38.0% base oil, 0.2 to 1.0% diphenylamine, 1, 3 to 5, 5% colloidal graphite and 1.0 to 4.5% ozocerite.
  • the product is suitable for the lubrication and protection of various wire ropes under oceanic climatic conditions such as seaport, sea ship, offshore drilling platforms, etc.
  • the abovementioned lubricants do not meet all of the abovementioned requirements, namely that they can be used in a wide temperature range and also in the presence of water in addition to a good lubricating effect and also the requirements for
  • the invention is therefore based on the object of a lubricant
  • an environmentally compatible grease comprising: a) from 50% by weight to 90% by weight of a biodegradable base oil, in particular a biodegradable ester as base oil, b) from 3% by weight to 25% by weight and / or 7 wt% to 20 wt% of a thickener selected from
  • polystyrene resin a polymer selected from polyisobutylene, polyisobutylene / butene copolymer, polymethacrylates, polyesters, preferably complex esters, in particular complex esters
  • the grease has a dropping point according to standard DIN ISO 2176 of over 150 ° C, for example from 150 ° C to 300 ° C and / or from 170 ° C to 300 ° C and / or from 200 ° C up to 290 ° C.
  • the grease has an upper service temperature (OGT) according to the DIN standard 58397 part 1 of at least 150 ° C, for example from 150 ° C to 200 ° C and / or from 150 ° C.
  • the lubricating grease there is preferably at least 75% by weight, for example from 75% by weight to 100% by weight, more preferably at least 80% by weight, for example from 80% by weight to 100% by weight and / or from 85% by weight to 100 %
  • the grease can also contain up to 25% by weight of non-biodegradable components, provided that they are not bioaccumulating and / or only minimally toxic.
  • the lubricating grease according to the invention therefore fulfills the criteria for environmentally compatible
  • components a) to c) have no negative influence on the zinc layer of galvanized steel cables and, in particular, do not react with the zinc layer.
  • the grease contains at least 50% by weight as component a),
  • component a) is based on the total amount of grease.
  • a biodegradable base oil or a biodegradable ester means a base oil and / or an ester which is biodegradable in accordance with the OECD 301 A-F or OECD 306 standard.
  • mixtures of different base oils and / or different esters can also be used. So that the lubricant
  • the base oil or the ester must also have no toxicity.
  • biodegradable base oils and in particular biodegradable esters can be used as component a), provided that they have sufficient thermal stability.
  • Preferred biodegradable base oils are base oils and in particular esters, which have thermal stability, which can be determined using TGA (DIN 51006;
  • Evaporation loss greater than 1% by weight means thermally unstable) of over 150 ° C, for example in the range from 150 ° C to 200 ° C.
  • the base oil and in particular the ester preferably also have a rather low volatility.
  • Preferred biodegradable base oils are therefore base oils and in particular esters, which have a volatility, measured according to DIN 58397 after 7d, 150 ° C. of ⁇ 10% by weight, preferably ⁇ 5% by weight.
  • the grease also has a rather low volatility.
  • Preferred lubricating greases are therefore lubricating greases which have a volatility, measured according to DIN 58397 after 7d, 150 ° C. of ⁇ 10% by weight, preferably ⁇ 5% by weight.
  • the base oil and especially the ester preferably show high hydrolytic stability.
  • preferred biodegradable base oils are base oils and / or esters which, measured in accordance with DIN ASTM D-2619 (with an extended running time of 400 h, 93 ° C.), have a TAN delta (change in acid content) of 0.0 mg KOH / g have from 20 to 20, more preferably from 0.0 to 15 mg KOH / g.
  • the base oils and especially the esters preferably show a low acid content (TAN) according to DIN EN 12634, preferred biodegradable base oils and in particular esters an acid content (TAN) of less than 5 mg KOH / g, for example from 0.01 mg to 5 mg KOH / g, more preferably less than 1 mg KOH / g, for example from 0.01 mg KOH / g to 1 mg KOH / g.
  • TAN low acid content
  • preferred biodegradable base oils and in particular esters an acid content (TAN) of less than 5 mg KOH / g, for example from 0.01 mg to 5 mg KOH / g, more preferably less than 1 mg KOH / g, for example from 0.01 mg KOH / g to 1 mg KOH / g.
  • the viscosity of the biodegradable base oil is preferably at least 18 mm 2 / s, for example from 18 mm 2 / s to 1200 mm 2 / s and / or at least 100 mm 2 / sec, for example from 100 mm 2 / sec to 1200 mm 2 / s s and / or from 120 to 500 mm 2 / sec and / or from 120 to 300 mm 2 / sec, each measured according to DIN EN ISO 3104 at 40 ° C.
  • the viscosity of preferred mixtures of base oils measured according to DIN 51562 part 1 at 40 ° C is at least 18 mm 2 / s, for example from 18 mm 2 / s to 1200 mm 2 / s and / or 18 mm 2 / s to 500 mm 2 / s and / or 18 to 200 mm 2 / s.
  • the viscosity of preferred biodegradable esters is preferably at least 50 mm 2 / sec, for example from 50 mm 2 / sec to 1000 mm 2 / s and / or from 50 mm 2 / sec to 1200 mm 2 / s, more preferably at least 100 mm 2 / sec, for example from 100 mm 2 / sec to 1000 mm 2 / s and / or from 100 mm 2 / sec to 1200 mm 2 / s and in particular from 130 to 1000 mm 2 / sec and / or from 130 mm 2 / sec up to 1200 mm 2 / s, each measured according to DIN EN ISO 3104 at 40 ° C.
  • the biodegradable ester is a synthetic ester.
  • the ester is particularly preferably an ester on a renewable basis.
  • a particularly preferred ester according to the invention is a polyol ester, in particular (Trimethylolpropane) esters, pentaerytrite esters, mixtures and / or complex esters thereof.
  • Particularly preferred (trimethylolpropane) esters are esters of
  • Cio-C22 carboxylic acids Trimethylolpropane and branched or unbranched and saturated or unsaturated Cio-C22 carboxylic acids.
  • the acids can be mono- and / or dicarboxylic acids.
  • Dicarboxylic acids can be used
  • Pentaerytrite esters are esters of pentaerytrite and branched or unbranched and saturated or unsaturated CIO-C22 carboxylic acids.
  • Very particularly preferred esters are esters of trimethylolpropane or pentaerythritol with saturated or unsaturated branched Ci8-carboxylic acids, in particular with oleic acid, isostearic acid mixtures and / or complex esters thereof.
  • esters are esters of trimethylolpropane with saturated or unsaturated, branched or unbranched, C8-C2o-carboxylic acids, and / or Cio-C22-carboxylic acids, in particular with sebacic acid, stearic acid and isostearic acid, mixtures and / or complex esters thereof.
  • esters are complex esters
  • Trimethylolpropane with saturated, branched or unbranched, C8-C20-carboxylic acids and / or Cio-C22-carboxylic acids, especially with
  • esters are complex esters
  • Trimethylolpropane with a mixture of at least two saturated or unsaturated, branched or unbranched, C8-C2o-carboxylic acids and / or Cio-C22-carboxylic acids, at least one first carboxylic acid being a saturated or unsaturated, branched or unbranched C8-C20-dicarboxylic acid and / or Cio-C22 dicarboxylic acid and at least one second acid is a saturated or unsaturated, branched or unbranched C8-C20 carboxylic acid and / or Cio-C22 carboxylic acid.
  • first carboxylic acid being a saturated or unsaturated, branched or unbranched C8-C20-dicarboxylic acid and / or Cio-C22 dicarboxylic acid
  • at least one second acid is a saturated or unsaturated, branched or unbranched C8-C20 carboxylic acid and / or Cio-C22 carboxylic acid.
  • esters are complex esters of trimethylolpropane with a mixture of at least two saturated, branched or unbranched, C8-C20 Carboxylic acids and / or Cio-C22-carboxylic acids, at least one first carboxylic acid being a saturated, unbranched C8-Ci2-dicarboxylic acid,
  • sebacic acid in particular sebacic acid
  • at least one second acid is a saturated, branched or unbranched Ci5-C2o-carboxylic acid, in particular
  • Stearic acid isostearic acid or a mixture thereof.
  • component a) is not a triglyceride, since triglycerides have unsatisfactory hydrolytic and oxidative or chemical stability, at least for some applications.
  • Suitable biodegradable base oils are polyalphaolefins and / or polyglycols.
  • biodegradable polyalphaolefins have a viscosity measured according to DIN 51562 part 1 at 100 ° C. of at most 6 mm 2 / s, for example from 2 mm 2 / s to 6 mm 2 / s and / or 2 mm 2 / s to 5 mm 2 / s and / or 2 to 4 mm 2 / s.
  • biodegradable polyglycols are oil-soluble
  • Polyglycols These preferably have a viscosity measured according to DIN 51562 part 1 at 40 ° C. of at most 150 mm 2 / s, for example from 18 mm 2 / s to 150 mm 2 / s and / or 18 mm 2 / s to 68 mm 2 / s and / or 18 to 46 mm 2 / s.
  • the grease contains a thickener selected from biodegradable calcium soaps (b1)) in an amount of 3 to 12% by weight, more preferably 4% to 10% by weight, in particular 4% to 7% by weight % By weight, bentonites (b2)) in an amount of 3% by weight to 25% by weight and / or 3.5% by weight to 20% by weight and / or 4 to 12% by weight, more preferably 4 % By weight to 10% by weight and mixtures thereof.
  • the amount of the thickener is, according to the invention, 3% by weight to 25% by weight and / or 7% by weight to 20% by weight.
  • the proportion of component b) is based on the total amount of grease.
  • An advantage of using calcium soap as a thickener is that it increases the resistance to water, especially in combination with component c2).
  • a biodegradable calcium soap is understood to mean a calcium soap which is biodegradable in accordance with the OECD 301 A-F and / or OECD 306 standard.
  • the calcium soap In order for the lubricant to meet the requirements for EAL, the calcium soap must also have no or only minimal toxicity.
  • Preferred calcium soaps are water-resistant, in particular they have a static water resistance according to DIN 51807 T1.
  • calcium soaps are preferred over bentonites because they have a higher thickening effect and better biodegradability. Mixtures of different calcium soaps or bentonites can also be used.
  • Calcium soaps of fatty acids in particular C8-C26 fatty acids, in particular calcium 12-hydroxystearate, are particularly preferred.
  • mixtures of calcium soaps and bentonites can also be used.
  • this embodiment is less preferred, at least when using galvanized steel cables, since zinc corrosion is deteriorated compared to the isolated use of calcium soaps or bentonites.
  • the base oil as component c) contains from 1% by weight to 40% by weight of additives.
  • the base oil contains 4% by weight to 40% % By weight, more preferably from 5% by weight to 40% by weight, more preferably from 7% by weight to 40% by weight and in particular from 10% by weight to 35% by weight
  • the proportion of component c) is based on the total amount of grease.
  • the additives of component c) comprise from 1 to 12% by weight and / or 4 to 12% by weight, preferably from 4% by weight to 10% by weight, of fumed silica and / or polytetrafluoroethylene as component c1).
  • the proportion of component d) is based on the total amount of grease.
  • the pyrogenic silicon dioxide is selected from silica with a specific surface area of 90 to 130 m 2 / g. Also preferred is hydrophobicized fumed silica, in particular one using dichlorodimethylsilane
  • Component c1) contributes to improving the dropping point of the grease and thereby to its temperature resistance in the sense of an increase in the upper service temperature (OGT).
  • component c1) has the advantage that it acts as a co-thickener and can thereby contribute to stabilizing the thickener system.
  • component c2) the additives of component c) include
  • polystyrene resin a polymer selected from polyisobutylene, polyisobutylene / butene copolymer, polymethacrylates, polyesters, preferably
  • a complex ester is understood to be a polyester which, by reaction of polyols with dicarboxylic acids, and optionally Monocarboxylic acids is produced.
  • the proportion of component c2) is 2% by weight to 45% by weight, preferably from 2% by weight to 25% by weight, more preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 17 % By weight, based on the total amount of grease.
  • the polymers of component c2) preferably have a viscosity, measured according to DIN 51562 part 1 at 100 ° C., of at least 600 mm 2 / s, more preferably of at least 800 mm 2 / s and / or at least 1000 mm 2 / s and / or at least 1500 mm 2 / s and / or at least 4000 mm 2 / s,
  • Polyisobutylene / butene copolymer since these are inexpensive raw materials and have no hydrolyzable groups, such as ester groups. Polymers that are biodegradable are also preferred.
  • component c2) is advantageous since, as a toxicologically unobjectionable adhesion promoter, it still has the adhesion, measured according to ASTM D 4049, of ⁇ 50% by weight loss, for example of ⁇ 30% by weight loss
  • the lubricating grease therefore preferably has a weight loss in a water spray-off test according to ASTM D 4049 of ⁇ 50% by weight loss, for example of ⁇ 30% by weight loss, more preferably of ⁇ 25%% by weight.
  • component c3) the additives of component c) include
  • a solid lubricant preferably selected from alkaline earth salts, in particular calcium carbonate, calcium stearate, graphite, melamine cyanurate, zinc sulfide (ZnS), molybdenum sulfide (MoS2) and mixtures thereof.
  • the proportion of component c3) is based on the total amount of grease.
  • Solid lubricants which are less preferred according to the invention are dithiocarbamates, in particular ash-free dithiocarbamates, bis-stearoyl-ethylenediamine and mixtures thereof. It has been found in practical tests that the use of these compounds has a negative effect on the corrosion of the zinc layer. This is also disadvantageous from an environmental point of view, since zinc oxide is toxic to aquatic organisms, which is formed when zinc is corroded.
  • the lubricating grease prefferably be the first of 0.5% by weight and in particular of 0.5 to 2.8% by weight of succinic acid derivatives
  • component c4) Contains corrosion protection agents, in particular amidized succinic acid half-esters as component c4).
  • the proportion of component c4) is based on the total amount of grease.
  • the proportion of component c4) is based on the total amount of grease.
  • Component c4) has a neutralization number (NZ) (DIN 53402) of 70 to 100 mg KOH / g.
  • the grease contains as component c5) a second corrosion protection agent, preferably selected from alkaline earth oxides, in particular calcium oxide and / or
  • An advantage of the aforementioned components is that they offer good corrosion protection and are not toxic. Magnesium oxide, disodium sebaccate and / or mixtures thereof are particularly preferred.
  • component c5) has one
  • Particle size distribution d10 from 1 to 10 pm, more preferably from 3 to 8 pm, more preferably from 4 to 6 pm and in particular from 5 pm and / or a particle size distribution d50 from 10 to 30 pm, more preferably from 13 to 22 pm, more preferably from 15 to 20 pm and in particular from 17 pm and / or a particle size distribution d90 from 30 to 50 pm, yet
  • component c5) has a particle size distribution d50 of less than 25 pm, for example from 5 pm to 25 pm and / or from 5 pm to 20 pm.
  • component c5) The advantage of using component c5) is that it can act as a basic reserve in addition to increasing the corrosion protection of the grease. In addition, it was found in practical tests that magnesium oxide as component c5) in combination with c4) has a synergistic effect.
  • the proportion of component c5) is preferably in the range from 0.3 to 5% by weight, more preferably from 0.5 to 2.5% by weight and in particular from 1% by weight to 2.3% by weight.
  • the proportion of component c5) is in each case
  • the grease can also other common additives,
  • the grease contains an antioxidant as component c6).
  • This is preferably selected from non-toxic or only minimally toxic antioxidants.
  • the proportion of the antioxidant is preferably in the
  • Component c6 based on the total amount of grease.
  • Antioxidants which are particularly preferred according to the invention are phenolic and / or amine antioxidants.
  • the grease comprises: a) from 50% by weight to 90% by weight of a biodegradable ester as the base oil,
  • a thickener selected from b1) from 3% by weight to 12% by weight of biodegradable calcium soap, b2) from 4% by weight to 12% by weight of bentonite,
  • the grease comprises: a) from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, even more preferably from 65% by weight to 75% by weight
  • Pentaerythritol esters in particular pentaerythritol esters from pentaerythritol and isostearic acid, as base oil,
  • c1) from 1% by weight to 12% by weight and / or from 4% by weight to 12% by weight, preferably from 4% by weight to 10% by weight of pyrogenic silicon dioxide, c2) from 2% by weight to 45% by weight .% and / or from 2% by weight to 25% by weight, more preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 17% by weight, polyisobutylene,
  • % By weight, more preferably from 1% by weight to 9% by weight and in particular from 1.5% by weight to 8% by weight of calcium carbonate as the solid lubricant.
  • this comprises
  • Grease a) from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, still more preferably from 65% by weight to 75% by weight
  • Pentaerythritol esters in particular pentaerythritol esters from pentaerythritol and isostearic acid, as base oil, b) from 3% by weight to 25% by weight of a thickener selected from b1) from 3% by weight to 12% by weight, more preferably from 4% by weight to
  • c1) from 1% by weight to 12% by weight and / or from 4% by weight to 12% by weight, preferably from 4% by weight to 10% by weight of pyrogenic silicon dioxide, c2) from 2% by weight to 45% by weight .% and / or from 2% by weight to 25% by weight, more preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 17% by weight, polyisobutylene,
  • % By weight, more preferably from 1% by weight to 9% by weight and in particular from 1.5% by weight to 8% by weight of calcium carbonate as solid lubricant,
  • c6) from 0.3 to 3% by weight, more preferably from 0.5 to 2% by weight, and in particular from 0.8% by weight to 1.5% by weight of a phenolic antioxidant.
  • the grease comprises: a) from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, even more preferably from 65% by weight to 75% by weight of complex esters , in particular complex esters of trimethylolpropane with a mixture of at least two saturated or unsaturated, branched or unbranched, C8-C20-carboxylic acids, at least one first carboxylic acid being a saturated or unsaturated, branched or unbranched C8-C2o-dicarboxylic acid, and at least one second acid being a saturated or unsaturated, branched or unbranched C8-C20-carboxylic acid, as base oil,
  • c1) from 1% by weight to 12% by weight and / or from 4% by weight to 12% by weight, preferably from 4% by weight to 10% by weight of pyrogenic silicon dioxide, c2) from 2% by weight to 45% by weight .% and / or from 2% by weight to 25% by weight, more preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 17% by weight, polyisobutylene,
  • % By weight, more preferably from 1% by weight to 9% by weight and in particular from 1.5% by weight to 8% by weight of calcium carbonate as the solid lubricant.
  • this comprises
  • Lubricating grease a) from 50% by weight to 90% by weight, more preferably from 60% by weight to 80% by weight, even more preferably from 65% by weight to 75% by weight of complex esters, in particular complex esters of trimethylolpropane with a mixture of at least two saturated, or unsaturated, branched or unbranched, C8-C20-carboxylic acids, at least one first Carboxylic acid is a saturated, or unsaturated, branched or unbranched C8-C20-dicarboxylic acid, and at least one second acid is a saturated or unsaturated, branched or unbranched C8-C20-carboxylic acid as base oil,
  • a thickener selected from b1) from 3% by weight to 12% by weight, more preferably from 4% by weight to 10% by weight, even more preferably from 4% by weight to 7% by weight, Ca-12-hydroxystearate,
  • c1) from 1% by weight to 12% by weight and / or from 4% by weight to 12% by weight, preferably from 4% by weight to 10% by weight, pyrogenic silicon dioxide, c2) from 2% by weight to 45 % By weight and / or from 2% by weight to 25% by weight, more preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 17% by weight, polyisobutylene,
  • % By weight, more preferably from 1% by weight to 9% by weight and in particular from 1.5% by weight to 8% by weight of calcium carbonate as solid lubricant,
  • c6) from 0.3 to 3% by weight, more preferably from 0.5 to 2% by weight, and in particular from 0.8% by weight to 1.5% by weight of a phenolic antioxidant.
  • Another object of the present invention is the use of the grease for coating steel cables, especially galvanized
  • Example 1 Production of a grease according to the invention
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2) and c3).
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the grease 2 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity. This fulfills that
  • a grease according to the invention is obtained by mixing components a), b1), b2), c1), c2) and c3).
  • the components of the grease 3 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or minimal toxicity.
  • the lubricating grease 3 according to the invention therefore fulfills the criteria for environmentally compatible
  • Example 3 shows the physicochemical properties of Example 3:
  • a grease according to the invention is obtained by mixing components a), b1), b2) c1), c2) and c3).
  • the components of the grease 4 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity. This fulfills that
  • Grease 4 according to the invention the criteria for environmentally friendly
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2) and c3).
  • the components of the grease 5 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity. This fulfills that
  • Grease 5 according to the invention the criteria for environmentally friendly
  • An inventive grease is obtained by mixing components a), b1), b2) c1), c2), c3), c4), c5) and c6).
  • the components of the grease 6 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity. This fulfills that
  • Grease 6 according to the invention the criteria for environmentally friendly
  • Example 6 shows the physicochemical properties of Example 6:
  • Example 7 Production of a grease according to the invention
  • a grease according to the invention is obtained by mixing components a), b2), c1), c2), c3), c5) and c6).
  • the components of the grease 7 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity.
  • the grease 7 according to the invention meets the criteria for environmentally friendly
  • Example 7 shows the physicochemical properties of Example 7:
  • Example 8 Production of a grease according to the invention
  • a lubricating grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the grease 8 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity.
  • the grease 8 according to the invention meets the criteria for environmentally friendly
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the grease 9 according to the invention are also biodegradable, if not biodegradable then not bioaccumulating, and have no or only minimal toxicity.
  • the grease 9 according to the invention meets the criteria for environmentally friendly
  • Example 9 shows the physicochemical properties of Example 9:
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the lubricating grease 10 according to the invention are also biodegradable, if not then not biodegradable
  • Example 11 Production of a grease according to the invention
  • a grease according to the invention is obtained by mixing components a), b2), c1), c2), c3), c5) and c6).
  • the components of the grease 11 according to the invention are also biodegradable, if not then not biodegradable
  • Example 12 Production of a grease according to the invention
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the grease 12 according to the invention are also biodegradable, if not then not biodegradable
  • Example 12 shows the physicochemical properties of Example 12:
  • a grease according to the invention is obtained by mixing components a), b1), c1), c2), c3), c5) and c6).
  • the components of the grease 13 according to the invention are also biodegradable, if not then not biodegradable
  • Example 13 shows the physico-chemical properties of Example 13:

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  • Lubricants (AREA)

Abstract

L'invention concerne une graisse lubrifiante écologique destinée à des câbles en acier, en particulier des câbles en acier galvanisés, comprenant a) de 50 % en poids à 90 % en poids d'une huile de base biodégradable, en particulier d'un ester biodégradable utilisé comme huile de base, b) de 3 % en poids à 25 % en poids et/ou de 7 % en poids à 20 % en poids d'un agent d'épaississement choisi parmi b1) de 3 % en poids à 12 % en poids d'un savon calcique biodégradable, b2) de 3 % en poids à 25 % en poids et/ou de 3,5 % en poids à 20 % en poids et/ou de 4 % en poids à 12 % en poids de bentonite, b3) et des mélanges de ces derniers, c) de 4 % en poids à 40 % en poids, de préférence de 7 % en poids à 40 % en poids d'additifs, comprenant c1) de 1 % en poids à 12 % en poids et/ou de 4 % en poids à 12 % en poids d'un dioxyde de silicium pyrogéné et/ou de polytétrafluoréthylènes et des mélanges de ces derniers, c2) de 2 % en poids à 45 % en poids et/ou de 2 % en poids à 25 % en poids d'un polyester choisi parmi des polyisobutylènes, des copolymères polyisobutylènes/butènes, des polyméthacrylates, des polyesters, de préférence des esters complexes, en particulier des esters complexes parmi un néopentylglycol/acide dimère/2-éthylhexanol et des mélanges de ces derniers, c3) de 0,5 % en poids à 20 % en poids et/ou de 1 % en poids à 10 % en poids d'une substance lubrifiante solide.
EP19740328.0A 2018-07-09 2019-07-09 Graisse lubrifiante écologique destinée à des câbles en acier Active EP3820978B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102018005397 2018-07-09
DE102018008362.5A DE102018008362A1 (de) 2018-07-09 2018-10-23 Umweltverträgliches Schmierfett für Stahlseile
PCT/EP2019/068344 WO2020011758A1 (fr) 2018-07-09 2019-07-09 Graisse lubrifiante écologique destinée à des câbles en acier

Publications (2)

Publication Number Publication Date
EP3820978A1 true EP3820978A1 (fr) 2021-05-19
EP3820978B1 EP3820978B1 (fr) 2022-08-24

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EP19740328.0A Active EP3820978B1 (fr) 2018-07-09 2019-07-09 Graisse lubrifiante écologique destinée à des câbles en acier

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US (1) US11421181B2 (fr)
EP (1) EP3820978B1 (fr)
JP (1) JP7095124B2 (fr)
KR (1) KR102555949B1 (fr)
CN (1) CN112424325B (fr)
AU (1) AU2019301866C1 (fr)
BR (1) BR112020025205B1 (fr)
DE (1) DE102018008362A1 (fr)
DK (1) DK3820978T3 (fr)
SG (1) SG11202100005WA (fr)
WO (1) WO2020011758A1 (fr)

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CN114517121A (zh) * 2020-11-20 2022-05-20 中国石油天然气股份有限公司 极地钢丝绳保养专用脂
FR3134112B1 (fr) * 2022-04-05 2024-04-12 Totalenergies Onetech Graisses lubrifiantes biodégradables.
CN117025277B (zh) * 2023-06-14 2024-06-04 无锡中石油润滑脂有限责任公司 一种大型升船机用可生物降解润滑脂及其制备方法

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Also Published As

Publication number Publication date
AU2019301866A1 (en) 2020-12-03
EP3820978B1 (fr) 2022-08-24
CN112424325B (zh) 2022-09-09
DE102018008362A1 (de) 2020-01-09
SG11202100005WA (en) 2021-02-25
KR102555949B1 (ko) 2023-07-14
US20210277323A1 (en) 2021-09-09
JP2021535231A (ja) 2021-12-16
KR20210005903A (ko) 2021-01-15
US11421181B2 (en) 2022-08-23
AU2019301866C1 (en) 2022-06-09
CN112424325A (zh) 2021-02-26
BR112020025205A2 (pt) 2021-03-30
BR112020025205B1 (pt) 2023-10-31
DK3820978T3 (da) 2022-11-14
JP7095124B2 (ja) 2022-07-04
WO2020011758A1 (fr) 2020-01-16
AU2019301866B2 (en) 2021-11-25

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