EP4176027B1 - Graisse à base de polyurée contenant des carbonates et son utilisation - Google Patents

Graisse à base de polyurée contenant des carbonates et son utilisation Download PDF

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Publication number
EP4176027B1
EP4176027B1 EP21739966.6A EP21739966A EP4176027B1 EP 4176027 B1 EP4176027 B1 EP 4176027B1 EP 21739966 A EP21739966 A EP 21739966A EP 4176027 B1 EP4176027 B1 EP 4176027B1
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Prior art keywords
weight
polyurea
grease composition
composition according
seal
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German (de)
English (en)
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EP4176027C0 (fr
EP4176027A1 (fr
Inventor
Hans Jürgen ERKEL
Olaf Binkle
Torsten Goerz
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Fuchs SE
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Fuchs SE
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Priority to HRP20240241TT priority Critical patent/HRP20240241T8/hr
Priority to RS20240291A priority patent/RS65283B1/sr
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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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/04—Mixtures of base-materials 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
    • 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
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/84—Esters of carbonic acid
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • 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
    • 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
    • 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
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the invention relates to polyurea grease compositions containing polyurea thickeners and at least one organic carbonate, lubrication points or components containing the polyurea grease composition and a seal comprising a sealing material made of fluorinated elastomers and the use of the greases.
  • Lubricants For tribosystems, as they are used in many technical applications, it is important to use lubricants to reduce friction and wear on the contact surfaces of moving parts. Depending on the area of application, lubricants of different consistencies can be used. Lubricating oils have a liquid and flowable consistency, while lubricating greases have a semi-solid to solid - often gel-like - consistency.
  • a lubricating grease The characteristic of a lubricating grease is that a liquid oil component is absorbed and held by a thickener component.
  • lubricating greases essentially include a thickener that is distributed in a base oil.
  • a lubricating grease of high utility value depending on the application requirements, a high degree of practical experience is required.
  • Greases are often used in encapsulated or sealed environments to protect the lubrication point from water, minimize grease loss and prevent entry of particles such as sand or dust.
  • Typical applications for lubricating greases are the lubrication of rolling bearings, plain bearings, gears or constant velocity joint shafts.
  • Polyurea lubricating greases are often used for lubrication points that are exposed to high temperatures and/or aggressive environments. If sealing materials are used under such operating conditions, fluorinated elastomers that are particularly thermally and chemically resilient are often used when selecting the sealing material. The combination of such a lubricating grease/sealing material pairing is often limited because the fluorinated elastomers tend to harden and even become brittle in the presence of the polyurea lubricating greases.
  • US20150299608 A1 describes a polyurea lubricating grease and its elastomer compatibility.
  • the object of the present invention is to improve the performance properties of polyurea lubricating greases, for example with regard to consistency, shear stability and service life and in particular the lubricating grease should not post-harden or post-harden as little as possible.
  • polyurea lubricating greases should be made available which have improved compatibility with fluorinated elastomers, such as those used as sealing materials, whereby the lubricating grease's performance properties should not be negatively influenced by any additives to increase compatibility with fluorinated elastomers.
  • additives can be used beyond c), such as: d) at least one additive, preferably in an amount of 0.5 to 40% by weight and in particular 2 to 10% by weight.
  • the polyurea fat composition optionally further contains 1 to 20% by weight, preferably 1 to 15% by weight, of a further thickener based on a soap and/or complex soap thickener.
  • Polyurea fat compositions Mixed fats containing polyurea thickeners and soap and/or complex soap thickeners are also referred to herein as polyurea fat compositions.
  • polyurea fat composition and polyurea fat(s) are used synonymously below.
  • the base oil preferably has a kinematic viscosity of 20 to 2500 mm 2 /s, in particular 40 to 500 mm 2 /s, in each case at 40 °C.
  • the base oils can be classified as mineral oils or synthetic oils.
  • Mineral oils include, for example, naphthenic-based mineral oils and paraffin-based mineral oils, classified according to API Group I. Chemically modified aromatic and low-sulfur mineral oils with a low proportion of saturated compounds and improved viscosity/temperature behavior compared to Group I oils, classified according to API Group II and III, are also suitable.
  • Synthetic oils that may be mentioned include, in particular, polyethers, esters, polyalphaolefins, polyglycols and alkyl aromatics and mixtures thereof, as well as silicone oils.
  • the polyether compound can have free hydroxyl groups, but can also be completely etherified or end groups esterified and/or made from a starting compound with one or more hydroxyl and/or carboxyl groups (-COOH).
  • Polyphenyl ethers, possibly alkylated, are also possible as sole components or, better yet, as mixed components.
  • esters of an aromatic di-, tri- or tetracarboxylic acid with one or in a mixture of C2 to C22 alcohols, esters of adipic acid, sebacic acid, trimethylolopropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic branched or unbranched, saturated or unsaturated C2 to C22 carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as individual components or in any mixture.
  • the polyurea thickeners are organic thickener systems which are obtainable by reacting one or more amine components with one or more isocyanate components.
  • the starting materials for producing the polyurea thickener(s) are primary amines and isocyanates.
  • the amines are monoaminohydrocarbyl, di- or polyaminohydrocarbylene compounds.
  • the hydrocarbyl or hydrocarbylene groups each preferably have 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms.
  • the hydrocarbylene group preferably has aliphatic groups, in particular alkyl or alkylene groups. Suitable amines or suitable polyureas are, for example, in EP 0508115 A1 from page 1, line 51 to page 16 mentioned below.
  • Mono- and/or polyisocyanates are suitable as isocyanate components, the polyisocyanates preferably being hydrocarbons with two isocyanate groups.
  • the isocyanates have 5 to 20, preferably 6 to 15, carbons and preferably contain aromatic groups.
  • Either the amine component is mono-, di- or polyfunctional or the isocyanate component is mono-, di- or polyfunctional or both.
  • the polyurea thickeners are available as a reaction product of diisocyanates with C6 to C20 hydrocarbyl monoamines.
  • the reaction products of mono-isocyanates, possibly plus additional diisocyanates, with diamines can also be present.
  • the polyurea thickeners typically do not have a polymeric character, but are, for example, dimers, trimers or tetramers.
  • isocyanates of the type R-NCO can also be used, where R represents a hydrocarbon radical with preferably 5 to 20 carbon atoms.
  • the polyurea thickener is preferably prepared by in-situ reaction of the amine and isocyanate components in the base oil.
  • additional inorganic thickeners can be bentonites, such as montmorillonite (the sodium ions of which may be exchanged or partially exchanged by organically modified ammonium ions), aluminosilicates, clays, hydrophobic and hydrophilic silica, if necessary together with oil-soluble polymers (e.g. polyolefins, poly( meth)acrylates, polyisobutylenes, polybutenes or polystyrene copolymers) can be used as co-thickeners.
  • oil-soluble polymers e.g. polyolefins, poly( meth)acrylates, polyisobutylenes, polybutenes or polystyrene copolymers
  • the bentonites, aluminosilicates, clays, silica, amorphous silicon dioxide and/or oil-soluble polymers can be added to produce the base fat or added later as an additive in the second step.
  • no inorganic thickeners are used, in particular no bentonites, aluminosilicates, clays, silica, and amorphous silicon dioxide, each individually.
  • Soap or complex soap thickeners based on calcium, lithium or aluminum salts are particularly suitable as organic thickeners.
  • the soap is available, for example, as a reaction product of, for example, calcium hydroxide, lithium hydroxide or aluminum alkoxide with a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, in particular with 16 to 20 carbon atoms, optionally substituted, for example by hydroxy, as an ester or anhydride.
  • Esterified dicarboxylic acid semiamides (C12 - C24) based on terephthalic acid can also be used.
  • the corresponding fats are also called soap thickeners here.
  • the soap becomes a complex soap due to the presence of a complexing agent.
  • Suitable complexing agents are: (a) the alkali metal salt (preferably lithium salt), alkaline earth metal salt (preferably calcium salt) or aluminum salt of a saturated or unsaturated mono-carboxylic acid or also hydroxycarboxylic acids with 2 to 8, in particular 2 to 4 carbon atoms or a di-carboxylic acid with 2 to 16 , in particular 2 to 12 carbon atoms, each optionally substituted, and/or (b) the alkali metal and/or alkaline earth metal salt of boric acid and/or phosphoric acid, in particular their reaction products with LiOH and/or Ca(OH) 2 .
  • Simple, mixed or complex soaps based on Li, Na, Mg, Ca, Al, Ti salts and carboxylic acids or sulfonic acids can be added during base fat production or later as an additive. Alternatively, these soaps can also be formed in situ during the production of the fats.
  • stearate benzoate hydroxyaluminates can be used to produce aluminum complex soap-thickened lubricating greases.
  • Lithium 12-hydroxystearate thickeners are typical representatives of lithium soap fats
  • calcium 12-hydroxystearate thickeners are typical for calcium soap fats.
  • the polyurea thickener and the soap or complex soap thickener are used together, with Ca soaps or Ca complex soaps being particularly preferred, for example in a mixing ratio of 10:1 to 1:10, in particular 5:1 to 1 : 5 (each mass : mass).
  • Soap or complex soap thickeners and polyurea thickeners are then preferably used together at 5 to 25% by weight based on the polyurea fat composition of claim 1, the polyurea thickener being used at least 1% by weight, preferably at least 1%. 5% by weight, each based on the polyurea fat composition.
  • Polymer powders such as polyamides, polyimides or PTFE, melamine cyanurate, graphite, metal oxides, boron nitride, silicates, e.g. magnesium silicate hydrate (talc), sodium tetraborate, potassium tetraborate, metal sulfides such as e.g. B. molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts, for example of alkali and alkaline earth metals, such as calcium carbonate, sodium and calcium phosphates, can be used. Likewise soot or other carbon-based solid lubricants such as nanotubes.
  • lignin derivatives such as alkali metal or alkaline earth metal lignin sulfonates, in particular calcium lignin sulfonates, can be used to achieve specific properties, for example 2 to 15% by weight (according to WO2011095155A1 or US 8507421 B2 ).
  • the organic carbonates have 4 to 8 carbon atoms.
  • the residues or components of the organic carbonates are hydrocarbons (apart from the carbonate group itself), that is, the organic carbonate is not heteroatom-substituted.
  • Cyclic carbonates in particular with 4 to 8, in particular 4 or 5 carbon atoms, are preferred. Examples are diethyl carbonate, methyl ethyl carbonate; Dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diisobutyl carbonate,.
  • cyclic organic carbonates examples include propylene carbonate (4-methyl-1,3-dioxolan-2-one), 2,3-butylene carbonate (4,5-dimethyl-1,3-dioxolan-2-one) or 1, 2-Butylene carbonate (4-ethyl-1,3-dioxolan-2-one), hexahydro-1,3-benzodioxol-2-one or 1,3-benzodioxol-2-one can be used, with propylene carbonate being preferably used.
  • the organic cyclic carbonate can be added to the polyurea fat as an additive during production, but preferably after the thickener system has been completely formed in the cooling phase.
  • the lubricating grease compositions according to the invention contain customary additives against corrosion, oxidation and for protection against metal influences, which act as chelate compounds, radical scavengers, reaction layer formers and the like. Additives that improve the hydrolysis resistance of ester base oils, such as carbodiimides or epoxides, can also be added.
  • the wt.% information refers to the overall composition and applies independently of each other. A component that is assigned to one of the groups a), b), c) or d) cannot simultaneously be a component of another group a) to d).
  • the wt.% information adds up to 100 wt.% for each selection of components, including any optional components not mentioned above.
  • the thickener is used in such a way that the composition contains so much thickener that a cone penetration value (rolled penetration) of 220 to 430 mm/10 (at 25 ° C), preferably 265 to 385 mm/10, is obtained (determined according to DIN ISO 2137).
  • the polyurea in the polyurea grease composition is generally produced by in situ reaction of the above-mentioned amines and isocyanates, preferably in the base oil.
  • a further thickener component is added to the polyurea base fat, such as the soap or complex soap thickener, this is done, for example, after the base fat has been produced during the cooling curve at a suitable temperature (e.g. at 140 to 115 ° C. Addition of the soap or complex soap thickener, in particular the Ca- soap or the Ca complex soap).
  • the base fat is preferably heated to temperatures of over 120°C or, better, greater than 150°C.
  • the conversion to the base fat takes place in a heated reactor, which can also be designed as an autoclave or vacuum reactor.
  • a second step the formation of the thickener structure is completed by cooling and, if necessary, additional components such as additives and/or base oil are added to set the desired consistency or the desired property profile.
  • the second step can be carried out in the reactor of the first step, but preferably the base fat is transferred from the reactor into a separate stirred tank for cooling and mixing in any additional components.
  • the lubricating greases according to the invention are particularly suitable for use in or for plain bearings, roller bearings, gears or constant velocity joint shafts.
  • the lubricating greases according to the invention, containing predominantly polyurea thickeners as thickeners, are particularly suitable as high-temperature greases.
  • fluorinated elastomers as materials for seals of various designs is often dictated by the operating conditions such as high temperatures and/or chemically aggressive media, as these materials have exceptional resistance to heat, weather conditions and numerous chemicals.
  • Fluorororubbers (often abbreviated as FKM or FPM) belong to the class of fluorinated elastomers. Depending on the desired fluoroelastomer properties, diamine, bisphenolic or peroxidic crosslinks are used for crosslinking. Fluororubbers are rubbers that have vinylidene (di)fluoride (VDF) as one of their monomers as a common feature. The two main types of fluororubbers are copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) and terpolymers of VDF, HFP and tetrafluoroethylene (TFE). Typical commercial products for fluororubbers are sold under the brands Viton ® , Tecnoflon ® , Dyneon ® or Dai-El ® . distributed.
  • fluorinated elastomers such as: E.g. perfluoro rubber (FFKM), tetrafluoroethylene/propylene rubbers (FEPM) and fluorinated silicone rubbers (FVMQ).
  • FFKM perfluoro rubber
  • FEPM tetrafluoroethylene/propylene rubbers
  • FVMQ fluorinated silicone rubbers
  • sealing materials are used in the form or as part of seals at the lubrication points where the polyurea grease is used. Seals are a widely differentiated class of important construction elements.
  • sealing points can be divided into static and dynamic.
  • Lubrication is particularly necessary for moving parts, so seals often refer to dynamic sealing points.
  • static housing seal e.g. of gearboxes as leakage protection, is also included as an example of static seals.
  • the seals are designed, for example, as O-rings or profile rings, radial shaft seals, mechanical seals, stuffing box seals, flat seals, lip seals, wipers, sealing cords.
  • Examples of applications include radial shaft seals for generator shafts, stuffing box seals for pumps, mechanical seals for chemical reactors or bead mills (sealing the stirrer shaft), shaft seals in dryers, screw conveyors and conveyor belts, sealing elements for hydraulic and pneumatic systems (presses, construction vehicles, etc.) and Seals for rolling bearings and plain bearings.
  • the thickener-oil mixture was then heated to a final temperature of 160 ° C over the course of 2 hours. After the reaction mixture had cooled to a temperature of 100 ° C, 15.0 g of Irganox L101 and 15.0 g of Irganox L115 were added. The mixture was cooled to 60 ° C and the desired amount of propylene carbonate (0 - 1% by weight) was added. Finally, the lubricating grease was homogenized using a colloid mill.
  • group I oil mineral oil, paraffinic; 110 cSt at 40 ° C
  • group I oil mineral oil, paraffinic; 110 cSt at 40 ° C
  • the contents of the reaction vessel were heated to 60 ° C with stirring.
  • 91.5 g of n-octylamine were then added dropwise to the contents of the reaction vessel.
  • An exothermic reaction took place with the formation of the thickener.
  • the reaction mixture was heated to a final temperature of 160 ° C within 2 hours with stirring and then cooled to 60 ° C.
  • the desired amount of propylene carbonate (0-1% by weight) was then added and the fat was finally homogenized using a colloid mill.
  • Group I oil paraffinic; 480cSt at 40°C
  • Group II oil hard hydrogenated, paraffinic; 105-110cSt at 40°C
  • the properties of the polyurea grease obtained containing calcium soap are summarized in Table 3.
  • the dropping point was determined according to DIN ISO 2176. ⁇ i>Table 3 ⁇ /i> B3-A B3-B B3-C Propylene carbonate 0% 0.3% 1% RP-SF 253 281 273 RP-24h 233 239 242 WP60 272 289 286 WP60000 285 304 294 ⁇ P 60-60000 13 15 8th Dropping point 272.7°C 270.0°C 264.2°C ⁇ Shore A +8 +4 +1 ⁇ weight +1.7% + 1.6% +1.7% ⁇ volume +2.6% + 0.6% +2.6%
  • the compatibility of polyurea greases with fluorinated elastomers is determined using a vinylidene fluoride-hexafluoropropylene copolymer (Type: SRE-FKM/2X according to DIN ISO 13226).
  • SRE-FKM/2X vinylidene fluoride-hexafluoropropylene copolymer
  • test specimens with a diameter of 30mm and a thickness of 2mm were punched out of an elastomer plate made of SRE-FKM/2X.
  • the test specimens were stored in the polyurea fats described above at 180°C or 160°C for 7 days and then evaluated.
  • the bending tests were carried out by bending the elastomer over a tube with a diameter of 3cm and 1cm. The elasticity of the elastomer was evaluated.
  • the usage properties in terms of service life and post-curing behavior can be improved by adding carbonates.
  • reaction mixture was heated to a final temperature of 160 ° C within 3 hours.
  • the reactor contents were then cooled to 135°C, followed by the addition of 180.0 grams of calcium 12-hydroxystearate.
  • the mixture was stirred for 30 minutes at a constant temperature.
  • the reaction was cooled to 60°C with continued stirring, followed by the addition of 10.0 grams of an amine antioxidant (Irganox L57).
  • the base fat batch was then divided into parts A and B. Part B was transferred to a planetary mixer, 0.5% propylene carbonate was added at 25 ° C and mixed for 15 minutes.
  • Example 4A without propylene carbonate
  • Example 4B with 0.5% by weight of propylene carbonate
  • Example 4 A Example 4 B
  • Example 4 C Propylene carbonate [wt.%] 0 0.5 1.0 Temperature when adding the propylene carbonate 25°C 25°C 135°C RP-SF / DIN ISO 2137 296 306 293 RP-24h at 25°C / DIN ISO 2137 283 287 269 RP-24h at 100°C / DIN ISO 2137 215 221 225 ⁇ RP-24h (25°C vs.
  • the FE9 test of the fats reveals another advantage of organic carbonates.
  • the downtimes F10 and F50 could be improved by over 50% by adding propylene carbonate.

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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)
  • Sealing Material Composition (AREA)
  • Sealing Devices (AREA)
  • Sealing Of Bearings (AREA)
  • Rolling Contact Bearings (AREA)

Claims (15)

  1. - Composition de graisse à base de polyurée présentant :
    a) au moins une huile de base ;
    b) au moins un épaississant polyurée ; et
    c) au moins un carbonate organique, le carbonate organique présentant 4 à 8 atomes de carbone,
    ladite composition présentant :
    a) 55 à 95 % en poids de l'huile de base ;
    b) 1 à 20 % en poids de l'épaississant polyurée ; et
    c) 0,1 à 10 % en poids du carbonate organique.
  2. - Composition de graisse à base de polyurée selon la revendication 1, caractérisée par le fait que la composition présente :
    a) 70 à 90 % en poids de l'huile de base ;
    b) 1,5 à 15 % en poids de l'épaississant polyurée ; et
    c) 0,2 à 5 % en poids, de façon particulièrement préférée 0,5 à 2 % en poids, du carbonate organique.
  3. - Composition de graisse à base de polyurée selon l'une des revendications 1 ou 2, caractérisée par le fait que la composition présente en outre :
    d) 0,5 à 40 % en poids, en particulier 2 à 10 % en poids, d'additifs ;
    e) 0 à 20 % en poids, en particulier 0 à 5 % en poids, d'épaississants inorganiques ; et
    f) 0 à 20 % en poids, en particulier 0,1 à 15 % en poids, de lubrifiants solides.
  4. - Composition de graisse à base de polyurée selon au moins l'une des revendications précédentes, caractérisée par le fait que la composition présente en outre :
    g) 0 à 20 % en poids, en particulier 1 à 15 %, d'autres épaississants organiques, en particulier des épaississants savons ou savons complexes à base de savons de calcium, de lithium ou d'aluminium, en particulier de savons de lithium.
  5. - Composition de graisse à base de polyurée selon au moins l'une des revendications précédentes, dans laquelle ladite composition ne contient pas de bentonites, d'aluminosilicates, d'argiles, de silice, de dioxyde de silicium amorphe et en particulier ne contient pas d'épaississants inorganiques.
  6. - Composition de graisse à base de polyurée selon au moins l'une des revendications précédentes, dans laquelle le carbonate organique est un carbonate cyclique, en particulier le carbonate de propylène.
  7. - Composition de graisse à base de polyurée selon au moins l'une des revendications précédentes, caractérisée par le fait que la composition présente une valeur de pénétration de cône pour la pénétrabilité travaillée de 220 à 430 mm/10 à 25°C, de préférence de 265 à 385 mm/10 à 25°C, déterminée selon la norme ISO 2137.
  8. - Composition de graisse à base de polyurée selon au moins l'une des revendications précédentes, dans laquelle l'huile de base présente une viscosité cinématique de 20 à 2500 mm2/s, de préférence de 40 à 500 mm2/s, dans chaque cas à 40°C.
  9. - Point de lubrification présentant la composition de graisse à base de polyurée selon au moins l'une des revendications précédentes et un joint d'étanchéité comportant un matériau d'étanchéité, le matériau d'étanchéité constitant en un fluoropolymère élastique.
  10. - Composant présentant :
    a) au moins un point de lubrification ;
    b) un dispositif d'étanchéité comportant un matériau d'étanchéité, le matériau d'étanchéité consistant en un fluoropolymère élastique ; et
    c) la composition de graisse à base de polyurée selon au moins l'une des revendications 1 à 7 en contact avec le point de lubrification et le dispositif d'étanchéité.
  11. - Point de lubrification selon la revendication 9 ou composant selon la revendication 10, dans lequel le fluoropolymère élastique est un élastomère de caoutchouc fluoré.
  12. - Point de lubrification selon la revendication 9 ou composant selon la revendication 10, dans lequel le dispositif d'étanchéité est un joint torique ou une bague profilée, un joint radial pour arbre, une garniture étanche à anneau glissant, un joint de presse-étoupe, un joint plat, un joint à lèvre, un joint racleur ou un cordon d'étanchéité.
  13. - Composant selon la revendication 10, dans lequel le composant est un arbre, un engrenage, un piston, une articulation, un palier à rouleaux ou un palier lisse.
  14. - Utilisation de la composition de graisse à base de polyurée selon l'une des revendications 1 à 7 pour un point de lubrification ou un composant selon l'une des revendications 9 à 13.
  15. - Procédé de production de la composition de graisse à base de polyurée selon au moins l'une des revendications 1 à 8, dans lequel le procédé comporte la production d'une polyurée dans au moins une partie de l'huile de base à chaud et l'addition du carbonate organique a lieu après la production de la polyurée dans l'huile de base et lors du refroidissement à une température entre 100° et 135°C.
EP21739966.6A 2020-07-03 2021-07-01 Graisse à base de polyurée contenant des carbonates et son utilisation Active EP4176027B1 (fr)

Priority Applications (2)

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HRP20240241TT HRP20240241T8 (hr) 2020-07-03 2021-07-01 Poliurea masti koje sadrže karbonate i njihova primjena
RS20240291A RS65283B1 (sr) 2020-07-03 2021-07-01 Masti za podmazivanje na bazi poliuree koje sadrže karbonate i njihova primena

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DE102020117671.6A DE102020117671B4 (de) 2020-07-03 2020-07-03 Schmierstellen aufweisend eine Polyharnstoff-Schmierfett-Zusammensetzung und eine Dichtung umfassend ein Dichtmaterial aus fluorierten Elastomeren und die Verwendung der Polyharnstoff-Schmierfett-Zusammensetzung für eine Schmierstelle umfassend eine derartige Dichtung
PCT/DE2021/100568 WO2022002317A1 (fr) 2020-07-03 2021-07-01 Graisses lubrifiantes à base de polyurée contenant des carbonates, et leur utilisation

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EP (1) EP4176027B1 (fr)
JP (1) JP7719108B2 (fr)
KR (1) KR20230035334A (fr)
CN (1) CN115843307A (fr)
AU (1) AU2021302154B2 (fr)
BR (1) BR112022026813A2 (fr)
CA (1) CA3182878A1 (fr)
DE (1) DE102020117671B4 (fr)
ES (1) ES2972947T3 (fr)
HR (1) HRP20240241T8 (fr)
HU (1) HUE065479T2 (fr)
MA (1) MA60203B1 (fr)
MX (1) MX2022016216A (fr)
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RS (1) RS65283B1 (fr)
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BR112022026813A2 (pt) 2023-04-25
PL4176027T3 (pl) 2024-05-06
CA3182878A1 (fr) 2022-01-06
EP4176027C0 (fr) 2023-12-20
WO2022002317A1 (fr) 2022-01-06
AU2021302154B2 (en) 2025-12-18
ZA202212961B (en) 2024-01-31
RS65283B1 (sr) 2024-03-29
KR20230035334A (ko) 2023-03-13
MX2022016216A (es) 2023-02-01
MA60203B1 (fr) 2024-03-29
HRP20240241T1 (hr) 2024-05-24
DE102020117671A1 (de) 2021-10-21
JP2023532131A (ja) 2023-07-26
US12054691B2 (en) 2024-08-06
HUE065479T2 (hu) 2024-05-28
ES2972947T3 (es) 2024-06-17
HRP20240241T8 (hr) 2024-06-07
AU2021302154A1 (en) 2023-03-02
DE102020117671B4 (de) 2022-06-09
EP4176027A1 (fr) 2023-05-10
CN115843307A (zh) 2023-03-24
US20230257677A1 (en) 2023-08-17

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