EP4090723A1 - Lithium complex hybrid grease - Google Patents

Lithium complex hybrid grease

Info

Publication number
EP4090723A1
EP4090723A1 EP21704440.3A EP21704440A EP4090723A1 EP 4090723 A1 EP4090723 A1 EP 4090723A1 EP 21704440 A EP21704440 A EP 21704440A EP 4090723 A1 EP4090723 A1 EP 4090723A1
Authority
EP
European Patent Office
Prior art keywords
weight
lithium complex
hydrogenated
bearings
group
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
EP21704440.3A
Other languages
German (de)
French (fr)
Other versions
EP4090723B1 (en
Inventor
Stefan Grundei
Daniel CHALL
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 EP4090723A1 publication Critical patent/EP4090723A1/en
Application granted granted Critical
Publication of EP4090723B1 publication Critical patent/EP4090723B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02—Mixtures of base-materials and thickeners
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18—Ethers, e.g. epoxides
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • 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
    • C10M117/06—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having more than one carboxyl group bound to an acyclic carbon atom or cycloaliphatic carbon atom
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    • 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
    • C10M2205/026—Butene
    • C10M2205/0265—Butene 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
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C10M2205/063—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes 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
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates 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
    • C10M2207/10—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
    • C10M2207/1256—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 used as thickening agent
    • 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
    • C10M2207/127—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
    • C10M2207/1276—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 used as thickening agent
    • 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
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • C10M2207/2855—Esters of aromatic polycarboxylic acids 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
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C10M2207/2865—Esters of polymerised unsaturated acids 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/0606—Perfluoro polymers 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • C10M2213/0623—Polytetrafluoroethylene [PTFE] used as base material
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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 present invention relates to the provision of a new lithium complex hybrid grease on the basis of a lithium complex grease in combination with a PFPE grease, which can be used at high temperature, is not laked and has a low tendency to harden.
  • the invention also relates to the use of the new lithium complex hybrid greases in components in the vehicle sector.
  • Hybrid fats are mixtures that consist of at least two base oils that cannot be mixed with one another.
  • Hybrid fats which contain urea or urea / PTFE mixtures as thickeners and ester / PFPE as immiscible base oil components, represent an important group of these fats fluorine-free fats can be reached up to 270 ° C, which is possible with pure PTPE / PFPE fats.
  • These products can also be adapted to specific requirements more easily than is possible with pure PFPE / PTFE greases.
  • Only very few soluble additives are known for PFPE oils, so that, for example, the corrosion protection properties of PFPE oils can only be improved to a limited extent.
  • PFPE / PTFE greases solid substances such as sodium nitrite or magnesium oxide are therefore used as corrosion protection.
  • the even distribution of a solid on the surface of a component is much more difficult to guarantee than the wetting of the surface of a component with an oil that contains a dissolved corrosion protection additive. Therefore, the additives contained in the non-fluorine-containing liquid phase of a hybrid grease can have properties such as Achieve corrosion protection better than is possible with a pure PFPE / PTFE grease.
  • the reduction in the content of PFPE oils in the hybrid fat and the lower density of the hybrid fat also result in significant cost advantages.
  • ester / PFPE / PTFE / urea fats which are described for example in EP0902828 IB1 or the ester / PTFE / urea fats, as described for example in US Pat. No. 6,063,743, have the disadvantage that these fats are used at high temperatures Tend to post-harden and have very little oil separation. In addition, they can sometimes be critical when used with certain elastomers, so that they cannot be used in a wide range, such as roller bearings, in corrugated cardboard plants. In addition, the fluorinated fats are very expensive, so that there is also a need for hybrid fats that can be produced inexpensively with the same or even better properties than the fluorinated fats.
  • Lithium complex greases have a higher oil separation and a lower tendency to harden at high temperatures compared to ester / urea greases.
  • the upper service temperature is significantly lower than with urea hybrid greases, which is often associated with excessive oil separation or is due to the use of base oils such as poly-alpha-olefins or mineral oils, which are less thermally stable.
  • One object of the present invention was therefore to provide a lithium complex hybrid grease with which the aforementioned disadvantages are overcome and which has correspondingly sufficient oil separation and low hardening even at high temperatures.
  • this object could be achieved in that lithium complex greases containing polyisobutylene and esters are combined with PFPE oils or PFPE greases, in particular PFPE / PTFE greases, and thus a high temperature performance can be achieved that is linked to the esters / urea / P FPE hybrid fats, but does not have their disadvantages.
  • the oil separation can be done by selecting the proportions of the two fats be set so that the oil separation is lower than with the two greases used for the mixture.
  • a method for lubricating or greasing components in particular in roller bearings, slide bearings, transport and control chains in vehicle technology, is provided that includes the application of the lubricant composition according to the invention.
  • a method for lubricating or greasing roller bearings in continuous casting plants, transport roller bearings in continuous ovens, open toothed rings in rotary kilns, tube mills, drums and mixers, bearings in corrugated cardboard plants or film stretching plants, bearings for plants for the production and transport of food is provided that the Comprises applying the lubricant composition according to the invention.
  • the lubricant composition according to the invention comprises
  • esters which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
  • a preferred lubricant composition according to the invention comprises
  • esters which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
  • a particularly preferred lubricant composition according to the invention comprises
  • esters which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
  • a particularly preferred lubricant composition according to the invention comprises
  • esters which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
  • Another preferred lubricant composition according to the invention comprises
  • esters which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
  • the lubricants according to the invention can contain additives and (H) solid lubricants as further components (G).
  • Component (A) is contained in the lubricant composition according to the invention in an amount of 70 to 7% by weight, preferably 60 to 15% by weight.
  • Component (A) is an ester or a mixture of esters, the ester being selected from the group consisting of trimellitic acid esters which, as alkoxy groups, have linear or branched alkyl groups containing 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the Alkoxy groups can be identical or different, pyromellitic acid esters, preferably tetrakis (2-ethylhexyl) pyromellitate, hydrogenated or unhydrogenated dimer acid esters, preferably bis (2-ethylhexyl) dimerate, estolides.
  • trimellitic acid esters which, as alkoxy groups, have linear or branched alkyl groups containing 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the Alkoxy groups can be identical or different, pyromellitic acid esters, preferably tetrakis (2-ethylhexyl) pyromellitate, hydrogenated or unhydrogenated dimer
  • Estolides are understood as meaning esters which contain oligomeric units built up from homopolymers of hydroxycarboxylic acids, for example of 12-hydroxystearic acid, or unsaturated carboxylic acids, for example such as oleic acid. Suitable estolides are described, for example, in US 6,018,063, US 6,316,649, WO 2018/177588 A1 and US 2013/0261325 A1.
  • Component (B) is a polyisobutylene or polybutene and is present in the composition according to the invention in an amount of from 0.5 to 20% by weight, preferably from 1.5 to 15% by weight.
  • Component (B) is a polymer, as described, for example, in Synthetics, Mineral Oils And Bio Based Lubricants Chemistry And Technology, Second Edition, Editor Leslie R. Rudnik, authors M. Casserino, J. Corthouts, CRC Press 2013, Pages 273-300, (ISBN 978-1-4398-5537-9).
  • the properties of the fat according to the invention can be in be influenced in a desired manner.
  • the polyisobutylene can be used in non-hydrogenated, hydrogenated or fully hydrogenated form, and a mixture of non-hydrogenated, hydrogenated and fully hydrogenated polyisobutylene can also be used.
  • Fully hydrogenated polyisobutylenes are preferably used.
  • the non-hydrogenated polyisobutylenes contain an unsaturated end group due to the manufacturing process.
  • Hydrogenated or partially hydrogenated polyisobutylenes are understood as meaning those polymers whose bromine number is lower by at least 20% compared to unhydrogenated polyisobutylene of the same number-average molecular mass.
  • the bromine number for a non-hydrogenated polyisobutylene with Mn of 1300 g / mol is 14 g of bromine per 100 g of polyisobutylene.
  • the bromine number in fully hydrogenated polyisobutylenes is below 7 g of bromine per 100 g of polyisobutylene.
  • the bromine number is determined according to ASTM D2170-09 (reaproved 2018).
  • the polyisobutylene has a number average molecular weight from 115 to 10,000 g / mol, preferably from 500 to 5000 g / mol.
  • the number average molecular weight is determined according to ISO 16014-1, edition 2019-05 using gel permeation chromatography.
  • Component (C) is contained in the lubricant composition according to the invention in an amount of 1 to 18% by weight, preferably 4 to 14% by weight.
  • Component (C) is a lithium complex soap.
  • Lithium complex soaps are mixtures of lithium salts of monofunctional carboxylic acids, preferably carboxylic acids containing 8 to 22 carbon atoms, particularly preferably carboxylic acids containing 14 to 20 carbon atoms, particularly preferably 12-hydroxystearic acid and / or stearic acid with the lithium salts of higher functional carboxylic acids, preferably dicarboxylic acids with 6 to 14 carbon atoms, particularly preferably azelaic acid, sebacic acid and dodecanedioic acid.
  • Lithium complex soaps can additionally contain short-chain carboxylic acids such as acetic acid and lactic acid and / or phosphonic acids and / or boric acid as a further acid component.
  • Component (D) is a perfluoropolyether (PFPE) according to formula (I):
  • PFPE oils are sold, for example, under the brand name Aflunox ® , Krytox ® , Fomblin ® and Demnum ® .
  • the PFPE oils are contained in the lubricant composition according to the invention in amounts of 5 to 70% by weight, preferably 15 to 50% by weight.
  • the lithium complex hybrid grease according to the invention can in addition to
  • Lithium complex thickeners comprise further thickeners (E).
  • the further thickening agents (E) are contained in the lubricant composition according to the invention in amounts of 1 to 30% by weight, preferably 3 to 20% by weight.
  • the further thickening agents (E) in the hybrid grease according to the invention are selected from the group consisting of Al complex soaps, single metal soaps of the elements of the first and second main groups of the periodic table without lithium, metal complex soaps of the elements of the first and second main groups of the periodic table without lithium , Bentonites, sulfonates, silicates, Aerosil, polyimides or PTFE or a mixture of the aforementioned thickeners.
  • a particularly preferred further thickening agent is PTFE.
  • the preferred PTFE is called Micropowder used, which is produced thermally or by irradiating high molecular weight PTFE with a reduction in molecular weight.
  • the hybrid greases according to the invention can contain further oils (F) which are contained in the lubricant composition according to the invention in amounts of 0 to 20% by weight, preferably 2 to 20% by weight.
  • Component (F) is selected from the group consisting of mineral oil, alkylated benzenes, alkylated naphthalenes, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, alkylated diphenyl ethers, phloroglucinic esters, estolides and / or poly-alpha-olefins, alpha-olefin copolymers, metallocene catalyzed polyalfa-olefins.
  • Preferred further oils are alkylated diphenyl ether oils.
  • Alkylated Diphenyletheröle be marketed under the brand name Hilube ® by the company. Moresco.
  • the alkyl groups contain between 10 and 20 carbon atoms. On average, between one and three alkyl groups are bound to the basic diphenyl ether unit.
  • the lubricant composition according to the invention further comprises from 0 to 10% by weight, preferably from 0.1 to 10% by weight, of additives (G), which are used individually or in combination.
  • Component (G) is selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers. It is possible to use both additives that are soluble in component (A) and additives that are soluble in the PFPE oils of component (D) or also insoluble in both oil phases.
  • antioxidants examples include styrenated diphenylamines, diaromatic amines, phenolic resins, thiophenolic resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, octylated / butylated diphenylamine, di-alpha-tocopherol, di-tert-butyl-phenol or di-tert-butyl-4-methylphenol, benzene propanoic acid, sulfur-containing phenolic compounds, phenolic compounds and mixtures of these components.
  • suitable anti-corrosion additives metal deactivators or ion complexing agents.
  • These include triazoles, imidazolines, N-methylglycine (sarcosine), benzotriazole derivatives, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; n-Methyl-N (1-oxo-9-octadecenyl) glycine, mixture of phosphoric acid and mono- and diisooctyl esters reacted with (Cn-14) -alkylamines, mixture of phosphoric acid and mono- and diisooctyl esters reacted with tert-alkylamine and primary (Ci2-14) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates.
  • IRGAMET ® 39 IRGACOR ® DSS G, Amin O; Sarkosyl O ® (Ciba), COBRATEC ® 122, CUVAN ® 303, VANLUBE ® 9123, CI-426, CI-426EP, CI-429 and CI-498th
  • anti-wear additives are amines, amine phosphates, phosphates, thiophosphates and mixtures of these components. Most of the compounds mentioned have organic groups.
  • the commercially available anti-wear additives include IRGALUBE ® TPPT, IRGALUBE ® 232, IRGALUBE ® 349, IRGALUBE ® 211 and ADDITIN ® RC3760 Liq 3960, FIRC-SHUN ® FG 1505 and FG 1506, NA-LUBE ® KR-015FG, LUBEBOND ® , FLUORO ® ® FG, SYNALOX ® 40-D, ACHESON ® FGA 1820 and ACHESON ® FGA 1810.
  • PFPE derivatives can also be included as additives.
  • Further suitable substances are described, for example, in WO01 / 72759A1, WO 01 / 27916A1, EP1070074B1, EP1659165B1 and US2015011446A1.
  • the lubricant compositions according to the invention can contain solid lubricants (H) which are selected from the group consisting of BN, pyrophosphate, Zn oxide, Mg oxide, pyrophosphates, thiosulfates, Mg carbonate, Ca carbonate, Ca stearate, Zn sulfide, Mo sulfide, W sulfide, Sn sulfide, graphite, graphene, nanotubes, Si02 modifications or a mixture thereof.
  • the solid lubricants (H) are contained in the lubricant composition according to the invention in amounts of 0 to 10% by weight, preferably 2 to 5% by weight.
  • the lubricant composition according to the invention is used in the field of components, in particular in roller bearings, slide bearings, transport and timing chains in vehicle technology, rail vehicles, conveyor technology, film stretching systems, corrugated cardboard systems, roller bearings, fan bearings, bearings for traction motors, for the lubrication of bevel and bevel gears Helical gears, springs, screws and compressors, pneumatic components, fittings, and from machine components and in systems where there is occasional, unintentional contact with food.
  • Fig. 1 shows the worked penetration 60dT
  • Figure 2 shows the oil separation, i.e. the loss of oil from the grease.
  • the production of the lubricant composition according to the invention is not restricted and can be carried out by any suitable method.
  • the production of the lubricant production according to the invention can for example be carried out in such a way that a base oil mixture is produced with components (A) and / or (B) and / or (F).
  • the acids required for the lithium complex thickener (C) and an aqueous lithium hydroxide solution are melted in this base oil mixture, which is completely or only partially placed in a suitable reaction vessel containing heating, cooling and stirring equipment admitted.
  • the acids can be added individually and neutralized, or the monocarboxylic acid is first added and neutralized and, in a second step, the higher-functionality carboxylic acid is added and neutralized.
  • the brew is heated to 130 ° C to drive off water.
  • the swelling of the thickener is carried out by thermal treatment at 150 ° C to 210 ° C.
  • the thermally treated brew is then cooled, whereby part of the base oil mixture can also be used.
  • the components (D), (E), (G), (H) and possibly not used for the base oil mixture (A), (B) and (F) are added at a suitable temperature and prehomogenized by stirring.
  • Solid lubricant additives that are soluble in the base oil mixture are added, for example, at temperatures above their melting point.
  • Liquid additives or non-melting additives / solid lubricants / thickener components are added at temperatures below 80 ° C.
  • the lithium complex hybrid grease produced in this way can be homogenized using suitable equipment such as three-roll mills, colloid mills or Gaulin.
  • the lubricant composition according to the invention is produced in one process.
  • the addition of the PFPE oil (D) and the optional thickener component (E) in the process described above can be omitted, so that a lithium complex grease is produced.
  • Components (D) and (E) can be combined to a PFPE fat by stirring and homogenizing as described above.
  • Lithium complex grease and PFPE grease can be combined in a second process step and the lubricant composition according to the invention can be produced therefrom with stirring and homogenization.
  • Production can also be carried out using continuous processes, in which case Li-complex ready-made soap in powder form can also be used.
  • Lithium complex soap grease (fat A) and a PFPE / PTFE grease (fat B) are produced separately and the two fats A and B are mixed in different proportions, stirred and homogenized by rolling.
  • a lithium complex grease consisting of 77% of a mixture of an alkyl diphenyl ether (100 mm7sec / 40 ° C) and trimellitic acid ester as well as fully hydrogenated polyisobutylene (fully hydrogenated, Mn approx. 1300 g / mol) is used as the base oil, with a viscosity of 220 mm at 40 ° C 2 / sec results, then 15% lithium complex of azelaic acid and 12-hydroxystearic acid and 8% of an additive package consisting of amine antioxidants, phosphates, thiadiazoles, triazoles and amine phosphates are added.
  • the worked penetration is 270 1/10 mm (see table 1)
  • a PFPE / PTFE grease is used, containing 70% a mixture of linear and branched PFPE, kinematic viscosity 200 mm 2 / sec at 40 ° C, 26% PTFE micropowder, average particle size d 50 (laser diffraction, DIN ISO 9277) approx. 5 ⁇ m, specific surface (DIN ISO 9277) approx. 5 m 2 / g, and 4% disodium sebacate produced as an anti-corrosion additive.
  • the worked penetration is 286 1/10 mm (see table 1)
  • Example 2 (B2) Mixture of fat A and fat B in a ratio of 30% by weight to 70% by weight.
  • a urea hybrid fat consisting of 50% by weight of fat B and 50% by weight of a urea fat is produced.
  • the urea fat consists of a mixture of a trimellitic acid ester and a reaction product of octylamine and oleylamine with an MDI / TDI mixture as a urea thickener, as well as additives.
  • the base oil viscosity is approx. 80 mm 2 / sec.
  • the worked penetration is 265 mnrVsec (see Table 2)
  • a urea hybrid fat consisting of a complex ester, based on dimer acid, V 40 apr. 400 mm'Vsec at 40 ° C and branched PFPE oil with a kinematic viscosity of approx. 400 mm 2 / sec in a mass ratio of 2: 1.
  • the urea thickener is 10% contained and is a reaction product of octylamine and oleylamine with an MDI / TDI mixture. In addition, it contains 8% by weight of PTFE powder (as for fat B) and 5% by weight of soluble additives (antioxidants, amine phosphates). The worked penetration is 290 mm 2 / sec (see Table 2)
  • Table 1 shows the general characteristics of the lithium complex hybrid greases according to the invention of Examples B1 to B5 and the greases A and B, Table 1
  • Table 2 shows the data of comparative examples VG1 to 2.
  • the compositions according to the invention show a lower oil separation than the fats A and B from which they were produced.
  • This behavior shows the unexpected synergistic effect caused by the composition according to the invention.
  • the oil separation almost achieves the low values of the two comparison products VG1 and VG2.
  • the reduction in oil separation in comparison to grease B shows the advantage over pure PFPE / PTFE greases.
  • the lubricant compositions according to the invention were checked for their thermal stability and the results were compared primarily with those of the urea hybrid greases. For this purpose, investigations were carried out with regard to evaporation and viscosity under a temperature load of 5 g of fat weighed in in a stainless steel bowl at 200 ° C. The results are shown in Tables 3 and 4.
  • the evaporation loss is determined according to DIN standard 58397. Three stainless steel evaporation loss trays are required for each fat sample. The geometry of the bowls is described in the standard for determining the evaporation loss (DIN 58397). At the beginning, the respective empty weight of the bowls is determined. The three evaporation loss trays are then filled with the fat sample. It is important to ensure that the grease is applied without air bubbles. The surface is smoothed with a scraper and excess fat that has got into the recess on the edge of the bowl is removed. The dishes are then stored in a standard laboratory drying cabinet with convection with the flap closed at the appropriate test temperature (here 200 ° C).
  • the shear viscosity is determined according to DIN standard 53019 part 1 and part 3.
  • the fat samples are transferred to three stainless steel evaporation-loss trays.
  • the geometry of the bowls is described in the standard for determining the evaporation loss (DIN 58397).
  • the dishes are then stored in a standard laboratory drying cabinet with circulation at the appropriate test temperature (here 200 ° C). After the specified period of time (48h, 96h, 144h and 168h), the trays are removed from the drying cabinet and allowed to cool.
  • the starting value for the shear viscosity is determined for each grease before the thermal load.
  • the shear viscosity is measured with a device that is used as standard to determine theological parameters of lubricants (e.g. rheometer MCR 302 from Anton Paar).
  • a cone-plate system (DIN EN ISO 3219 and DIN 53019) is used, preferably with a measuring cone with a diameter of 25 mm.
  • the required amount of fat sample is based on typical amounts that are required for theological measurements.
  • the measurement duration is 120 s, of which 60 s are tempering or holding times. Measurements are made at a constant shear rate of 300 1 / s and a temperature of 25 ° C.
  • the value that can be read off after 90 s represents the shear viscosity for the respective fat sample.
  • the mean value is calculated from the three individual values determined and then given.
  • VG2 shows a shear viscosity of 100,000 mPas after just 96 hours and is no longer lubricious.
  • VG1 shows twice as high a shear viscosity than all compositions B1 to B5 according to the invention, see Table 4.
  • the PFPE / PTFE grease shows the lowest evaporation losses in the test.
  • the shear viscosity of Examples B1, B2 and B4 according to the invention after a test time of 168 hours is lower than that of fat B and thus shows more favorable hardening behavior.
  • the hardening behavior of the lubricants according to the invention is more favorable at high temperatures than in the case of urea hybrid greases. Surprisingly, it was even found that with some of the compositions according to the invention even less hardening occurs than with a PFPE / PTFE grease. Surprisingly, it was also found that the oil separation behavior of the lubricants according to the invention can be set and thus adapted to different requirements by selecting certain mixing ratios of greases A (lithium complex grease) and B (PTFE / PFPE grease).
  • a lubricant according to the invention can be produced in various ways.
  • a lithium complex grease (fat C) and a PFPE / PTFE grease (fat D) are produced separately and then mixed in a kettle at a ratio of 40 to 60% by weight while stirring.
  • the resulting lithium complex hybrid grease B6 is then homogenized using a three-roll mill.
  • the lithium complex grease is produced identically to fat C, but when it cools down, the components of fat D are added, so that the lubricant composition according to the invention is produced in one operation.
  • the lubricant composition B6 according to the invention is also finally rolled.
  • a lithium complex grease consisting of 80% by weight of a mixture of an alkyl diphenyl ether (100 mnfVsec at 40 ° C) and a trimellitic acid ester as well as fully hydrogenated polyisobutylene (fully hydrogenated, Mn approx. 1300 g / mol) is produced as the base oil, with a viscosity at 40 ° C of 100 mm 2 / sec results.
  • 15% by weight of a lithium complex of azelaic acid and 12-hydroxystearic acid and 5% by weight of an additive package consisting of amine antioxidants and phosphates are provided. The fulled penetration is 327 1/10 mm.
  • the fulled penetration is 286 1/10 mm
  • B6 can be used as a lubricant according to production example 1 and production example 2 with both production variants.

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Abstract

The invention relates to a novel lithium complex hybrid grease based on a lithium complex grease in combination with a PFPE grease. The novel lithium complex hybrid grease can be used at higher temperatures, does not form layers in the process, and exhibits a low hardening tendency. The invention additionally relates to the use of the novel lithium complex hybrid grease in components in the automotive field and in the industrial field.

Description

Lithiumkomplexhybridfett Lithium complex hybrid grease
Beschreibung description
Die vorliegende Erfindung betrifft die Bereitstellung eines neuen Lithiumkomplexhybridfettes auf der Basis eines Lithiumkomplexfettes in Kombination mit einem PFPE-Fett, das bei hoher Temperatur eingesetzt werden kann, dabei nicht verlackt, und eine geringe Verhärtungstendenz zeigt. Des Weiteren betrifft die Erfindung die Verwendung der neuen Lithiumkomplexhybridfette in Bauteilen im Fahrzeugbereich. The present invention relates to the provision of a new lithium complex hybrid grease on the basis of a lithium complex grease in combination with a PFPE grease, which can be used at high temperature, is not laked and has a low tendency to harden. The invention also relates to the use of the new lithium complex hybrid greases in components in the vehicle sector.
Hybridfette sind Mischungen, die mindestens aus zwei Basisölen bestehen, die nicht miteinander mischbar sind. So stellen Hybridfette, die als Verdicker Harnstoff oder Harnstoff/PTFE-Gemische und Ester/PFPE als nicht mischbare Grundölkomponenten enthalten, eine wichtige Gruppe dieser Fette dar. Mit diesen Fetten ist es möglich, eine Temperaturlücke zwischen ca. 180°C, wie sie bei fluorfreien Fetten erreicht werden, bis zu 270°C, die mit reinen PTPE/PFPE-Fetten möglich sind, zu schließen. Auch können diese Produkte an bestimmte Anforderungen leichter angepasst werden, als dies mit reinen PFPE/PTFE-Fetten möglich ist. Für PFPE Öle sind nämlich nur sehr wenige lösliche Additive bekannt, sodass beispielsweise die Korrosionsschutzeigenschaften von PFPE Ölen nur bedingt verbessert werden können. Bei PFPE/PTFE Fetten werden daher feste Stoffe wie Natriumnitrit oder Magnesiumoxid als Korrosionsschutz eingesetzt. Die gleichmäßige Verteilung eines Feststoffes auf der Oberfläche eines Bauteiles ist aber viel schwieriger zu gewährleisten als die Benetzung der Oberfläche eines Bauteiles mit einem Öl, das ein gelöstes Korrosionsschutzadditiv enthält. Daher können die in der nicht fluorhaltigen flüssigen Phase enthaltenen Additive eines Hybridfettes Eigenschaften wie Korrosionsschutz besser bewerkstelligen als es bei einem reinen PFPE/PTFE Fett möglich ist. Durch die Reduktion des Gehaltes an PFPE Ölen im Hybridfett und die geringere Dichte des Hybridfettes ergeben sich zudem signifikante Kostenvorteile. Die Ester/PFPE/PTFE/Harnstoff-Fette, die beispielsweise in der EP0902828 IB1 beschrieben sind oder die Ester/PTFE/Harnstoff-Fette, wie sie beispielsweise in der US 6,063,743 beschrieben sind, haben den Nachteil, dass diese Fette bei hohen Temperaturen zur Nachhärtung neigen und sehr geringe Ölabscheidungen haben. Darüber hinaus können sie teilweise kritisch beim Einsatz mit bestimmten Elastomeren sein, so dass sie nicht in einem weiten Spektrum, wie z.B. Rollenlagern, in Wellpappenanlagen eingesetzt werden können. Darüber hinaus sind die fluorierten Fette sehr teuer, so dass auch ein Bedarf an Hybridfetten besteht, die kostengünstig mit den gleichen oder noch besseren Eigenschaften als die fluorierten Fette hergestellt werden können. Hybrid fats are mixtures that consist of at least two base oils that cannot be mixed with one another. Hybrid fats, which contain urea or urea / PTFE mixtures as thickeners and ester / PFPE as immiscible base oil components, represent an important group of these fats fluorine-free fats can be reached up to 270 ° C, which is possible with pure PTPE / PFPE fats. These products can also be adapted to specific requirements more easily than is possible with pure PFPE / PTFE greases. Only very few soluble additives are known for PFPE oils, so that, for example, the corrosion protection properties of PFPE oils can only be improved to a limited extent. In the case of PFPE / PTFE greases, solid substances such as sodium nitrite or magnesium oxide are therefore used as corrosion protection. The even distribution of a solid on the surface of a component is much more difficult to guarantee than the wetting of the surface of a component with an oil that contains a dissolved corrosion protection additive. Therefore, the additives contained in the non-fluorine-containing liquid phase of a hybrid grease can have properties such as Achieve corrosion protection better than is possible with a pure PFPE / PTFE grease. The reduction in the content of PFPE oils in the hybrid fat and the lower density of the hybrid fat also result in significant cost advantages. The ester / PFPE / PTFE / urea fats, which are described for example in EP0902828 IB1 or the ester / PTFE / urea fats, as described for example in US Pat. No. 6,063,743, have the disadvantage that these fats are used at high temperatures Tend to post-harden and have very little oil separation. In addition, they can sometimes be critical when used with certain elastomers, so that they cannot be used in a wide range, such as roller bearings, in corrugated cardboard plants. In addition, the fluorinated fats are very expensive, so that there is also a need for hybrid fats that can be produced inexpensively with the same or even better properties than the fluorinated fats.
Lithiumkomplexfette weisen eine höhere Ölabscheidung und eine geringere Verhärtungstendenz bei hohen Temperaturen verglichen mit Ester/Harnstoff-Fetten auf. Allerdings ist die obere Gebrauchstemperatur deutlich niedriger als bei Harnstoffhybridfetten, was oft mit einer zu hohen Ölabscheidung in Zusammenhang gebracht wird oder aber auf die Verwendung von Grundölen wie Poly-alpha-olefinen oder Mineralölen, die thermisch weniger beständig sind, zurückzuführen ist. Lithium complex greases have a higher oil separation and a lower tendency to harden at high temperatures compared to ester / urea greases. However, the upper service temperature is significantly lower than with urea hybrid greases, which is often associated with excessive oil separation or is due to the use of base oils such as poly-alpha-olefins or mineral oils, which are less thermally stable.
Eine Aufgabe der vorliegenden Erfindung bestand daher darin, ein Lithiumkomplexhybridfett bereitzustellen, mit dem die vorstehend genannten Nachteile überwunden werden und das eine entsprechend ausreichende Ölabscheidung und eine geringe Verhärtung selbst bei hohen Temperaturen aufweist. One object of the present invention was therefore to provide a lithium complex hybrid grease with which the aforementioned disadvantages are overcome and which has correspondingly sufficient oil separation and low hardening even at high temperatures.
Diese Aufgabe konnte überraschenderweise dadurch gelöst werden, dass Lithiumkomplexfette, die Polyisobutylen und Ester enthalten mit PFPE-Ölen oder PFPE-Fetten, insbesondere PFPE/PTFE-Fetten kombiniert werden und so eine Hochtemperaturperformance erreicht werden kann, die an die Este r/Harn stoff/P FPE- Hybridfette heranreicht, aber nicht deren Nachteile aufweist. Überraschenderweise kann die Ölabscheidung durch Auswahl der Mengenanteile der beiden Fette so eingestellt werden, dass die Ölabscheidung niedriger als bei den beiden zur Mischung verwendeten Fetten liegt. Surprisingly, this object could be achieved in that lithium complex greases containing polyisobutylene and esters are combined with PFPE oils or PFPE greases, in particular PFPE / PTFE greases, and thus a high temperature performance can be achieved that is linked to the esters / urea / P FPE hybrid fats, but does not have their disadvantages. Surprisingly, the oil separation can be done by selecting the proportions of the two fats be set so that the oil separation is lower than with the two greases used for the mixture.
Des Weiteren wird ein Verfahren zur Schmierung oder zum Fetten von Bauteilen, insbesondere in Wälzlagern, Gleitlagern, Transport- und Steuerketten in der Fahrzeugtechnik bereitgestellt, dass das Aufträgen der erfindungsgemäßen Schmiermittelzusammensetzung umfasst. Furthermore, a method for lubricating or greasing components, in particular in roller bearings, slide bearings, transport and control chains in vehicle technology, is provided that includes the application of the lubricant composition according to the invention.
Außerdem wird ein Verfahren zur Schmierung oder zum Fetten von Laufrollenlagern in Stranggießanlagen, Transportrollenlagern in Durchlauföfen, von offenen Zahnkränzen in Drehrohröfen, Rohrmühlen, Trommeln und Mischern, von Lagern in Wellpappanlagen oder Folienreckanlagen, Lagern zur Anlagen zur Herstellung und Transport von Lebensmitteln bereitgestellt, dass das Aufträgen der erfindungsgemäßen Schmiermittelzusammensetzung umfasst. In addition, a method for lubricating or greasing roller bearings in continuous casting plants, transport roller bearings in continuous ovens, open toothed rings in rotary kilns, tube mills, drums and mixers, bearings in corrugated cardboard plants or film stretching plants, bearings for plants for the production and transport of food is provided that the Comprises applying the lubricant composition according to the invention.
Die erfindungsgemäße Schmierstoffzusammensetzung umfasst The lubricant composition according to the invention comprises
(A) einen Ester oder Mischung von Estern, die insbesondere ausgewählt werden aus der Gruppe bestehend aus Trimellithsäureestern, Pyromellithsäureestern, Dimersäureestern, Estoliden, (A) an ester or mixture of esters, which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
(B) Polyisobutylenen, (B) polyisobutylenes,
(C) Lithiumkomplexseifen und (C) lithium complex soaps and
(D) PFPE-Öle. (D) PFPE oils.
Eine bevorzugte erfindungsgemäße Schmierstoffzusammensetzung umfasst A preferred lubricant composition according to the invention comprises
(A) einen Ester oder Mischung von Estern, die insbesondere ausgewählt werden aus der Gruppe bestehend aus Trimellithsäureestern, Pyromellithsäureestern, Dimersäureestern, Estoliden, (A) an ester or mixture of esters, which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
(B) Polyisobutylenen, (B) polyisobutylenes,
(C) Lithiumkomplexseifen, (C) lithium complex soaps,
(D) PFPE-Öle und (D) PFPE oils and
(E) ein weiteres Verdickungsmittel. Eine besonders bevorzugte erfindungsgemäße Schmierstoffzusammensetzung umfasst (E) another thickener. A particularly preferred lubricant composition according to the invention comprises
(A) einen Ester oder Mischung von Estern, die insbesondere ausgewählt werden aus der Gruppe bestehend aus Trimellithsäureestern, Pyromellithsäureestern, Dimersäureestern, Estoliden, (A) an ester or mixture of esters, which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
(B) Polyisobutylenen, (B) polyisobutylenes,
(C) Lithiumkomplexseifen, (C) lithium complex soaps,
(D) PFPE-Öle und (D) PFPE oils and
(E) PTFE als weiteres Verdickungsmittel. (E) PTFE as a further thickening agent.
Eine insbesonders bevorzugte erfindungsgemäße Schmierstoffzusammensetzung umfasst A particularly preferred lubricant composition according to the invention comprises
(A) einen Ester oder Mischung von Estern, die insbesondere ausgewählt werden aus der Gruppe bestehend aus Trimellithsäureestern, Pyromellithsäureestern, Dimersäureestern, Estoliden, (A) an ester or mixture of esters, which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
(B) Polyisobutylenen, (B) polyisobutylenes,
(C) Lithiumkomplexseifen, (C) lithium complex soaps,
(D) PFPE-Öle und (D) PFPE oils and
(F) ein weiteres Grundöl, wobei akylierte Diphenylether bevorzugt sind. (F) Another base oil, with alkylated diphenyl ethers being preferred.
Eine weitere bevorzugte erfindungsgemäße Schmierstoffzusammensetzung umfasstAnother preferred lubricant composition according to the invention comprises
(A) einen Ester oder Mischung von Estern, die insbesondere ausgewählt werden aus der Gruppe bestehend aus Trimellithsäureestern, Pyromellithsäureestern, Dimersäureestern, Estoliden, (A) an ester or mixture of esters, which are selected in particular from the group consisting of trimellitic acid esters, pyromellitic acid esters, dimer acid esters, estolides,
(B) Polyisobutylenen, (B) polyisobutylenes,
(C) Lithiumkomplexseifen, (C) lithium complex soaps,
(D) PFPE-Öle, (D) PFPE oils,
(E) ein weiteres Verdickungsmittel und (E) another thickener and
(F) alkylierte Diphenylether. (F) alkylated diphenyl ethers.
Die erfindungsgemäßen Schmierstoffe können als weitere Komponente (G) Additive und (H) Festschmierstoffe enthalten. Komponente (A) The lubricants according to the invention can contain additives and (H) solid lubricants as further components (G). Component (A)
Die Komponente (A) ist in einer Menge von 70 bis 7 Gew.-%, bevorzugt 60 bis 15 Gew.-% in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten. Component (A) is contained in the lubricant composition according to the invention in an amount of 70 to 7% by weight, preferably 60 to 15% by weight.
Die Komponente (A) ist ein Ester oder ein Gemisch von Estern, wobei der Ester ausgewählt wird aus der Gruppe bestehend aus Trimellithsäureestern, die als Alkoxygruppen lineare oder verzweigte Alkylgruppen aufweisen, die 6 bis 18 Kohlenstoffatome enthalten, bevorzugt 8 bis 14 Kohlenstoffatome, wobei die Alkoxygruppen gleich oder verschieden sein können, Pyromellithsäureestern, bevorzugt Tetrakis(2-ethylhexyl)pyromellitat, hydrierte oder unhydrierte Dimersäureester, bevorzugt Bis(2-ethylhexyl)dimerat, Estolide. Component (A) is an ester or a mixture of esters, the ester being selected from the group consisting of trimellitic acid esters which, as alkoxy groups, have linear or branched alkyl groups containing 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the Alkoxy groups can be identical or different, pyromellitic acid esters, preferably tetrakis (2-ethylhexyl) pyromellitate, hydrogenated or unhydrogenated dimer acid esters, preferably bis (2-ethylhexyl) dimerate, estolides.
Unter Estoliden versteht man Ester, die oligomere Einheiten aufgebaut aus Homopolymeren von Hydroxycarbonsäuren, beispielsweise von 12- Hydroxystearinsäure oder ungesättigten Carbonsäuren, beispielsweise wie Ölsäure enthalten. Geeignete Estolide sind beispielsweise in der US 6,018,063, US 6,316,649, WO 2018/177588 A1 und der US 2013/0261325 A1 beschrieben. Estolides are understood as meaning esters which contain oligomeric units built up from homopolymers of hydroxycarboxylic acids, for example of 12-hydroxystearic acid, or unsaturated carboxylic acids, for example such as oleic acid. Suitable estolides are described, for example, in US 6,018,063, US 6,316,649, WO 2018/177588 A1 and US 2013/0261325 A1.
Komponente (B) Component (B)
Die Komponente (B) ist ein Polyisobutylen oder Polybuten und in einer Menge von 0,5 bis 20 Gew.-% in der erfindungsgemäßen Zusammensetzung vorhanden, bevorzugt werden 1 ,5 bis 15 Gew.-% eingesetzt. Component (B) is a polyisobutylene or polybutene and is present in the composition according to the invention in an amount of from 0.5 to 20% by weight, preferably from 1.5 to 15% by weight.
Bei Komponente (B) handelt es sich um ein Polymer, wie es beispielsweise in Synthetics, Mineral Oils And Bio Based Lubricants Chemistry And Technology, Second Edition, Editor Leslie R. Rudnik, Autoren M. Casserino, J. Corthouts, CRC Press 2013, Pages 273 - 300, (ISBN 978-1-4398-5537-9) beschrieben wird. Component (B) is a polymer, as described, for example, in Synthetics, Mineral Oils And Bio Based Lubricants Chemistry And Technology, Second Edition, Editor Leslie R. Rudnik, authors M. Casserino, J. Corthouts, CRC Press 2013, Pages 273-300, (ISBN 978-1-4398-5537-9).
Durch geeignete Wahl des Polyisobutylens, insbesondere im Hinblick auf Hydrierungsgrad und Molekulargewicht, können die Eigenschaften des erfindungsgemäßen Fetts, beispielsweise deren kinematische Viskosität, in erwünschter Weise beeinflusst werden. Das Polyisobutylen kann in nicht hydrierter, hydrierter oder vollhydrierter Form eingesetzt werden, ebenso kann eine Mischung aus nicht hydriertem, hydriertem und vollhydriertem Polyisobutylen verwendet werden. Bevorzugt werden vollhydrierte Polyisobutylene eingesetzt. Die nicht hydrierten Polyisobutylene enthalten herstellungsbedingt eine ungesättigte Endgruppe. Unter hydrierten bzw. teilhydrierten Polyisobutylenen werden solche Polymere verstanden, deren Bromzahl im Vergleich zum unhydrierten Polyisobutylen gleicher zahlengemittelten Molekularmasse um mindestens 20% geringer ist. So beträgt die Bromzahl für ein nicht hydriertes Polyisobutylen mit Mn von 1300 g/mol 14 g Brom pro 100 g Polyisobutylen. Die Bromzahl bei vollhydrierten Polyisobutylenen liegt unter 7 g Brom pro 100 g Polyisobutylen. Die Bromzahl wird gemäß ASTM D2170-09 (reaproved 2018) bestimmt. By a suitable choice of the polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, the properties of the fat according to the invention, for example its kinematic viscosity, can be in be influenced in a desired manner. The polyisobutylene can be used in non-hydrogenated, hydrogenated or fully hydrogenated form, and a mixture of non-hydrogenated, hydrogenated and fully hydrogenated polyisobutylene can also be used. Fully hydrogenated polyisobutylenes are preferably used. The non-hydrogenated polyisobutylenes contain an unsaturated end group due to the manufacturing process. Hydrogenated or partially hydrogenated polyisobutylenes are understood as meaning those polymers whose bromine number is lower by at least 20% compared to unhydrogenated polyisobutylene of the same number-average molecular mass. The bromine number for a non-hydrogenated polyisobutylene with Mn of 1300 g / mol is 14 g of bromine per 100 g of polyisobutylene. The bromine number in fully hydrogenated polyisobutylenes is below 7 g of bromine per 100 g of polyisobutylene. The bromine number is determined according to ASTM D2170-09 (reaproved 2018).
Gemäß einer weiteren bevorzugten Ausführungsform weist das Polyisobutylen ein zahlenmittleres Molekulargewicht von 115 bis 10000 g/mol, vorzugsweise von 500 bis 5000 g/mol auf. Das Zahlenmittlere Molekulargewicht wird nach ISO 16014-1 , Ausgabe 2019-05 mittels Gelpermeationschromatographie bestimmt. According to a further preferred embodiment, the polyisobutylene has a number average molecular weight from 115 to 10,000 g / mol, preferably from 500 to 5000 g / mol. The number average molecular weight is determined according to ISO 16014-1, edition 2019-05 using gel permeation chromatography.
Komponente (C) Component (C)
Die Komponente (C) ist in einer Menge von 1 bis 18 Gew.-%, bevorzugt 4 bis 14 Gew.- % in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten. Component (C) is contained in the lubricant composition according to the invention in an amount of 1 to 18% by weight, preferably 4 to 14% by weight.
Bei der Komponente (C) handelt es sich um eine Lithiumkomplexseife. Unter Lithiumkomplexseifen versteht man Gemische von Lithiumsalzen aus monofunktionellen Carbonsäuren, bevorzugt Carbonsäuren die 8 bis 22 Kohlenstoffatome enthalten, insbesondere bevorzugt Carbonsäuren die 14 bis 20 Kohlenstoffatome enthalten, insbesondere bevorzugt 12-Hydroxystearinsäure und/oder Stearinsäure mit den Lithiumsalzen höherfunktionellen Carbonsäuren, bevorzugt Dicarbonsäuren mit 6 bis 14 Kohlenstoffatomen, insbesondere bevorzugt Azelainsäure, Sebacinsäure und Dodecandisäure. Lithiumkomplexseifen können zusätzlich kurzkettige Carbonsäuren wie Essigsäure und Milchsäure und/oder Phosphonsäuren und/oder Borsäure als weiter Säurekomponente enthalten. Component (C) is a lithium complex soap. Lithium complex soaps are mixtures of lithium salts of monofunctional carboxylic acids, preferably carboxylic acids containing 8 to 22 carbon atoms, particularly preferably carboxylic acids containing 14 to 20 carbon atoms, particularly preferably 12-hydroxystearic acid and / or stearic acid with the lithium salts of higher functional carboxylic acids, preferably dicarboxylic acids with 6 to 14 carbon atoms, particularly preferably azelaic acid, sebacic acid and dodecanedioic acid. Lithium complex soaps can additionally contain short-chain carboxylic acids such as acetic acid and lactic acid and / or phosphonic acids and / or boric acid as a further acid component.
Komponente (D) Component (D)
Die Komponente (D) ist ein Perfluorpolyether (PFPE) gemäß der Formel (I): Component (D) is a perfluoropolyether (PFPE) according to formula (I):
RI-(0-CF2)V-(0-C2F4)W-(0- CsFeMO- CFCF3)y- (O- CF2CF(CF3)) z -O-R2 (I) wobei Ri und R2 identisch oder verschieden sind und ausgewählt werden aus -CF3, -C2F5, oder -C3F7 , v, w, x, y, z sind ganze Zahlen von > 0 bis 500. PFPE-Öle werden beispielsweise unter dem Markennamen Aflunox®, Krytox®, Fomblin® und Demnum® vertrieben. RI- (0-CF 2 ) V- (0-C 2 F4) W - (0- CsFeMO- CFCF 3 ) y - (O- CF 2 CF (CF 3 )) z -O-R2 (I) where Ri and R2 are identical or different and are selected from -CF 3 , -C2F5, or -C 3 F7, v, w, x, y, z are integers from> 0 to 500. PFPE oils are sold, for example, under the brand name Aflunox ® , Krytox ® , Fomblin ® and Demnum ® .
Die PFPE Öle sind in Mengen von 5 bis 70 Gew.-%, bevorzugt zu 15 bis 50 Gew.-% in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten. The PFPE oils are contained in the lubricant composition according to the invention in amounts of 5 to 70% by weight, preferably 15 to 50% by weight.
Komponente (E) Component (E)
Das erfindungsgemäße Lithiumkomplexhybridfett kann neben demThe lithium complex hybrid grease according to the invention can in addition to
Lithiumkomplexverdicker weitere Verdickungsmittel (E) umfassen. Lithium complex thickeners comprise further thickeners (E).
Die weiteren Verdickungsmittel (E) sind in Mengen von 1 bis 30 Gew.-%, bevorzugt 3 bis 20 Gew.-% in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten. The further thickening agents (E) are contained in the lubricant composition according to the invention in amounts of 1 to 30% by weight, preferably 3 to 20% by weight.
Die weiteren Verdickungsmittel (E) in dem erfindungsgemäßen Hybridfett werden ausgewählt aus der Gruppe bestehend aus Al-Komplexseifen, Metall-Einfachseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems ohne Lithium, Metall-Komplexseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems ohne Lithium, Bentonite, Sulfonate, Silikate, Aerosil, Polyimide oder PTFE oder einer Mischung der vorgenannten Verdickungsmittel. Ein besonders bevorzugtes weiteres Verdickungsmittel ist PTFE. Das bevorzugte PTFE wird als Mikropulver eingesetzt, das thermisch oder durch Bestrahlen von hochmolekularem PTFE unter Abbau des Molekulargewichtes hergestellt wird. The further thickening agents (E) in the hybrid grease according to the invention are selected from the group consisting of Al complex soaps, single metal soaps of the elements of the first and second main groups of the periodic table without lithium, metal complex soaps of the elements of the first and second main groups of the periodic table without lithium , Bentonites, sulfonates, silicates, Aerosil, polyimides or PTFE or a mixture of the aforementioned thickeners. A particularly preferred further thickening agent is PTFE. The preferred PTFE is called Micropowder used, which is produced thermally or by irradiating high molecular weight PTFE with a reduction in molecular weight.
Komponente (F) Component (F)
Die erfindungsgemäßen Hybridfette können weitere Öle (F) enthalten, die in Mengen von 0 bis 20 Gew.-%, bevorzugt zu 2 bis 20 Gew.-% in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten sind. The hybrid greases according to the invention can contain further oils (F) which are contained in the lubricant composition according to the invention in amounts of 0 to 20% by weight, preferably 2 to 20% by weight.
Die Komponente (F) wird ausgewählt aus der Gruppe bestehend aus Mineralöl, alkylierten Benzolen, alkylierte Naphthaline, aliphatischen Carbonsäure- und Dicarbonsäureestern, Fettsäuretriglyceriden, alkylierte Diphenylether, Phloroglucinester, Estolide und/oder Poly-alpha-olefinen, alpha-Olefin-Copolymere, Metallocen katalysierte Poly-alfa-olefine. Bevorzugte weitere Öle sind alkylierte Diphenyletheröle. Alkylierte Diphenyletheröle werden beispielsweise unter dem Markennamen Hilube® von der Fa. Moresco vertrieben. Die Alkylgruppen enthalten zwischen 10 und 20 Kohlenstoffatome. Im Mittel sind zwischen einer und drei Alkylgruppen an die Diphenylether-Grundeinheit gebunden. Component (F) is selected from the group consisting of mineral oil, alkylated benzenes, alkylated naphthalenes, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, alkylated diphenyl ethers, phloroglucinic esters, estolides and / or poly-alpha-olefins, alpha-olefin copolymers, metallocene catalyzed polyalfa-olefins. Preferred further oils are alkylated diphenyl ether oils. Alkylated Diphenyletheröle be marketed under the brand name Hilube ® by the company. Moresco. The alkyl groups contain between 10 and 20 carbon atoms. On average, between one and three alkyl groups are bound to the basic diphenyl ether unit.
Komponente (G) Component (G)
Das erfindungsgemäße Schmierstoffzusammensetzung umfasst des Weiteren von 0 bis 10 Gew.%, bevorzugt von 0,1 bis 10 Gew.-% Additive (G), die einzeln oder in Kombination eingesetzt werden. The lubricant composition according to the invention further comprises from 0 to 10% by weight, preferably from 0.1 to 10% by weight, of additives (G), which are used individually or in combination.
Die Komponente (G) wird ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV- Stabilisatoren, ausgewählt werden. Es können sowohl Additive verwendet werden, die in der Komponente (A) löslich als auch Additive, die in den PFPE-Ölen der Komponente (D) löslich oder aber auch in beiden Ölphasen unlöslich sind. Component (G) is selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers. It is possible to use both additives that are soluble in component (A) and additives that are soluble in the PFPE oils of component (D) or also insoluble in both oil phases.
Beispiele für Antioxidantien sind styrolisierte Diphenylamine, diaromatische Amine, Phenolharze, Thiophenolharze, Phosphite, butyliertes Hydroxytoluol, butyliertes Hydroxyanisol, Phenyl-alpha-naphthylamin, Phenyl-beta-naphthylamin, octyliertes/butyliertes Diphenylamin, di-alpha-Tocopherol, di-tert.-butyl-Phenol oderdi- tert.butyl-4-methylphenol, Benzolpropansäure, schwefelhaltige Phenolverbindungen, Phenolverbindungen und Mischungen dieser Komponenten. Examples of antioxidants are styrenated diphenylamines, diaromatic amines, phenolic resins, thiophenolic resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, octylated / butylated diphenylamine, di-alpha-tocopherol, di-tert-butyl-phenol or di-tert-butyl-4-methylphenol, benzene propanoic acid, sulfur-containing phenolic compounds, phenolic compounds and mixtures of these components.
Beispiele für geeignete Korrosionsschutzadditive, Metalldesaktivatoren oder lonen- Komplexbildner enthalten. Hierzu zählen Triazole, Imidazoline, N-Methylglycin (Sarcosin), Benzotriazolderivate, N,N-Bis(2-ethylhexyl)-ar-methyl-1 H-benzotriazol-1- methanamin; n-Methyl-N(1-oxo-9-octadecenyl)glycin, Gemisch aus Phosphorsäure und Mono-und Diisooctylester umgesetzt mit (Cn-14)-Alkylaminen, Gemisch aus Phosphorsäure und Mono-und Diisooctylester umgesetzt mit tert.-Alkylamin und primären (Ci2-14)-Aminen, Dodekansäure, Triphenylphosphorthionat und Aminphosphate. Kommerziell erhältliche Additive sind die folgenden: IRGAMET® 39, IRGACOR® DSS G, Amin O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 und CI-498. Contain examples of suitable anti-corrosion additives, metal deactivators or ion complexing agents. These include triazoles, imidazolines, N-methylglycine (sarcosine), benzotriazole derivatives, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; n-Methyl-N (1-oxo-9-octadecenyl) glycine, mixture of phosphoric acid and mono- and diisooctyl esters reacted with (Cn-14) -alkylamines, mixture of phosphoric acid and mono- and diisooctyl esters reacted with tert-alkylamine and primary (Ci2-14) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates. Commercially available additives are the following: IRGAMET ® 39, IRGACOR ® DSS G, Amin O; Sarkosyl O ® (Ciba), COBRATEC ® 122, CUVAN ® 303, VANLUBE ® 9123, CI-426, CI-426EP, CI-429 and CI-498th
Weitere Verschleißschutzadditive sind Amine, Aminphosphate, Phosphate, Thiophosphate, und Mischungen dieser Komponenten. Meistens weisen die genannten Verbindungen organische Gruppen auf. Zu den kommerziell erhältlichen Verschleißschutzadditiven gehören IRGALUBE® TPPT, IRGALUBE® 232, IRGALUBE® 349, IRGALUBE® 211 und ADDITIN® RC3760 Liq 3960, FIRC-SHUN® FG 1505 und FG 1506, NA-LUBE® KR-015FG, LUBEBOND®, FLUORO® FG, SYNALOX® 40-D, ACHESON® FGA 1820 und ACHESON® FGA 1810. Further anti-wear additives are amines, amine phosphates, phosphates, thiophosphates and mixtures of these components. Most of the compounds mentioned have organic groups. The commercially available anti-wear additives include IRGALUBE ® TPPT, IRGALUBE ® 232, IRGALUBE ® 349, IRGALUBE ® 211 and ADDITIN ® RC3760 Liq 3960, FIRC-SHUN ® FG 1505 and FG 1506, NA-LUBE ® KR-015FG, LUBEBOND ® , FLUORO ® ® FG, SYNALOX ® 40-D, ACHESON ® FGA 1820 and ACHESON ® FGA 1810.
Als Additive können auch PFPE-Derivate enthalten sein. Beispielsweise PFPE- Carbonsäuren, deren Metall- und Ammoniumsalze, deren Ester- und Amid-Derivate. Weitere geeignete Substanzen sind beispielsweise in WO01/72759A1 , WO 01/27916A1 , EP1070074B1 , EP1659165B1 und US2015011446A1 beschrieben. PFPE derivatives can also be included as additives. For example PFPE carboxylic acids, their metal and ammonium salts, their ester and amide derivatives. Further suitable substances are described, for example, in WO01 / 72759A1, WO 01 / 27916A1, EP1070074B1, EP1659165B1 and US2015011446A1.
Komponente (H) Component (H)
Des Weiteren können die erfindungsgemäßen Schmierstoffzusammensetzungen Festschmierstoffe (H) enthalten, die ausgewählt werden aus der Gruppe bestehend aus BN, Pyrophosphat, Zn-Oxid, Mg-Oxid, Pyrophosphate, Thiosulfate, Mg-Carbonat, Ca-Carbonat, Ca-Stearat, Zn-Sulfid, Mo-sulfid, W-sulfid, Sn-Sulfid, Graphite, Graphen, Nano-Tubes, Si02-Modifikationen oder eine Mischung daraus enthalten. Die Festschmierstoffe (H) sind in Mengen von 0 bis 10 Gew.-%, bevorzugt 2 bis 5 Gew.- % in der erfindungsgemäßen Schmierstoffzusammensetzung enthalten. Furthermore, the lubricant compositions according to the invention can contain solid lubricants (H) which are selected from the group consisting of BN, pyrophosphate, Zn oxide, Mg oxide, pyrophosphates, thiosulfates, Mg carbonate, Ca carbonate, Ca stearate, Zn sulfide, Mo sulfide, W sulfide, Sn sulfide, graphite, graphene, nanotubes, Si02 modifications or a mixture thereof. The solid lubricants (H) are contained in the lubricant composition according to the invention in amounts of 0 to 10% by weight, preferably 2 to 5% by weight.
Die erfindungsgemäße Schmierstoffzusammensetzung wird im Bereich von Bauteilen, insbesondere in Wälzlagern, Gleitlagern, Transport- und Steuerketten in der Fahrzeugtechnik, bei Schienenfahrzeugen, der Fördertechnik, bei Folienreckanlagen, bei Wellpappanlagen, von Laufrollenlagern, Lüfterlagern, Lagern von Traktionsmotoren, zur Schmierung von Kegelrad- und Stirnradgetrieben, Federn, Schrauben und Kompressoren, Pneumatikkomponenten, Armaturen, und von Maschinenbauteilen und in Anlagen, bei denen es zum gelegentlichen, unbeabsichtigten Kontakt mit Lebensmitteln kommt, eingesetzt. The lubricant composition according to the invention is used in the field of components, in particular in roller bearings, slide bearings, transport and timing chains in vehicle technology, rail vehicles, conveyor technology, film stretching systems, corrugated cardboard systems, roller bearings, fan bearings, bearings for traction motors, for the lubrication of bevel and bevel gears Helical gears, springs, screws and compressors, pneumatic components, fittings, and from machine components and in systems where there is occasional, unintentional contact with food.
Die beigefügten Figuren zeigen die Vorteile der erfindungsgemäßen Lithiumhybridkomplexfette: The attached figures show the advantages of the lithium hybrid complex greases according to the invention:
Fig. 1 zeigt die Walkpenetration 60dT, Fig. 1 shows the worked penetration 60dT,
Fig. 2 zeigt die Ölabscheidung, d.h. den Verlust des Öls aus dem Schmierfett. Figure 2 shows the oil separation, i.e. the loss of oil from the grease.
Die Erfindung nun anhand der folgenden Beispiele näher erläutert. The invention will now be explained in more detail with reference to the following examples.
Herstellung der erfindungsgemäßen Schmierstoffzusammensetzunqen Production of the lubricant compositions according to the invention
Die Herstellung der erfindungsgemäßen Schmierstoffzusammensetzung ist nicht eingeschränkt und kann nach allen geeigneten Verfahren durchgeführt werden. The production of the lubricant composition according to the invention is not restricted and can be carried out by any suitable method.
Die Herstellung der erfindungsgemäßen Schmierstoffherstellung kann beispielsweise so erfolgen, dass mit den Komponenten (A) und/oder (B) und/oder (F) ein Grundölgemisch hergestellt wird. In diesem Grundölgemisch, das komplett oder nur teilweise in einem geeigneten Reaktionsbehälter, der Heiz-, Kühl- und Rühreinrichtungen enthält, vorgelegt wird, werden die für den Lithiumkomplexverdicker (C) erforderlichen Säuren eingeschmolzen und eine wässrige Lithiumhydroxidlösung zugegeben. Dadurch bildet sich ein Sud, der die Lithiumseifen der Carbonsäuren enthält. Die Säuren können einzeln zugegeben und neutralisiert werden oder aber es wird erst die Monocarbonsäure zugegeben und neutralisiert und in einem zweiten Schritt die höherfunktionelle Carbonsäure zugegeben und neutralisiert. Der Sud wird auf 130°C erhitzt um Wasser auszutreiben. Die Quellung des Verdickers (Lithiumkomplexseife) wird durch thermische Behandlung bei 150°C bis 210°C durchgeführt. Der thermisch behandelte Sud wird dann abgekühlt, wobei auch ein Teil des Grundölgemisches verwendet werden kann. Die Komponenten (D), (E), (G), (H) und eventuell nicht für das Grundölgemisch verwendeten (A), (B) und (F) werden bei einer geeigneten Temperatur zugegeben und durch Rühren vorhomogenisiert. The production of the lubricant production according to the invention can for example be carried out in such a way that a base oil mixture is produced with components (A) and / or (B) and / or (F). The acids required for the lithium complex thickener (C) and an aqueous lithium hydroxide solution are melted in this base oil mixture, which is completely or only partially placed in a suitable reaction vessel containing heating, cooling and stirring equipment admitted. This creates a brew that contains the lithium soaps of the carboxylic acids. The acids can be added individually and neutralized, or the monocarboxylic acid is first added and neutralized and, in a second step, the higher-functionality carboxylic acid is added and neutralized. The brew is heated to 130 ° C to drive off water. The swelling of the thickener (lithium complex soap) is carried out by thermal treatment at 150 ° C to 210 ° C. The thermally treated brew is then cooled, whereby part of the base oil mixture can also be used. The components (D), (E), (G), (H) and possibly not used for the base oil mixture (A), (B) and (F) are added at a suitable temperature and prehomogenized by stirring.
Feste Schmierstoffadditive, die im Grundölgemisch löslich sind, werden beispielsweise bei Temperaturen oberhalb ihres Schmelzpunktes zugegeben. Flüssige Additive oder nicht schmelzende Additive/FestschmierstoffeA/erdickerkomponenten werden bei Temperaturen unter 80°C zugegeben. Das so hergestellte Lithiumkomplexhybridfett kann durch geeignete Geräte wie Dreiwalzwerke, Kolloidmühlen oder Gaulin homogenisiert werden. Solid lubricant additives that are soluble in the base oil mixture are added, for example, at temperatures above their melting point. Liquid additives or non-melting additives / solid lubricants / thickener components are added at temperatures below 80 ° C. The lithium complex hybrid grease produced in this way can be homogenized using suitable equipment such as three-roll mills, colloid mills or Gaulin.
In dem so beschriebenen Verfahren wird die erfindungsgemäße Schmierstoffzusammensetzung in einem Prozess hergestellt. Alternativ kann die Zugabe des PFPE-Öles (D) und der optionalen Verdickerkomponente (E) in dem oben beschriebenen Verfahren unterbleiben, so dass ein Lithiumkomplexfett entsteht. Die Komponenten (D) und (E) können durch Rühren, Homogenisieren wie oben beschrieben zu einem PFPE-Fett vereinigt werden. Lithiumkomplexfett und PFPE-Fett können in einem zweiten Verfahrensschritt vereinigt werden und daraus unter Rühren und Homogenisieren die erfindungsgemäße Schmierstoffzusammensetzung hergestellt werden. In the method described in this way, the lubricant composition according to the invention is produced in one process. Alternatively, the addition of the PFPE oil (D) and the optional thickener component (E) in the process described above can be omitted, so that a lithium complex grease is produced. Components (D) and (E) can be combined to a PFPE fat by stirring and homogenizing as described above. Lithium complex grease and PFPE grease can be combined in a second process step and the lubricant composition according to the invention can be produced therefrom with stirring and homogenization.
Die Herstellung kann auch mit kontinuierlichen Verfahren erfolgen, wobei auch Li- Komplex-Fertigseife in Pulverform verwendet werden kann. Production can also be carried out using continuous processes, in which case Li-complex ready-made soap in powder form can also be used.
Beispiel 1 Herstellung mehrerer erfindungsgemäßer Schmierstoffzusammensetzungen, Vergleich mit den zur Herstellung verwendeten Lithiumkomplexfett bzw. PFPE/PTFE- Fett, Vergleich mit Harnstoff Hybridfetten example 1 Production of several lubricant compositions according to the invention, comparison with the lithium complex grease or PFPE / PTFE grease used for production, comparison with urea hybrid greases
Herstellung Manufacturing
Lithiumkomplexseifenfett (Fett A) und ein PFPE/PTFE-Fett (Fett B) werden separat hergestellt und die beiden Fette A und B in unterschiedlichen Verhältnissen vermischt, gerührt und durch Walzen homogenisiert. Lithium complex soap grease (fat A) and a PFPE / PTFE grease (fat B) are produced separately and the two fats A and B are mixed in different proportions, stirred and homogenized by rolling.
Fett A Fat A
Es wird ein Lithiumkomplexfett bestehend aus 77 % einer Mischung eines Alkyldiphenylether (100 mm7sec/40°C) und Trimellithsäureester sowie vollhydriertem Polyisobutylen (vollhydriert, Mn ca. 1300 g/mol) als Grundöl, wobei sich eine Viskosität bei 40°C von 220 mm2/sec ergibt, hergestellt, dann werden 15 % Lithiumkomplex aus Azelainsäure und 12-Hydroxystearinsäure, sowie 8 % eines Additivpackages bestehend aus aminischen Antioxidantien, Phosphaten, Thiadiazolen, Triazolen und Aminphosphaten zugegeben. Die Walkpenetration liegt bei 270 1/10 mm (siehe Tabelle 1) A lithium complex grease consisting of 77% of a mixture of an alkyl diphenyl ether (100 mm7sec / 40 ° C) and trimellitic acid ester as well as fully hydrogenated polyisobutylene (fully hydrogenated, Mn approx. 1300 g / mol) is used as the base oil, with a viscosity of 220 mm at 40 ° C 2 / sec results, then 15% lithium complex of azelaic acid and 12-hydroxystearic acid and 8% of an additive package consisting of amine antioxidants, phosphates, thiadiazoles, triazoles and amine phosphates are added. The worked penetration is 270 1/10 mm (see table 1)
Fett B Fat B
Es wird ein PFPE/PTFE-Fett, enthaltend zu 70 % eine Mischung aus linearem und verzweigtem PFPE, kinematische Viskosität 200 mm2/sec bei 40°C, 26 % PTFE- Mikropulver, durchschnittliche Teilchengröße d 50 (Laserbeugung, DIN ISO 9277) ca. 5 pm, spezifische Oberfläche (DIN ISO 9277) ca. 5 m2/g, und 4 % Dinatriumsebacat als Korrosionschutzadditiv hergestellt. Die Walkpenetration liegt bei 286 1/10 mm (siehe Tabelle 1) A PFPE / PTFE grease is used, containing 70% a mixture of linear and branched PFPE, kinematic viscosity 200 mm 2 / sec at 40 ° C, 26% PTFE micropowder, average particle size d 50 (laser diffraction, DIN ISO 9277) approx. 5 μm, specific surface (DIN ISO 9277) approx. 5 m 2 / g, and 4% disodium sebacate produced as an anti-corrosion additive. The worked penetration is 286 1/10 mm (see table 1)
Beispiel 1 (B1) Example 1 (B1)
Mischung aus Fett A und Fett B im Verhältnis 10 Gew.-% zu 90 Gew.-%. Mixture of fat A and fat B in a ratio of 10% by weight to 90% by weight.
Beispiel 2 (B2) Mischung aus Fett A und Fett B im Verhältnis 30 Gew.-% zu 70 Gew.-%. Example 2 (B2) Mixture of fat A and fat B in a ratio of 30% by weight to 70% by weight.
Beispiel 3 (B3) Example 3 (B3)
Mischung aus Fett A und Fett B im Verhältnis 50 Gew.-% zu 50 Gew.-%. Mixture of fat A and fat B in a ratio of 50% by weight to 50% by weight.
Beispiel 4 (B4) Example 4 (B4)
Mischung aus Fett A und Fett B im Verhältnis 70 Gew.-% zu 30 Gew.-%. Mixture of fat A and fat B in a ratio of 70% by weight to 30% by weight.
Beispiel 5 (B5) Example 5 (B5)
Mischung aus Fett A und Fett B im Verhältnis 90 Gew.-% zu 10 Gew.-%. Verqleichsbeispiel 1 (VG1) Mixture of fat A and fat B in a ratio of 90% by weight to 10% by weight. Comparative example 1 (VG1)
Es wird ein Harnstoffhybridfett bestehend zu 50 Gew.-% aus Fett B und zu 50 Gew.- % aus einem Harnstofffett hergestellt. Das Harnstofffett besteht aus einer Mischung eines Trimellitsäureesters und einem Reaktionsprodukt aus Octylamin und Oleylamin mit einem MDI/TDI-Gemisch als Harnstoffverdicker, sowie Additiven. Die Grundölviskosität liegt bei ca. 80 mm2/sec. Die Walkpenetration liegt bei 265 mnrVsec (siehe Tabelle 2) A urea hybrid fat consisting of 50% by weight of fat B and 50% by weight of a urea fat is produced. The urea fat consists of a mixture of a trimellitic acid ester and a reaction product of octylamine and oleylamine with an MDI / TDI mixture as a urea thickener, as well as additives. The base oil viscosity is approx. 80 mm 2 / sec. The worked penetration is 265 mnrVsec (see Table 2)
Verqleichsbeispiel 2 (VG2) Comparison example 2 (VG2)
Es wird ein Harnstoffhybridfett bestehend aus einem Komplexester, Dimersäure basiert, V 40 apr. 400 mm'Vsec bei 40°C und verzweigtem PFPE-ÖI mit einer kinematischen Viskosität von ca. 400 mm2/sec im Massenverhältnis 2:1 hergestellt. Der Harnstoffverdicker ist zu 10 % enthalten und ist ein Reaktionsprodukt aus Octylamin und Oleylamin mit einem MDI/TDI-Gemisch. Darüber hinaus sind 8 Gew.- % PTFE-Pulver (wie bei Fett B) und 5 Gew.-% lösliche Additive (Antioxidantien, Aminphosphate) enthalten. Die Walkpenetration liegt bei 290 mm2/sec (siehe Tabelle 2) A urea hybrid fat consisting of a complex ester, based on dimer acid, V 40 apr. 400 mm'Vsec at 40 ° C and branched PFPE oil with a kinematic viscosity of approx. 400 mm 2 / sec in a mass ratio of 2: 1. The urea thickener is 10% contained and is a reaction product of octylamine and oleylamine with an MDI / TDI mixture. In addition, it contains 8% by weight of PTFE powder (as for fat B) and 5% by weight of soluble additives (antioxidants, amine phosphates). The worked penetration is 290 mm 2 / sec (see Table 2)
Tabelle 1 zeigt die allgemeinen Kenndaten der erfindungsgemäßen Lithumkomplexhybridfette der Beispiele B1 bis B5 und der Fette A und B, Tabelle 1 Table 1 shows the general characteristics of the lithium complex hybrid greases according to the invention of Examples B1 to B5 and the greases A and B, Table 1
Tabelle 2 zeigt die Daten der Vergleichsbeispiele VG1 bis 2. Table 2 shows the data of comparative examples VG1 to 2.
Tabelle 2 Table 2
Wie in Figur 1 (Walkpenetration der erfindungsgemäßen Zusammensetzungen) zu erkennen ist, ergibt sich besonders für die Zusammensetzungen B2, B3 und B4 eine niedrigere Walkpenetration als für die beiden eingesetzten Fette A und B. Dies zeigt einen unerwarteten synergistischen Effekt durch die Kombination der beiden Fetttypen zu den erfindungsgemäßen Zusammensetzungen. As can be seen in FIG. 1 (milled penetration of the compositions according to the invention), a lower milled penetration results, especially for compositions B2, B3 and B4, than for the two fats A and B used. This shows an unexpected synergistic effect due to the combination of the two types of fat to the compositions according to the invention.
Wie in Figur 2 (Ölabscheidung der erfindungsgemäßen Zusammensetzungen im Vergleich) zu erkennen ist, zeigen die erfindungsgemäßen Zusammensetzungen eine niedrigere Ölabscheidung als die Fette A und B, aus denen sie hergestellt wurden. Dieses Verhalten zeigt den unerwarteten synergistischen Effekt, der durch die erfindungsgemäße Zusammensetzung hervorgerufen wird. Die Ölabscheidung erreicht nahezu die niedrigen Werte der beiden Vergleichsprodukte VG1 und VG2. Die Reduktion der Ölabscheidung im Vergleich Fett B zeigt den Vorteil gegenüber den reinen PFPE/PTFE Fetten auf. As can be seen in FIG. 2 (oil separation of the compositions according to the invention in comparison), the compositions according to the invention show a lower oil separation than the fats A and B from which they were produced. This behavior shows the unexpected synergistic effect caused by the composition according to the invention. The oil separation almost achieves the low values of the two comparison products VG1 and VG2. The reduction in oil separation in comparison to grease B shows the advantage over pure PFPE / PTFE greases.
Auch legen die Daten nahe, dass ein gewünschtes Ölabscheidungsverhalten durch Wahl der Menge an Fetten A und B eingestellt werden kann. The data also suggest that a desired oil separation behavior can be set by choosing the amount of fats A and B.
Bestimmung des Verdampfunqsverlustes Determination of the evaporation loss
Die erfindungsgemäßen Schmierstoffzusammensetzungen wurden auf ihre thermische Beständigkeit überprüft und die Ergebnisse vor allem mit denen der Harnstoff-Hybridfette verglichen. Dazu wurden Untersuchungen hinsichtlich der Verdampfung und Viskosität unter Temperaturbelastung von 5 g Fett Einwaage in einem Edelstahl-Schälchen bei 200°C durchgeführt. Die Ergebnisse sind in den Tabellen 3 und 4 gezeigt. The lubricant compositions according to the invention were checked for their thermal stability and the results were compared primarily with those of the urea hybrid greases. For this purpose, investigations were carried out with regard to evaporation and viscosity under a temperature load of 5 g of fat weighed in in a stainless steel bowl at 200 ° C. The results are shown in Tables 3 and 4.
Der Verdampfungsverlust wird nach der DIN-Norm 58397 bestimmt. Für jede Fettprobe werden jeweils drei Verdampfungsverlustschalen aus nicht-rostendem Stahl benötigt. Die Geometrie der Schalen ist in der Norm zur Bestimmung des Verdampfungsverlustes (DIN 58397) beschrieben. Zu Beginn wird das jeweilige Leergewicht der Schalen ermittelt. Im Anschluss werden die drei Verdampfungsverlustschalen mit der Fettprobe gefüllt. Dabei ist darauf zu achten, das Fett luftblasenfrei aufzubringen. Mit einem Abstreifer wird die Oberfläche glattgestrichen und überschüssiges Fett, das in die Randvertiefung der Schale gelangt ist, wird entfernt. Die Schalen werden anschließend in einem gängigen Labor- Trockenschrank mit Konvektion bei geschlossener Klappe bei entsprechender Prüftemperatur (hier 200°C) eingelagert. Nach der jeweils vorgegebenen Zeitdauer (48h, 96h, 144h und 168h) entnimmt man die Schalen aus dem Trockenschrank und lässt diese erkalten. Anschließend werden die Schalen gewogen. Der Verdampfungsverlust wird aus der Differenz von Einwaage zu gemessenem Wert ermittelt. Aus den drei Einzelwerten wird ein Mittelwert bestimmt (VM) Zusammen mit dem Mittelwert der drei Einwaagen (AM) lässt sich der Verdampfungsverlust berechnen. V = (VM / AM)*100 [% ]. Nach dem Auswiegen werden die Schalen bis zum nächsten Zeitpunkt in den Trockenschrank gestellt. Dies wird solange wiederholt, bis 168h vergangen sind. The evaporation loss is determined according to DIN standard 58397. Three stainless steel evaporation loss trays are required for each fat sample. The geometry of the bowls is described in the standard for determining the evaporation loss (DIN 58397). At the beginning, the respective empty weight of the bowls is determined. The three evaporation loss trays are then filled with the fat sample. It is important to ensure that the grease is applied without air bubbles. The surface is smoothed with a scraper and excess fat that has got into the recess on the edge of the bowl is removed. The dishes are then stored in a standard laboratory drying cabinet with convection with the flap closed at the appropriate test temperature (here 200 ° C). After the specified period of time (48h, 96h, 144h and 168h), the trays are removed from the drying cabinet and allowed to cool. The bowls are then weighed. The evaporation loss is determined from the difference between the initial weight and the measured value. A mean value is determined from the three individual values (VM). Together with the mean value of the three weights (AM), the evaporation loss can be calculated. V = (VM / AM) * 100 [%]. After weighing, the dishes are placed in the drying cabinet until the next time. This is repeated until 168 hours have passed.
Tabelle 3 Table 3
Bestimmung der Scherviskosität Determination of the shear viscosity
Die Scherviskosität wird nach der DIN-Norm 53019 Teil 1 und Teil 3 bestimmt. Die Fettproben werden in jeweils drei Verdampfungsverlustschalen aus nicht-rostendem Stahl überführt. Die Geometrie der Schalen ist in der Norm zur Bestimmung des Verdampfungsverlustes (DIN 58397) beschrieben. Die Schalen werden anschließend in einem gängigen Labor-Trockenschrank mit Umwälzung bei entsprechender Prüftemperatur (hier 200°C) eingelagert. Nach der jeweils vorgegebenen Zeitdauer (48h, 96h, 144h und 168h) entnimmt man die Schalen aus dem Trockenschrank und lässt diese erkalten. Der Startwert für die Scherviskosität wird von jedem Fett vor der thermischen Belastung bestimmt. The shear viscosity is determined according to DIN standard 53019 part 1 and part 3. The fat samples are transferred to three stainless steel evaporation-loss trays. The geometry of the bowls is described in the standard for determining the evaporation loss (DIN 58397). The dishes are then stored in a standard laboratory drying cabinet with circulation at the appropriate test temperature (here 200 ° C). After the specified period of time (48h, 96h, 144h and 168h), the trays are removed from the drying cabinet and allowed to cool. The starting value for the shear viscosity is determined for each grease before the thermal load.
Die Messung der Scherviskosität erfolgt mit einem Gerät, das standardmäßig zur Bestimmung Theologischer Parameter von Schmierstoffen verwendet wird (z.B. Rheometer MCR 302 von Anton Paar). The shear viscosity is measured with a device that is used as standard to determine theological parameters of lubricants (e.g. rheometer MCR 302 from Anton Paar).
Eingesetzt wird dabei ein Kegel-Platte-System (DIN EN ISO 3219 und DIN 53019), bevorzugt mit einem Messkegel, der einen Durchmesser von 25 mm aufweist. Die benötigte Menge an Fettprobe orientiert sich an typischen Mengen, die für Theologische Messungen erforderlich sind. Die Messdauer beträgt 120 s, wovon 60 s Temperier- bzw. Haltezeit sind. Gemessen wird bei einer konstanten Scherrate von 300 1/s und einer Temperatur von 25°C. Der Wert, der nach 90 s abgelesen werden kann, stellt die Scherviskosität für die jeweilige Fettprobe dar. Aus den drei ermittelten Einzelwerten wird der Mittelwert gebildet und final angegeben. A cone-plate system (DIN EN ISO 3219 and DIN 53019) is used, preferably with a measuring cone with a diameter of 25 mm. The required amount of fat sample is based on typical amounts that are required for theological measurements. The measurement duration is 120 s, of which 60 s are tempering or holding times. Measurements are made at a constant shear rate of 300 1 / s and a temperature of 25 ° C. The value that can be read off after 90 s represents the shear viscosity for the respective fat sample. The mean value is calculated from the three individual values determined and then given.
Tabelle 4 Table 4
Die Fette der Beispiele 1 bis 5 wurden nun mit den Fetten der Vergleichsbeispiele 1 und 2 und den beiden Einzelfetten (A) und (B) hinsichtlich ihrer thermischen Beständigkeit verglichen. Die Ergebnisse sind in den Tabellen 5 und 6 gezeigt. The fats of Examples 1 to 5 were then compared with the fats of Comparative Examples 1 and 2 and the two individual fats (A) and (B) with regard to their thermal resistance. The results are shown in Tables 5 and 6.
Tabelle 5 Table 5
Tabelle 6 Table 6
Die obigen Ergebnisse zeigen, dass mit den erfindungsgemäßen Lithiumkomplexhybridfetten der Anstieg der Scherviskosität deutlich niedriger ausfällt als bei den Vergleichsprodukten VG1 und VG2. VG2 zeigt bereits nach 96 h eine Scherviskosität von 100.000 mPas und ist nicht mehr schmierfähig. VG1 zeigt nach 168 h Prüfzeit eine doppelt so hohe Scherviskosität als alle erfindungsgemäßen Zusammensetzungen B1 bis B5, siehe Tabelle 4. The above results show that with the lithium complex hybrid greases according to the invention, the increase in shear viscosity is significantly lower than with the comparison products VG1 and VG2. VG2 shows a shear viscosity of 100,000 mPas after just 96 hours and is no longer lubricious. After a test time of 168 h, VG1 shows twice as high a shear viscosity than all compositions B1 to B5 according to the invention, see Table 4.
Das PFPE/PTFE-Fett (Fett B) zeigt in dem Test erwartungsgemäß die geringsten Verdampfungsverluste. Überraschenderweise liegt die Scherviskosität der erfindungsgemäßen Beispiele B1 , B2 und B4 nach 168 h Prüfzeit niedriger als bei Fett B und zeigt damit günstigeres Verhärtungsverhalten. As expected, the PFPE / PTFE grease (grease B) shows the lowest evaporation losses in the test. Surprisingly, the shear viscosity of Examples B1, B2 and B4 according to the invention after a test time of 168 hours is lower than that of fat B and thus shows more favorable hardening behavior.
Insgesamt zeigt sich, dass das Verhärtungsverhalten der erfindungsgemäßen Schmierstoffe bei hohen Temperaturen günstiger ist als bei Harnstoff-Hybridfetten. Überraschenderweise wurde sogar gefunden, dass bei manchen der erfindungsgemäßen Zusammensetzungen sogar eine geringere Verhärtung auftritt als bei einem PFPE/PTFE-Fett. Überraschenderweise wurde auch gefunden, dass das Ölabscheidungsverhalten der erfindungsgemäßen Schmierstoffe durch Wahl von bestimmten Mischungsverhältnisses der Fette A (Lithiumkomplexfett) und B (PTFE/PFPE-Fett) eingestellt und somit auf unterschiedliche Anforderungen angepasst werden kann. Overall, it has been shown that the hardening behavior of the lubricants according to the invention is more favorable at high temperatures than in the case of urea hybrid greases. Surprisingly, it was even found that with some of the compositions according to the invention even less hardening occurs than with a PFPE / PTFE grease. Surprisingly, it was also found that the oil separation behavior of the lubricants according to the invention can be set and thus adapted to different requirements by selecting certain mixing ratios of greases A (lithium complex grease) and B (PTFE / PFPE grease).
Beispiel 2 Example 2
Herstellung eines erfindungsgemäßen Schmierstoffes mit unterschiedlichen Herstellverfahren Wie bereits beschrieben, können die erfindungsgemäßen Schmierstoffe auf verschiedene Weise hergestellt werden. Bei der Variante „im Kessel gemischt“ werden ein Lithiumkomplexfett (Fett C) und ein PFPE/PTFE-Fett (Fett D) getrennt hergestellt und dann in einem Kessel im Verhältnis 40 zu 60 Gew.-% unter Rühren gemischt. Das so entstehende Lithiumkomplexhybridfett B6 wird mit einem Dreiwalzwerk abschließend homogenisiert. Production of a lubricant according to the invention with different production processes As already described, the lubricants according to the invention can be produced in various ways. With the “mixed in the kettle” variant, a lithium complex grease (fat C) and a PFPE / PTFE grease (fat D) are produced separately and then mixed in a kettle at a ratio of 40 to 60% by weight while stirring. The resulting lithium complex hybrid grease B6 is then homogenized using a three-roll mill.
Bei der „in situ“ Herstellung wird das Lithiumkomplexfett identisch zum Fett C hergestellt, beim Abkühlen werden dann aber, abweichend auch die Bestandteile des Fettes D, zugegeben, sodass die erfindungsgemäße Schmierstoffzusammensetzung in einem Arbeitsgang hergestellt wird. Die erfindungsgemäße Schmierstoffzusammensetzung B6 wird ebenfalls abschließend gewalzt. In “in situ” production, the lithium complex grease is produced identically to fat C, but when it cools down, the components of fat D are added, so that the lubricant composition according to the invention is produced in one operation. The lubricant composition B6 according to the invention is also finally rolled.
Fett C Fat C
Es wird ein Lithiumkomplexfett bestehend aus 80 Gew.-%% einer Mischung eines Alkyldiphenylether (100 mnfVsec bei 40°C) und eines Trimellitsäureesters sowie vollhydriertem Polyisobutylen (vollhydriert, Mn ca. 1300 g/mol) als Grundöl hergestellt, wobei sich eine Viskosität bei 40°C von 100 mm2/sec ergibt. 15 Gew.-% eines Lithiumkomplexes aus Azelainsäure und 12-Hydroxystearinsäure, sowie 5 Gew.-% eines Additivpackages bestehend aus aminischen Antioxidantien, Phosphaten werden bereitgestellt. Die Walkpenetration liegt bei 327 1/10 mm. A lithium complex grease consisting of 80% by weight of a mixture of an alkyl diphenyl ether (100 mnfVsec at 40 ° C) and a trimellitic acid ester as well as fully hydrogenated polyisobutylene (fully hydrogenated, Mn approx. 1300 g / mol) is produced as the base oil, with a viscosity at 40 ° C of 100 mm 2 / sec results. 15% by weight of a lithium complex of azelaic acid and 12-hydroxystearic acid and 5% by weight of an additive package consisting of amine antioxidants and phosphates are provided. The fulled penetration is 327 1/10 mm.
Fett D Fat D
Es wird ein PFPE/PTFE-Fett, enthaltend zu 65 Gew.-% eine Mischung aus linearem und verzweigtem PFPE, einer kinematischen Viskosität von 145 mm2/sec bei 40°C, 33 Gew.-% PTFE-Mikropulver, durchschnittliche Teilchengröße d 50 (Laserbeugung, DIN ISO 9277) ca. 5 miti, spezifische Oberfläche (DIN ISO 9277) ca. 5 m2/g, und 2 Gew.- % Dinatriumsebacat als Korrosionschutzadditiv hergestellt. Die Walkpenetration liegt bei 286 1/10 mm A PFPE / PTFE grease containing 65% by weight of a mixture of linear and branched PFPE, a kinematic viscosity of 145 mm 2 / sec at 40 ° C., 33% by weight of PTFE micropowder, average particle size d 50 (laser diffraction, DIN ISO 9277) approx. 5 miti, specific surface (DIN ISO 9277) approx. 5 m 2 / g, and 2% by weight disodium sebacate as an anti-corrosion additive. The fulled penetration is 286 1/10 mm
Tabelle 7 Table 7
Daten des erfindungsgemäßen Beispiels B6 nach Beispiel 2 Data of example B6 according to the invention according to example 2
Tabelle 8 Table 8
Tabelle 9 Table 9
Beide Herstellungsvarianten liefern im Rahmen der Messgenauigkeit gleiche Werte. Aufgrund der vorliegenden Daten kann B6, nach Herstellungsbeispiel 1 und Herstellungsbeispiel 2, mit beiden Herstellvarianten als Schmierstoff eingesetzt werden. Both manufacturing variants deliver the same values within the scope of the measurement accuracy. On the basis of the data available, B6 can be used as a lubricant according to production example 1 and production example 2 with both production variants.
Somit ist gezeigt, dass die erfindungsgemäßen Schmierstoffzusammensetzungen mit unterschiedlichen Verfahren hergestellt werden können. It is thus shown that the lubricant compositions according to the invention can be produced using different processes.

Claims

Patentansprüche Claims
1. Lithiumkomplexhybridfett enthaltend 1. Containing lithium complex hybrid grease
(A) 70 bis 7 Gew.-% eines Esters oder eines Estergemisches, ausgewählt aus der Gruppe bestehend aus Trimellithsäureestern, die als Alkoxygruppe lineare oder verzweigte Alkylgruppen aufweisen, die 6 bis 18 Kohlenstoffatome enthalten, bevorzugt 8 bis 14 Kohlenstoffatome, wobei die Alkoxygruppe gleich oder verschieden sein können, Pyromellithsäureestern, hydrierte oder unhydrierte Dimersäuren, Estoliden, (A) 70 to 7% by weight of an ester or an ester mixture selected from the group consisting of trimellitic acid esters which have linear or branched alkyl groups as alkoxy groups which contain 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the alkoxy group being the same or can be different, pyromellitic acid esters, hydrogenated or unhydrogenated dimer acids, estolides,
(B) 0,5 bis 20 Gew.-% nicht hydriertes, hydriertes oder vollhydriertes Polyisobutylen oder deren Mischungen, (B) 0.5 to 20% by weight of non-hydrogenated, hydrogenated or fully hydrogenated polyisobutylene or mixtures thereof,
(C) 1 bis 18 Gew.-% Lithiumkomplexseifen und (C) 1 to 18% by weight lithium complex soaps and
(D) 5 bis 70 Gew.-% Perfluorpolyether (PFPE). (D) 5 to 70% by weight perfluoropolyether (PFPE).
2. Lithiumkomplexhybridfett nach Anspruch 1 des Weiteren enthaltend 2. Lithium complex hybrid grease according to claim 1 further containing
(E) 1 bis 30 Gew,-% eines weiteren Verdickungsmittels. (E) 1 to 30% by weight of a further thickener.
3. Lithiumkomplexhybridfett nach einem der vorherigen Ansprüche des Weiteren enthaltend 3. Lithium complex hybrid grease according to one of the preceding claims further containing
(F) 0 bis 20 Gew.-%, vorzugsweise 2 bis 20 Gew.-% einer weiteren Ölkomponente. (F) 0 to 20% by weight, preferably 2 to 20% by weight, of a further oil component.
4. Lithiumkomplexhybridfett nach einem der vorherigen Ansprüche des Weiteren enthaltend 4. Lithium complex hybrid grease according to one of the preceding claims further containing
(G) 0 bis 10 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% Additive, (G) 0 to 10% by weight, preferably 0.1 to 10% by weight of additives,
5. Lithiumkomplexhybridfett nach einem der vorherigen Ansprüche des Weiteren enthaltend 5. Lithium complex hybrid grease according to one of the preceding claims further containing
(H) 0 bis 10 Gew.-%, vorzugsweise 2 bis 5 Gew.-% Festschmierstoff. (H) 0 to 10% by weight, preferably 2 to 5% by weight, solid lubricant.
6. Lithiumkomplexhybridfett nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Pyromellithsäureester der Komponente (A) Tetrakis(2-ethylhexyl)pyromellitat und die Dimersäure Bis(2-ethylhexyl)dimerat ist. 6. Lithium complex hybrid grease according to one of the preceding claims, characterized in that the pyromellitic acid ester of component (A) is tetrakis (2-ethylhexyl) pyromellitate and the dimer acid is bis (2-ethylhexyl) dimerate.
7. Lithiumkomplexhybridfett nach Anspruch 2, dadurch gekennzeichnet, dass die Komponente (E) ausgewählt wird aus der Gruppe bestehend aus Al- Komplexseifen, Metall-Einfachseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems ohne Lithium, Metall-Komplexseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems ohne Lithium, Bentonite, Sulfonate, Silikate, Aerosil, Polyimide, PTFE oder einer Mischung daraus. 7. Lithium complex hybrid grease according to claim 2, characterized in that component (E) is selected from the group consisting of Al complex soaps, metal single soaps of the elements of the first and second main groups of the periodic table without lithium, metal complex soaps of the elements of the first and second main group of the periodic table without lithium, bentonites, sulfonates, silicates, Aerosil, polyimides, PTFE or a mixture thereof.
8. Lithiumkomplexhybridfett nach Anspruch 3, dadurch gekennzeichnet, dass die Komponente (F) wird ausgewählt aus der Gruppe bestehend aus Mineralöl, alkylierten Benzolen, alkylierte Naphthaline, aliphatischen Carbonsäure- und Dicarbonsäureestern, Fettsäuretriglyceriden, alkylierte Diphenylether, Phloroglucinester, und/oder Poly-alpha-olefinen, alpha-Olefin-Copolymere, Metallocen katalysierte Poly-alfa-olefine. 8. Lithium complex hybrid grease according to claim 3, characterized in that component (F) is selected from the group consisting of mineral oil, alkylated benzenes, alkylated naphthalenes, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, alkylated diphenyl ethers, phloroglucine esters, and / or poly-alpha -olefins, alpha-olefin copolymers, metallocene-catalyzed poly-alfa-olefins.
9. Lithiumkomplexhybridfett nach Anspruch 4, dadurch gekennzeichnet, dass die Komponente (G) ausgewählt wird aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV- Stabilisatoren. 9. Lithium complex hybrid grease according to claim 4, characterized in that component (G) is selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers.
10. Lithiumkomplexhybridfett nach Anspruch 5, dadurch gekennzeichnet, dass die Komponente (H) ausgewählt wird aus der Gruppe bestehend aus BN, Pyrophosphat, Zn-Oxid, Mg-Oxid, Pyrophosphate, Thiosulfate, Mg-Carbonat, Ca-Carbonat, Ca-Stearat, Zn-Sulfid, Mo-sulfid, W-sulfid, Sn-Sulfid, Graphite, Graphen, Nano-Tubes, SiC>2-Modifikationen oder einer Mischung daraus. 10. Lithium complex hybrid grease according to claim 5, characterized in that component (H) is selected from the group consisting of BN, pyrophosphate, Zn oxide, Mg oxide, pyrophosphates, thiosulfates, Mg carbonate, Ca carbonate, Ca stearate , Zn sulfide, Mo sulfide, W sulfide, Sn sulfide, graphite, graphene, nanotubes, SiC> 2 modifications or a mixture thereof.
11. Verwendung des Lithiumkomplexhybridfett nach einem der vorherigen11. Using the lithium complex hybrid grease according to one of the previous ones
Ansprüche zur Schmierung von Bauteilen, insbesondere in Wälzlagern, Gleitlagern, Transport- und Steuerketten in der Fahrzeugtechnik, bei Schienenfahrzeugen, der Fördertechnik, bei Folienreckanlagen, bei Wellpappanlagen, von Laufrollenlagern, Lüfterlagern, Lagern vonClaims for the lubrication of components, in particular in roller bearings, slide bearings, transport and control chains in vehicle technology, rail vehicles, conveyor technology, film stretching systems, corrugated cardboard systems, roller bearings, fan bearings, bearings from
Traktionsmotoren, zur Schmierung von Kegelrad- und Stirnradgetrieben, Federn, Schrauben und Kompressoren, Pneumatikkomponenten, Amaturen, und von Maschinenbauteilen und in Anlagen, bei denen es zum gelegentlichen, unbeabsichtigten Kontakt mit Lebensmitteln kommt. Traction motors, for the lubrication of bevel gears and spur gears, springs, screws and compressors, pneumatic components, fittings, and machine components and in systems where there is occasional, unintentional contact with food.
12. Verfahren zur Schmierung oder zum Fetten von Bauteilen, insbesondere in Wälzlagern, Gleitlagern, Transport- und Steuerketten in der Fahrzeugtechnik und bei Schienenfahrzeugen, das Verfahren umfasst: 12. A method for lubricating or greasing components, in particular in roller bearings, plain bearings, transport and control chains in vehicle technology and in rail vehicles, the method comprises:
Aufträgen einer Schmiermittelzusammensetzung auf die Oberfläche des Bauteils, das Schmiermittel umfasst: Applying a lubricant composition to the surface of the component, the lubricant comprising:
(A) 70 bis 7 Gew.-% eines Esters oder eines Estergemisches, ausgewählt aus der Gruppe bestehend aus Trimellithsäureestern, die als Alkoxygruppe lineare oder verzweigte Alkylgruppen aufweisen, die 6 bis 18 Kohlenstoffatome enthalten, bevorzugt 8 bis 14 Kohlenstoffatome, wobei die Alkoxygruppe gleich oder verschieden sein können, Pyromellithsäureestern, hydrierte oder unhydrierte Dimersäuren, Estoliden, (A) 70 to 7% by weight of an ester or an ester mixture selected from the group consisting of trimellitic acid esters which have linear or branched alkyl groups as alkoxy groups which contain 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the alkoxy group being the same or can be different, pyromellitic acid esters, hydrogenated or unhydrogenated dimer acids, estolides,
(B) 0,5 bis 20 Gew.-% nicht hydriertes, hydriertes oder vollhydriertes Polyisobutylen oder deren Mischungen, (B) 0.5 to 20% by weight of non-hydrogenated, hydrogenated or fully hydrogenated polyisobutylene or mixtures thereof,
(C) 1 bis 18 Gew.-% Lithiumkomplexseifen und (C) 1 to 18% by weight lithium complex soaps and
(D) 5 bis 70 Gew.-% Perfluorpolyether (PFPE). (D) 5 to 70% by weight perfluoropolyether (PFPE).
13. Verfahren zur Schmierung oder zum Fetten von Laufrollenlagern in Stranggießanlagen, Transportrollenlagern in Durchlauföfen, von offenen Zahnkränzen in Drehrohröfen, Rohrmühlen, Trommeln und Mischern, Lagern in Wellpappanlagen und Folienreckanlagen, Lagern in Anlagen zur Herstellung und Transport von Lebensmitteln, das Verfahren umfasst: 13. Process for the lubrication or greasing of roller bearings in continuous casting plants, transport roller bearings in continuous ovens, of open gear rings in rotary kilns, tube mills, drums and mixers, bearings in corrugated cardboard plants and film stretching plants, bearings in plants for the production and transport of foodstuffs, the process comprises:
Aufträgen einer Schmiermittelzusammensetzung auf die Oberfläche des Bauteils, das Schmiermittel umfasst: (A) 70 bis 7 Gew.-% eines Esters oder eines Estergemisches, ausgewählt aus der Gruppe bestehend aus Trimellithsäureestern, die als Alkoxygruppe lineare oder verzweigte Alkylgruppen aufweisen, die 6 bis 18 Kohlenstoffatome enthalten, bevorzugt 8 bis 14 Kohlenstoffatome, wobei die Alkoxygruppe gleich oder verschieden sein können, Pyromellithsäureestern, hydrierte oder unhydrierte Dimersäuren, Estoliden, Applying a lubricant composition to the surface of the component, the lubricant comprising: (A) 70 to 7% by weight of an ester or an ester mixture selected from the group consisting of trimellitic acid esters which have linear or branched alkyl groups as alkoxy groups which contain 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the alkoxy group being the same or can be different, pyromellitic acid esters, hydrogenated or unhydrogenated dimer acids, estolides,
(B) 0,5 bis 20 Gew.-% nicht hydriertes, hydriertes oder vollhydriertes Polyisobutylen oder deren Mischungen, (B) 0.5 to 20% by weight of non-hydrogenated, hydrogenated or fully hydrogenated polyisobutylene or mixtures thereof,
(C) 1 bis 18 Gew.-% Lithiumkomplexseifen und (C) 1 to 18% by weight lithium complex soaps and
(D) 5 bis 70 Gew.-% Perfluorpolyether (PFPE). (D) 5 to 70% by weight perfluoropolyether (PFPE).
14. Verfahren zur Reduktion der Verhärtung von Schmierfetten bei 200°C und/oder zur Reduktion der Ölabscheidung von Schmierfetten auf Laufrollenlagern in Stranggießanlagen, Transportrollenlagern in Durchlauföfen, von offenen Zahnkränzen in Drehrohröfen, Rohrmühlen, Trommeln und Mischern, Lagern in Wellpappanlagen und Folienreckanlagen, Lagern in Anlagen zur Herstellung und Transport von Lebensmitteln, das Verfahren umfasst: 14. Process to reduce the hardening of lubricating greases at 200 ° C and / or to reduce the oil separation of lubricating greases on roller bearings in continuous casting plants, transport roller bearings in continuous furnaces, open gear rings in rotary kilns, tube mills, drums and mixers, bearings in corrugated cardboard systems and film stretching systems, bearings in plants for the production and transport of food, the process includes:
Aufträgen einer Schmiermittelzusammensetzung auf die Oberfläche des Bauteils, das Schmiermittel umfasst: Applying a lubricant composition to the surface of the component, the lubricant comprising:
(A) 70 bis 7 Gew.-% eines Esters oder eines Estergemisches, ausgewählt aus der Gruppe bestehend aus Trimellithsäureestern, die als Alkoxygruppe lineare oder verzweigte Alkylgruppen aufweisen, die 6 bis 18 Kohlenstoffatome enthalten, bevorzugt 8 bis 14 Kohlenstoffatome, wobei die Alkoxygruppe gleich oder verschieden sein können, Pyromellithsäureestern, hydrierte oder unhydrierte Dimersäuren, Estoliden, (A) 70 to 7% by weight of an ester or an ester mixture selected from the group consisting of trimellitic acid esters which have linear or branched alkyl groups as alkoxy groups which contain 6 to 18 carbon atoms, preferably 8 to 14 carbon atoms, the alkoxy group being the same or can be different, pyromellitic acid esters, hydrogenated or unhydrogenated dimer acids, estolides,
(B) 0,5 bis 20 Gew.-% nicht hydriertes, hydriertes oder vollhydriertes Polyisobutylen oder deren Mischungen, (B) 0.5 to 20% by weight of non-hydrogenated, hydrogenated or fully hydrogenated polyisobutylene or mixtures thereof,
(C) 1 bis 18 Gew.-% Lithiumkomplexseifen und (C) 1 to 18% by weight lithium complex soaps and
(D) 5 bis 70 Gew.-% Perfluorpolyether (PFPE). (D) 5 to 70% by weight perfluoropolyether (PFPE).
EP21704440.3A 2020-05-13 2021-02-03 Lithium complex hybrid grease Active EP4090723B1 (en)

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