EP4176027A1 - Graisses lubrifiantes à base de polyurée contenant des carbonates, et leur utilisation - Google Patents

Graisses lubrifiantes à base de polyurée contenant des carbonates, et leur utilisation

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Publication number
EP4176027A1
EP4176027A1 EP21739966.6A EP21739966A EP4176027A1 EP 4176027 A1 EP4176027 A1 EP 4176027A1 EP 21739966 A EP21739966 A EP 21739966A EP 4176027 A1 EP4176027 A1 EP 4176027A1
Authority
EP
European Patent Office
Prior art keywords
polyurea
weight
composition according
seal
carbonate
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
EP21739966.6A
Other languages
German (de)
English (en)
Other versions
EP4176027B1 (fr
EP4176027C0 (fr
Inventor
Hans Jürgen ERKEL
Olaf Binkle
Torsten Goerz
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
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 Fuchs Petrolub SE filed Critical Fuchs Petrolub SE
Priority to HRP20240241TT priority Critical patent/HRP20240241T8/hr
Priority to RS20240291A priority patent/RS65283B1/sr
Publication of EP4176027A1 publication Critical patent/EP4176027A1/fr
Application granted granted Critical
Publication of EP4176027B1 publication Critical patent/EP4176027B1/fr
Publication of EP4176027C0 publication Critical patent/EP4176027C0/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
    • 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
    • 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—Semi-solids; greasy

Definitions

  • the invention relates to polyurea lubricating grease compositions containing polyurea thickener and at least one organic carbonate, lubrication points or components containing the polyurea lubricating grease composition and a seal comprising a sealing material made of fluorinated elastomers and the use of the lubricating greases.
  • Lubricants For tribological systems, as 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 characteristic of a lubricating grease is that a liquid oil component is absorbed and retained by a thickener component.
  • the pasty nature of a lubricating grease and its property of being spreadable and easily plastically deformable, together with the property of being able to adhere, ensures that the lubricating grease wets the lubrication point and that the lubricating effect unfolds on the tribologically stressed surfaces.
  • lubricating greases essentially comprise a thickening agent that is present in a base oil.
  • Lubricating greases are often used in encapsulated or sealed environments in order to protect the lubrication point from water, to minimize grease losses and to prevent the ingress of particles such as sand or dust.
  • Typical applications for lubricating greases are the lubrication of roller bearings, slide bearings, gears or constant velocity universal joint shafts.
  • Polyurea greases are often used for lubrication points that are exposed to high temperatures and / or aggressive environments. If sealing materials are used in such conditions of use, fluorinated elastomers that are more thermally and chemically particularly resilient are often used with regard to the selection of the sealing material. The combination of such a lubricating grease / sealing material pairing is often restricted, since the fluorinated elastomers tend to harden or even become brittle in the presence of the polyurea lubricating greases.
  • Carbonates such as ethylene carbonate (CN107903987 A) or propylene carbonate (US4298481 A) are known in lubricating greases as activators / dispersants for inorganic thickeners, but not as additives for polyurea thickeners.
  • 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 or as little post-hardening as possible. Furthermore, polyurea lubricating greases are to be made available which have improved compatibility with fluorinated elastomers, such as those used as sealing materials, whereby the lubricating grease should not be adversely affected in its performance properties by any additives to increase the compatibility with fluorinated elastomers. Summary of the invention
  • the polyurea fat composition according to the invention comprises: a) a base oil (optionally comprising a base oil mixture) in an amount of 55 to 95% by weight and preferably 70 to 90% by weight; b) at least one polyurea thickener in an amount of 1 to 20% by weight, preferably 1.5 to 15% by weight; c) at least one organic carbonate, the organic carbonate having 4 to 8 carbon atoms in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, particularly preferably 0.5 to 2% by weight.
  • additives can be used, 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 also 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 here as polyurea fat compositions.
  • polyurea fat composition and polyurea fat (s) are used synonymously.
  • Customary lubricating oils that are liquid at room temperature are suitable as base oils.
  • 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 mineral oils and paraffinic mineral oils, according to classification 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 are, in particular, polyethers, esters, polyalphaolefins, polyglycols and alkyl aromatics and their mixtures, as well as silicone oils.
  • the polyether compound can have free hydroxyl groups, but can also be completely etherified or end groups and / or be produced from a starter compound with one or more hydroxyl and / or carboxyl groups (-COOH).
  • Polyphenyl ethers, optionally alkylated, are also possible as sole components or, better still, as mixed components.
  • Esters of an aromatic di-, tri- or tetracarboxylic acid with one or 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 are suitable 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 can be obtained by reacting one or more amine components with one or more isocyanate components.
  • the starting materials for the production of the polyurea thickener are primary amines and isocyanates.
  • the amines are monoamino hydrocarbyl, di or polyamino hydrocarbylene compounds.
  • the hydrocarbyl or hydrocarbylene groups preferably each 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 mentioned, for example, in EP 0508115 A1 from page 1, line 51 to page 16 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 e.g. dimers, trimers or tetramers.
  • isocyanates of the R-NCO (monoisocyanate) type where R represents a hydrocarbon radical with preferably 5 to 20 carbon atoms.
  • diureas obtainable from diisocyanates and monoamines or tetraureas obtainable from diisocyanates, monoamine and diamine, each as defined above. are particularly preferred
  • the polyurea thickener is preferably produced by the in-situ reaction of the amine and isocyanate components in the base oil.
  • additional inorganic thickeners include bentonites such as montmorillonite (the sodium ions of which are exchanged or partially exchanged by organically modified ammonium ions), aluminosilicates, clays, hydrophobic and hydrophilic silicic acid, possibly together with oil-soluble polymers (e.g. polyolefins , Poly (meth) acrylates, polyisobutylenes, polybutenes or polystyrene copoly mers) can be used as co-thickeners.
  • 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, silicic acid, and amorphous silicon dioxide, in each case even individually.
  • Soap or complex soap thickeners based on calcium, lithium or aluminum salts are particularly suitable as organic thickeners.
  • the soap is available e.g. as a reaction product of e.g. calcium hydroxide, lithium hydroxide or aluminum alcoholate with a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, in particular with 16 to 20 carbon atoms, optionally substituted e.g. by hydroxyl, as an ester or anhydride.
  • Esterified dicarboxylic acid half-amides (C12 - C24) based on terephthalic acid can also be used.
  • the corresponding fats are also referred to here as fen thickeners.
  • the presence of a complexing agent turns the soap into a complex soap.
  • Suitable complexing agents are: (a) the alkali salt (preferably lithium salt), alkaline earth salt (preferably calcium salt) or aluminum salt of a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids with 2 to 8, in particular 2 to 4 carbon atoms or a dicarboxylic acid with 2 up to 16, in particular 2 to 12 carbon atoms, each optionally substituted, and / or (b) the alkali and / or alkaline earth salt of boric acid and / or phosphoric acid, in particular their reaction products with LiOH and / or Ca (OH) 2.
  • the alkali salt preferably lithium salt
  • alkaline earth salt preferably calcium salt
  • Simple, mixed or complex soaps based on Li, Na, Mg, Ca, Al, Ti salts and carboxylic acids or sulfonic acids can be added as an additive during the base fat manufacture or later. Alternatively, these soaps can also be formed in situ during the manufacture of the fats.
  • stearate benzoate hydroxyaluminates can be used to make aluminum complex soap thickened greases.
  • Lithium-12-hydroxystearate thickeners are typical representatives of lithium soap fats, calcium-12-hydroxystearate those 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).
  • Soaps or complex soap thickeners and polyurea thickeners are then preferably used together in an amount of 5 to 25% by weight in relation to the polyurea fat composition of claim 1, the polyurea thickener being used at least 1% by weight, preferably at least to 1.5 wt.%, each Weil in relation to the polyurea fat composition.
  • Solid lubricants such as 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.
  • soot or other carbon-based solid lubricants such as nanotubes.
  • Lignin derivatives such as alkali or alkaline earth lignin sulfonates, in particular calcium lignin sulfonates, can also be used to achieve specific properties, e.g. 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), ie the organic carbonate is not substituted by a heteroatom.
  • 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 ,.
  • organic carbonates for example, 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 are used, propylene carbonate being preferred is used.
  • the organic cyclic carbonate can be added as an additive to the polyurea fat 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 conventional 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.
  • Customary additives for the purposes of the invention are antioxidants, anti-wear agents, anti-corrosion agents, detergents, dyes, lubricity improvers, adhesion improvers, viscosity additives, friction reducers, high-pressure additives and metal deactivators. Examples are:
  • primary antioxidants such as amine compounds (e.g. alkylamines or 1-phenylaminonaphthalene), aromatic amines such as phenylnaphthylamines or diphenylamines or polymeric hydroxyquinolines (e.g. TMQ), phenol compounds (e.g. 2,6-di-tert-butyl-4 methylphenol), zinc dithiocarbamate or zinc dithiophosphate;
  • amine compounds e.g. alkylamines or 1-phenylaminonaphthalene
  • aromatic amines such as phenylnaphthylamines or diphenylamines or polymeric hydroxyquinolines (e.g. TMQ)
  • phenol compounds e.g. 2,6-di-tert-butyl-4 methylphenol
  • zinc dithiocarbamate or zinc dithiophosphate e.g. 2,6-di-tert-butyl-4 methylphenol
  • Secondary antioxidants such as phosphites, e.g. tris (2,4-di-tert-butylphenyl phosphite) or bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite or thioethers (e.g. cresol thioether);
  • High-pressure additives and / or anti-wear additives such as sulfur or organic sulfur compounds such as polysulfides or sulfurized olefins, overbased calcium sulfonates, thiophosphates, phosphorus compounds such as amine-neutralized alkyl phosphates; • inorganic or organic boron compounds, zinc dialkyldithiophosphate, organic bismuth compounds; Thiophosphonates such as triphenyl thiophosphate, phosphonates (phosphites) such as dioctyl phosphonate, alkyl sulfonates, thio carbamates such as methylene bis (dibutyldithiocarbamate and dithiocarbamate).
  • sulfur or organic sulfur compounds such as polysulfides or sulfurized olefins, overbased calcium sulfonates, thiophosphates, phosphorus compounds such as amine-neutralized alkyl phosphates
  • Active ingredients that improve "oiliness” such as C2 to C6 polyols, fatty acids, fatty acid esters or animal or vegetable oils;
  • Anti-corrosion agents such as sulfonates such as petroleum sulfonate, dinonylnaphthalene sulfonate or sorbitan esters; neutral or overbased calcium sulfonates, magnesium sulfonates, sodium sulfonates, calcium and sodium naphthalene sulfonates, sulfonic acid esters, disodium sebacate, calcium salicylates, amine phosphates, succinates;
  • Metal deactivators such as benzotriazoles such as methylbenzotriazole dialkylamine, sterically hindered phenols, sodium nitrite;
  • Viscosity improvers such as polymethacrylate, polyisobutylene, oligo dec-1-ene, polystyrenes;
  • MOsSkLnQz in which L are independently selected ligands having organogroups with carbon atoms, as disclosed in US 6172013 B1, in order to make the compound soluble or dispersible in the oil, where n ranges from 1 to 4, k ranges from 4 to 7, Q is selected from the group of neutral electron donor compounds consisting of amines, alcohols, phosphines and ethers, and z is in the range from 0 to 5 and comprises non-stoichiometric values (compare DE 102007048091 ); _ organic acids such as isostearic acid, functional polymers such as oleylamides, organic compounds based on polyether and amide, such as alkyl polyethylene glycol tetradecylene glycol ether, PIBSI (polyisobutylene succinic acid imide) or PIBSA (polyisobutylene succinic acid anhydride), parti-phosphonyl glyceride, parti- alglyceride.
  • the polyurea fat compositions are built up in particular as follows: a) 55 to 95% by weight, in particular 70 to 90% by weight, of the base oil; b) 1 to 20% by weight, in particular 1.5 to 15% by weight, of the polyurea thickener; c) 0.1 to 10% by weight, in particular 0.2 to 5% by weight, particularly preferably 0.5 to 2% by weight, of the organic carbonates; and from the following optional components: d) 0.5 to 40% by weight, in particular 2 to 10% by weight, additives; e) 0 to 20% by weight, in particular 0 to 5% by weight, of inorganic thickeners, such as amorphous S1O2 or silica; and f) 0 to 20% by weight, in particular 0.1 to 15% by weight, solid lubricants g) 0 to 20% by weight, in particular 1 to 15%, further organic thickeners, in particular soap or complex soap thickeners based on calcium -, lithium or aluminum soaps in addition to any other components such as lignin derivatives
  • the percentages by weight relate to the overall composition and apply independently of one another.
  • a component that is assigned to one of the groups a), b) c) or d) cannot be part of another group a) to d) at the same time.
  • the percentages by weight add up to 100 percent by weight 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 (worked 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 fat composition is generally made by the in-situ reaction of the above amines and isocyanates, preferably in the base oil. According to the method on which the present invention is based for the produc- tion of the polyurea fat composition, a preliminary stage (base fat) is first created by combining at least
  • Cooling the base fat and adding the additives preferably below 100 ° C or even below 80 ° C.
  • the soap or complex soap thickener is added to the polyurea base fat, this is done, for example, after the base fat has been prepared, 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 approx Soap or the calcium complex soap).
  • a suitable temperature e.g. at 140 to 115 ° C, addition of the soap or complex soap thickener, in particular the approx Soap or the calcium 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, further 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 the base fat is preferably transferred from the reactor to a separate stirred tank for cooling and mixing in the possibly further constituents.
  • What applies to pure polyurea fats can also be applied to mixed thickener systems with polyurea thickeners.
  • the production of polyurea fats with lime soap content (simple and complex soaps of hydroxymonocarboxylic acids, for example 12-hydroxystearic acid) is disclosed in US Pat. No. 5,084,193, for example.
  • the process of US 5084193 can also be used to produce the polyurea greases according to the invention.
  • the lubricating greases according to the invention are particularly suitable for use in or for plain bearings, roller bearings, gears or also constant velocity universal joint shafts.
  • the lubricating greases according to the invention, containing predominantly polyurea thickeners as thickeners, are particularly suitable as high-temperature greases.
  • the selection of fluorinated elastomers as materials for seals of various designs is often dictated by the conditions of use such as high temperature 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. For crosslinking, depending on the desired fluoroelastomer properties, e.g. diamine, bisphenolic or peroxide crosslinks are used. Fluoro rubbers are those rubbers that have vinylidene (di) fluoride (VDF) as one of their monomers as a common feature. The two most important types of fluororubbers are copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) and terpolymers of VDF, HFP and tetrafluoroethylene (TFE). Typical commercial products for fluoro rubbers are under the brands Viton®, Tecnoflon®, Dyneon® or Dai-El®. expelled.
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • TFE tetra
  • fluorinated Elastomers B. perfluorinated rubber (FFKM), tetrafluoroethylene / propylene rubbers (FEPM) and fluorinated silicone rubbers (FVMQ).
  • FFKM perfluorinated rubber
  • FEPM tetrafluoroethylene / propylene rubbers
  • FVMQ fluorinated silicone rubbers
  • the sealing materials are used in the form of 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. In principle, it can be divided into static and dynamic sealing points. Lubrication is particularly necessary for moving parts, so the seals often relate to dynamic sealing points. But the static housing seal, for example from gearboxes as leak protection, is also included as an example of static seals.
  • the seals are e.g. designed as O-rings or profile rings, radial shaft seals, mechanical seals, stuffing box seals, flat seals, lip seals, wipers, sealing cords.
  • Examples of applications are radial shaft seals for generator shafts, stuffing box seals for pumps, mechanical seals for chemical reactors or bead mills (sealing of 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 roller bearings and plain bearings.
  • Example 1 Production of the fats B1-A to B1-C 630 g of group II oil (hard-hydrogenated, paraffinic; 105-110 cSt at 40 ° C.) were placed in a heatable reaction vessel with a stirrer. 113.4 g of 4,4-methylene-bis-diphenyl diisocyanate were added and the contents of the reaction vessel were heated to 60 ° C. with stirring. 630 g of PAO 8 were placed in a further heatable vessel with a stirrer, and 87.6 g of p-toluidine and 9.0 g of cyclohexylamine were added. The contents of the jar were heated to 60 ° C.
  • group II oil hard-hydrogenated, paraffinic; 105-110 cSt at 40 ° C.
  • the properties of the resulting polyurea fat containing calcium soap are summarized in Table 3.
  • the dropping point was determined in accordance with DIN ISO 2176.
  • the compatibility of the polyurea greases with fluorinated elastomers is determined using a vinylidene fluoride-hexafluoropropylene copolymer (type: SRE-FKM / 2X according to DIN ISO 13226). For this purpose, test specimens with a diameter of 30 mm and a thickness of 2 mm were punched out of an elastomer plate made of SRE-FKM / 2X. The test specimens were stored in the polyurea greases described above at 180 ° C. or 160 ° C. for 7 days and then evaluated.
  • a vinylidene fluoride-hexafluoropropylene copolymer type: SRE-FKM / 2X according to DIN ISO 13226.
  • the evaluation of the fluorinated elastomers took place after wiping off the grease with a clean cloth by: a) Determination of the penetration hardness (Shore A) according to DIN EN ISO 7619-1, whereby the test specimen had a penetration hardness (Shore A) of 78 before the treatment, and b) bending tests by hand.
  • the bending tests were carried out by bending the elastomer over a tube with a diameter of 3 cm and 1 cm. The elasticity of the elastomer was evaluated.
  • the fluorinated elastomers When the propylene carbonate is used in polyurea grease, the fluorinated elastomers have less or no tendency to harden. According to the recommendation of the elastomer manufacturer, greases that cause a change in hardness of significantly more than 10 points with regard to the penetration hardness (Shore A) according to DIN EN ISO 7619-1 are considered incompatible with the elastomer concerned.
  • the addition of carbonates can improve the properties in terms of service life and post-hardening behavior.
  • 875.0 grams of Group I oil (paraffinic; 105-110cSt at 40 ° C) and 875.0g of Group II oil (hard-hydrogenated, paraffinic; 105-110cSt at 40 ° C) were placed in a heatable stirrer.
  • 31.5 grams of 4,4-methylene-bis-diphenyl diisocyanate (MDI) were added to this oil mixture.
  • MDI 4,4-methylene-bis-diphenyl diisocyanate
  • Example 4A without propylene carbonate
  • Example 4B with 0.5% by weight of propylene carbonate
  • the FE9 test of the fats reveals another advantage of the organic carbonates.
  • the downtimes F10 and F50 could be improved by more than 50% by adding propylene carbonate.

Landscapes

  • 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)

Abstract

L'invention concerne des compositions de graisses lubrifiantes à base de polyurée contenant des épaississants à base de polyurée et au moins un carbonate organique, des points de lubrification ou des composants contenant la composition de graisse lubrifiante à base de polyurée, un joint d'étanchéité comprenant un matériau d'étanchéité à partir d'élastomères fluorés et l'utilisation des graisses lubrifiantes.
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)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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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JP (1) JP2023532131A (fr)
KR (1) KR20230035334A (fr)
CN (1) CN115843307A (fr)
AU (1) AU2021302154A1 (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)
PL (1) PL4176027T3 (fr)
RS (1) RS65283B1 (fr)
WO (1) WO2022002317A1 (fr)
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JP2799634B2 (ja) 1991-03-07 1998-09-21 日本石油株式会社 等速ジョイント用グリース組成物
WO1993007242A1 (fr) 1991-10-08 1993-04-15 Chevron Research And Technology Company Additifs protegeant les joints d'etancheite au fluorocarbone destines aux huiles de graissage
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JP3978998B2 (ja) 2000-11-14 2007-09-19 日本精工株式会社 転がり軸受
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JP5991477B2 (ja) * 2012-10-31 2016-09-14 協同油脂株式会社 ハブユニット軸受用グリース組成物
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CN107903987A (zh) 2017-12-01 2018-04-13 苏州市宽道模具机械有限公司 一种抗磨耐高温润滑脂及其制备方法

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CN115843307A (zh) 2023-03-24
EP4176027B1 (fr) 2023-12-20
US12054691B2 (en) 2024-08-06
BR112022026813A2 (pt) 2023-04-25
MX2022016216A (es) 2023-02-01
ZA202212961B (en) 2024-01-31
CA3182878A1 (fr) 2022-01-06
MA60203B1 (fr) 2024-03-29
AU2021302154A1 (en) 2023-03-02
HRP20240241T8 (hr) 2024-06-07
PL4176027T3 (pl) 2024-05-06
JP2023532131A (ja) 2023-07-26
ES2972947T3 (es) 2024-06-17
RS65283B1 (sr) 2024-03-29
US20230257677A1 (en) 2023-08-17
KR20230035334A (ko) 2023-03-13
HRP20240241T1 (hr) 2024-05-24
EP4176027C0 (fr) 2023-12-20
WO2022002317A1 (fr) 2022-01-06
DE102020117671B4 (de) 2022-06-09
DE102020117671A1 (de) 2021-10-21
HUE065479T2 (hu) 2024-05-28

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