EP3234079B1 - High-temperature lubricants - Google Patents

High-temperature lubricants Download PDF

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Publication number
EP3234079B1
EP3234079B1 EP15801328.4A EP15801328A EP3234079B1 EP 3234079 B1 EP3234079 B1 EP 3234079B1 EP 15801328 A EP15801328 A EP 15801328A EP 3234079 B1 EP3234079 B1 EP 3234079B1
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EP
European Patent Office
Prior art keywords
group
oil
temperature grease
temperature
hydrogenated
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.)
Active
Application number
EP15801328.4A
Other languages
German (de)
French (fr)
Other versions
EP3234079A2 (en
Inventor
Karl EGERSDÖRFER
Thomas Kilthau
Stefan Grundei
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.)
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Publication date
Application filed by Klueber Lubrication Muenchen SE and Co KG filed Critical Klueber Lubrication Muenchen SE and Co KG
Priority to EP18000075.4A priority Critical patent/EP3372659B1/en
Priority to PL18000076T priority patent/PL3372660T3/en
Priority to DK18000076.2T priority patent/DK3372660T3/en
Priority to PL18000075T priority patent/PL3372659T3/en
Priority to EP18000076.2A priority patent/EP3372660B1/en
Publication of EP3234079A2 publication Critical patent/EP3234079A2/en
Application granted granted Critical
Publication of EP3234079B1 publication Critical patent/EP3234079B1/en
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication 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
    • C10M111/04Lubrication 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
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02Well-defined hydrocarbons
    • C10M105/06Well-defined hydrocarbons aromatic
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/36Esters of polycarboxylic acids
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/08Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
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    • C10M109/00Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
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    • C10M111/00Lubrication 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
    • C10M111/06Lubrication 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 compound of the type covered by group C10M109/00
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    • C10M169/04Mixtures of base-materials and additives
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/062Oxides; Hydroxides; Carbonates or bicarbonates
    • C10M2201/0626Oxides; Hydroxides; Carbonates or bicarbonates used as thickening agents
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
    • C10M2201/1026Silicates used as thickening agents
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    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
    • C10M2201/103Clays; Mica; Zeolites
    • C10M2201/1036Clays; Mica; Zeolites used as thickening agents
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10Compounds containing silicon
    • C10M2201/105Silica
    • C10M2201/1056Silica used as thickening agents
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06Well-defined aromatic compounds
    • C10M2203/065Well-defined aromatic compounds used as base material
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • C10M2205/0265Butene used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix 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
    • C10M2207/127Carboxylix 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
    • C10M2207/1276Carboxylix 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
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    • C10M2207/125Carboxylix 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
    • C10M2207/128Carboxylix 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
    • C10M2207/1285Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/285Esters of aromatic polycarboxylic acids
    • C10M2207/2855Esters of aromatic polycarboxylic acids used as base material
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    • C10M2207/28Esters
    • C10M2207/30Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
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    • C10M2213/00Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06Perfluoro polymers
    • C10M2213/062Polytetrafluoroethylene [PTFE]
    • C10M2213/0626Polytetrafluoroethylene [PTFE] used as thickening agents
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10Amides of carbonic or haloformic acids
    • C10M2215/102Ureas; Semicarbazides; Allophanates
    • C10M2215/1026Ureas; Semicarbazides; Allophanates used as thickening material
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    • C10M2215/14Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
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    • C10M2215/26Amines
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    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/08Resistance to extreme temperature
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76Reduction of noise, shudder, or vibrations
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    • C10N2040/02Bearings
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    • C10N2040/14Electric or magnetic purposes
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    • C10N2040/38Conveyors or chain belts
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy
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    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02Reduction, e.g. hydrogenation

Definitions

  • the invention relates to high-temperature lubricants, in particular greases based on alkyl aromatics, a fully hydrogenated or hydrogenated polyisobutylene or a mixture thereof and a thickener.
  • the invention also relates to the use of this high-temperature grease for continuous use temperatures of up to 250 ° C.
  • the lubricants have to fulfill a large number of other tasks: They have to cool, reduce friction, wear and power transmission, protect against corrosion and at the same time have a sealing effect.
  • the high-temperature greases should be quiet.
  • lubricants are not suitable for high-temperature applications because they are destroyed at high temperatures, for example via oxidation and / or thermal decomposition reactions and polymerizations, and their lubricating properties are severely restricted. During decomposition reactions, the lubricant is split into low-molecular volatile components. Their evaporation leads to undesirable changes in viscosity, loss of oil and excessive vapor formation. From this results in a loss of lubricating effect. The lubricants also lose their lubricating effect through polymerization due to the formation of insoluble polymerization products.
  • Synthetic esters are often used as base oils for high-temperature applications because they have very good oxidative, hydrolytic and thermal stability.
  • the lubricants In order to meet the diverse requirements of high-temperature applications, the lubricants must have, among other things, high stability, low coefficients of friction and high wear resistance. In order to be able to guarantee uniform lubrication even at high temperatures, a liquid lubricating film must remain between metal parts during the entire processing process. For this reason, the lubricant must only evaporate a little at the maximum processing temperature, form few residues and form as few cracking residues as possible.
  • lubricants ensure that a separating, load-transferring lubricating film is built up between parts sliding or rolling on each other. This ensures that the metallic surfaces do not touch each other and therefore no wear occurs.
  • the lubricants must therefore meet high requirements. These include extreme operating conditions such as very high or very low speeds, high temperatures caused by high speeds or external heating, very low temperatures, for example with bearings that work in a cold environment or that are used in the air and Space travel occur. Modern lubricants should also be able to be used under so-called clean room conditions in order to avoid room pollution from abrasion or the consumption of lubricants.
  • Lubricants when using modern lubricants, it should be avoided that they evaporate and thus "clog", ie that they become solid after a short application and no longer show any lubricating effect. Special requirements are also placed on lubricants when they are used in such a way that the running surfaces of the bearings are not attacked by low friction, the bearing surfaces run quietly, and long running times are achieved without relubrication. Lubricants also have to withstand the effects of forces such as centrifugal force, gravity and vibrations.
  • a lubricating grease can stimulate vibrations in the rolling bearing when it participates in circulation (rolling over, flexing), which are "lubricant noises" in the medium 300 to 1,800 Hz and high 1,800 to 10,000 Hz frequency bands, compared to the bearing noise in the low frequency band at 50 to 300 Hz.
  • the lubricant noise is superimposed by the noise peaks that occur when hard particles roll over the rolling elements in the form of shock pulses on the bearing ring.
  • the evaluation of the noise behavior is based on the SKF BeQuiet + method.
  • a fats are known which are in gel form, which are difficult to produce in a homogeneous and stable form. These difficulties can be caused, for example, by the thickening agent used or the base oil.
  • a fat is provided that is homogeneous, stable and effective and that the desired properties are achieved by the fact that lesser amounts of thickening agents and other additives are present in the fat.
  • a hydrogenated polymer of butene or isobutylene with a relatively low molecular weight was used and a small amount of thickener in the form of Al complex soaps was used.
  • the object of the present invention is to provide a high-temperature grease which meets the above-mentioned requirements.
  • the lubricating grease should exhibit a good lubricating effect over a long period of time at a high temperature.
  • the cracking residues formed should not be laked up, but should be able to be dissolved again by fresh fat.
  • the high-temperature lubricant should have good hydrolytic stability, be corrosion- and wear-resistant, as well as good oxidation resistance and good low-temperature behavior adapted to the requirements. This is defined for lubricating oils by the pour point and for lubricating greases by the flow pressure at low temperatures.
  • the high-temperature grease should exhibit good noise behavior, have long running times and essentially cause no signs of wear on the devices.
  • the high-temperature grease according to the invention is distinguished by excellent performance.
  • the high-temperature grease according to the invention shows high thermal stability combined with a long service life and good lubricating properties.
  • the viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm 2 / s, more preferably from 30 to 300 m 2 / s.
  • the high temperature grease according to the invention can contain a second oil which comprises an alkyl aromatic.
  • An aromatic is preferably used.
  • an aromatic is understood to mean a monocyclic, bicyclic or tricyclic ring system with four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings in a bicyclic or tricyclic ring system being aromatic.
  • a bicyclic ring system which preferably has 10 carbon atoms, is preferably used.
  • the aromatic is preferably substituted by one or more aliphatic substituents.
  • the aromatic is particularly preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.
  • an alkyl group is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 to 17 and in particular 6 to 15 carbon atoms.
  • An alkyl group can be linear or branched and is optionally substituted with one or more of the above-mentioned substituents.
  • the lubricating grease particularly preferably contains at least one aliphatically substituted naphthalene, in particular at least one alkyl-substituted naphthalene.
  • the naphthalene is preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.
  • the viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm 2 / s, more preferably from 30 to 300 m 2 / s.
  • the high-temperature grease according to the invention further comprises a polyisobutylene.
  • the polyisobutylene can be used in hydrogenated or fully hydrogenated form, and a mixture of hydrogenated and fully hydrogenated polyisobutylene can also be used. Fully hydrogenated polyisobutylenes are preferably used.
  • the polyisobutylene is present in the composition in an amount of 6 to 45 percent by weight, preferably 10 to 45 percent % By weight, in particular 15 to 45% by weight, are used.
  • the polyisobutylene has a number average molecular weight of 115 to 10,000 g / mol, preferably 160 to 5000 g / mol.
  • the high-temperature grease according to the invention also comprises from 0.1 to 10% by weight, additives, which are used individually or in combination and are selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants.
  • the high-temperature grease according to the invention also comprises a thickening agent.
  • the thickener in the high-temperature grease of the lubricant composition according to the invention is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatophenylmethane, 4,4'-diisocyanatodi- phenyl, 4,4'-diisocyanato-3-3'-dimethylphenyl, 4,4'-diisocyanato-3,3'-dimethylphenylmethane, which can be used individually or in combination, with an amine of the general formula R ' 2 -NR , or a diamine of the general formula R ' 2 -NR-NR' 2 , where R is an aryl, alky
  • additives for high-temperature oils and greases the following additives have particularly good physical and chemical properties:
  • antioxidants can reduce or even prevent the oxidation of the oil or fat according to the invention, especially when it is used. In the event of oxidation, undesirable free radicals can arise and, as a result, more decomposition reactions of the high-temperature lubricant occur.
  • the high temperature fat is stabilized by adding antioxidants.
  • Antioxidants particularly suitable according to the invention are the following compounds: Styrenated diphenylamines, diaromatic amines, phenolic resins, thiophenolic resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alphanaphthylamine, phenyl-beta-naphthylamine, octylated / butylated diphenylamine, dialpha-tocopherol, phenyl-phenyl-phenol, sulfur-propane, phenyl-tert-butyl-phenyl compounds , Phenolic compounds and mixtures of these components.
  • the high-temperature grease can also contain corrosion protection 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 (C 11-14 ) -alkylamines, mixture of phosphoric acid and mono- and diisooctyl esters reacted with tert-alkylamine and primary (C 12-14 ) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates.
  • metal deactivators or ion complexing agents include triazoles, imidazolines,
  • IRGAMET® 39 IRGACOR® DSS G, amine O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 and CI-498.
  • anti-wear additives are amines, amine phosphates, phosphates, thiophosphates, phosphorothionates and mixtures of these components.
  • 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 .®, FLUORBOND ® FG, SYNALOX® 40-D, ACHESON® FGA 1820 and ACHESON® FGA 1810.
  • the grease can contain solid lubricants such as PTFE, 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, SiO 2 modifications or a mixture thereof.
  • solid lubricants such as PTFE, 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, SiO 2 modifications or a mixture thereof.
  • the high-temperature grease according to the invention can contain, as a further base oil, an oil, preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, pyromellitic acid esters, diphenyl ethers, phloroglucinic esters and / or poly-alpha-olefins, alpha-olefin copolymers.
  • an oil preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, pyromellitic acid esters, diphenyl ethers, phloroglucinic esters and / or poly-alpha-olefins, alpha-olefin copolymers.
  • the high-temperature grease according to the invention due to its physical and chemical properties, is excellent for use in chains, roller and plain bearings, in vehicle technology, conveyor technology, mechanical engineering, office technology and in industrial systems and machines, but also in the Areas of household machines and consumer electronics. Due to its good temperature resistance, it can also be used at high operating temperatures of up to 260 ° C, preferably at temperatures of 150 to 250 ° C.
  • the invention also relates to a method for producing the above-described high-temperature grease, in which the base oils and the additives are mixed with one another.
  • Estolides or aliphatically substituted naphthalenes are placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil are added with stirring. Then the mixture is stirred for 1 hour to obtain a homogeneous mixture. The anti-wear agents and the antioxidant are added to the kettle at 60 ° C. while stirring. After approx. 1 hour, the finished oil can be filled into the containers provided.
  • the base oil is placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil and the thickener are added with stirring. The thickener results from an in situ reaction of the reactants used in the base oil. The mixture is then heated to 150 ° C. to 210 ° C., stirred for several hours and cooled again. In the cooling process at approx. 60 ° C, the necessary wear protection agents, antioxidants and corrosion protection agents are added. A homogeneous mixture of the fat is obtained by the final homogenization step using a roller, colloid mill or the Gaulin.
  • compositions of the high temperature greases are shown in Table 6. ⁇ u> Table 6 ⁇ /u> Type Li complex Li complex Li complex Di-urea Di-urea Di-urea Reference example 3
  • Example 7 Reference example 8 Trimellitic acid ester [% by weight] 60 0 0 65.2 0 0 Estolide [wt.%] 0 0 56 0 0 65.2 alkylated naphthalene [wt.%] 0 64 0 0 65.2 0 fully hydrogenated polyisobutylene [% by weight] 26th 25th 25th 25th 25th 25th 25th Additive package [wt.%] 4th 1 4th 1 1 1 Thickener concentration [wt.%] 10 10 15.0 8.8 8.8 8.8
  • the thickeners used in Examples 3 to 8 are: Reference example 3: LiOH, 12-hydroxystearic acid, azelaic acid, Example 4: LiOH, 12-hydroxystearic acid, azelaic acid, Reference example 5: LiOH, 12-hydroxystearic acid, azelaic acid, Reference example 6: Di-urea; Methylene-diphenyl-diisocyanate (MDI), octylamine, oleylamine Example 7: Di-urea; MDI, octylamine, oleylamine Reference example 8: Di-urea; MDI, octylamine, oleylamine
  • Oil separation has a decisive influence on the lubricating effect of a grease. It must be ensured that, on the one hand, the oil separation is not too high and the oil runs out of the bearing and is therefore no longer available to the tribo-system and, on the other hand, no oil separation can be observed and the lubricating effect of the grease is lost.
  • the oil separation should ideally be between 0.5 and 8 wt .-%, so that an optimal Can form a lubricating film in the bearing.
  • the greases in the examples were subjected to an FE 9 roller bearing test according to DIN 51 821, in which the service life of the greases examined is determined and the upper service temperature of lubricating greases in roller bearings at medium speeds and medium axial loads is determined.
  • Table 8 shows that the running times due to the use of PIB in conjunction with various base oils have long running times and are therefore suitable for high application temperatures in continuous operation.
  • Table 11 shows that there are significant differences when using fully hydrogenated and partially hydrogenated PIB. For example, it is no longer possible to partially dissolve the residue on the basis of the partially hydrogenated PIB, while the oil with the fully hydrogenated PIB has very good redissolving properties.

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Description

Die Erfindung betrifft Hochtemperaturschmierstoffe, insbesondere Fette auf Basis von Alkylaromaten, einem vollhydrierten oder hydrierten Polyisobutylen oder einer Mischung daraus und einem Verdickungsmittel. Die Erfindung betrifft ferner die Verwendung dieses Hochtemperaturfetts für Dauereinsatztemperaturen von bis zu 250°C.The invention relates to high-temperature lubricants, in particular greases based on alkyl aromatics, a fully hydrogenated or hydrogenated polyisobutylene or a mixture thereof and a thickener. The invention also relates to the use of this high-temperature grease for continuous use temperatures of up to 250 ° C.

Neben der Schmierwirkung müssen die Schmierstoffe noch eine Vielzahl weiterer Aufgaben erfüllen: Sie müssen kühlen, Reibung, Verschleiß und Kraftübertragung verringern, vor Korrosion schützen und gleichzeitig eine dichtende Wirkung aufweisen. Darüber hinaus sollten die Hochtemperaturfette geräuscharm sein.In addition to the lubricating effect, the lubricants have to fulfill a large number of other tasks: They have to cool, reduce friction, wear and power transmission, protect against corrosion and at the same time have a sealing effect. In addition, the high-temperature greases should be quiet.

Herkömmliche Schmierstoffe sind für Hochtemperaturanwendungen nicht geeignet, da sie bei hohen Temperaturen beispielsweise über Oxidations- und/oder thermische Zersetzungsreaktionen und Polymerisationen zerstört werden und ihre schmierenden Eigenschaften stark eingeschränkt werden. Bei Zersetzungsreaktionen wird der Schmierstoff in niedermolekulare flüchtige Komponenten gespalten. Deren Verdampfen führt zu unerwünschten Viskositätsänderungen, Ölverlust und zur übermäßigen Dampfbildung. Hieraus resultiert ein Verlust der Schmierwirkung. Auch durch Polymerisation verlieren die Schmierstoffe ihre Schmierwirkung aufgrund der Bildung unlöslicher Polymerisationsprodukte.Conventional lubricants are not suitable for high-temperature applications because they are destroyed at high temperatures, for example via oxidation and / or thermal decomposition reactions and polymerizations, and their lubricating properties are severely restricted. During decomposition reactions, the lubricant is split into low-molecular volatile components. Their evaporation leads to undesirable changes in viscosity, loss of oil and excessive vapor formation. From this results in a loss of lubricating effect. The lubricants also lose their lubricating effect through polymerization due to the formation of insoluble polymerization products.

Das Entfernen dieser Verschmutzungen erhöht die Wartungsarbeiten und produziert chemische Abfallstoffe, die aufwendig entsorgt werden müssen. Aufgrund der vermehrten Reinigungs- und Wartungsarbeiten erhöhen sich die Ausfallzeiten. Insgesamt führt die Verwendung von ungeeigneten Schmierstoffen bei Hochtemperaturanwendungen zu höheren Kosten, da die Arbeitsgeräte verschmutzen und ein höherer Bedarf an Schmierstoffen besteht. Darüber hinaus sinkt die Produktqualität.Removing this contamination increases maintenance work and produces chemical waste that is laborious to dispose of. Due to the increased cleaning and maintenance work, the downtimes increase. Overall, the use of unsuitable lubricants in high-temperature applications leads to higher costs, since the tools become dirty and there is a higher demand for lubricants. In addition, the product quality decreases.

Als Basisöle für Hochtemperaturanwendungen werden oftmals synthetische Ester eingesetzt, da diese über eine sehr gute oxidative, hydrolytische und thermische Stabilität verfügen.Synthetic esters are often used as base oils for high-temperature applications because they have very good oxidative, hydrolytic and thermal stability.

Um den vielfältigen Anforderungen bei Hochtemperaturanwendungen gerecht zu werden, müssen die Schmierstoffe unter anderem eine hohe Stabilität, niedrige Reibungsbeiwerte und hohe Verschleißfestigkeiten aufweisen. Um eine gleichmäßige Schmierung auch bei hohen Temperaturen gewährleisten zu können, muss während des gesamten Verarbeitungsprozesses ein flüssiger Schmierfilm zwischen Metallteilen bestehen bleiben. Deshalb darf der Schmierstoff bei der maximalen Verarbeitungstemperatur nur wenig verdampfen, wenig Rückstände bilden und möglichst wenig Vercrackungsrückstände bilden.In order to meet the diverse requirements of high-temperature applications, the lubricants must have, among other things, high stability, low coefficients of friction and high wear resistance. In order to be able to guarantee uniform lubrication even at high temperatures, a liquid lubricating film must remain between metal parts during the entire processing process. For this reason, the lubricant must only evaporate a little at the maximum processing temperature, form few residues and form as few cracking residues as possible.

Hohe Temperaturen treten oftmals bei der Verwendung in Ketten, Wälz- und Gleitlagern, in der Fahrzeugtechnik, der Fördertechnik, dem Maschinenbau, der Bürotechnik sowie in industriellen Anlagen und Maschinen, aber auch in den Bereichen der Haushaltsmaschinen und der Unterhaltungselektronik.High temperatures often occur when used in chains, roller and plain bearings, in vehicle technology, conveyor technology, mechanical engineering, office technology and in industrial systems and machines, but also in the areas of household machines and entertainment electronics.

In Wälz- und Gleitlagern sorgen Schmierstoffe dafür, dass zwischen aufeinander gleitenden oder abrollenden Teilen ein trennender, lastübertragender Schmierfilm aufgebaut wird. Damit wird erreicht, dass die metallischen Oberflächen sich nicht berühren und somit auch kein Verschleiß auftritt. Die Schmierstoffe müssen deshalb hohen Anforderungen genügen. Dazu gehören extreme Betriebsbedingungen, wie sehr hohe oder sehr niedrige Drehzahlen, hohe Temperaturen, die durch hohe Drehzahlen oder durch Fremderwärmung bedingt sind, sehr tiefe Temperaturen, beispielsweise bei Lagern, die in kalter Umgebung arbeiten oder, die bei der Verwendung in der Luft- und Raumfahrt auftreten. Ebenso sollten die modernen Schmierstoffe unter sogenannten Reinraumbedingungen einsetzbar sein, um die Raumverschmutzung durch den Abrieb bzw. den Verbrauch an Schmierstoffen zu vermeiden. Außerdem sollte bei der Anwendung der modernen Schmierstoffe vermieden werden, dass sie verdampfen und damit "verlacken", d.h., dass sie nach kurzer Anwendung fest werden und keine Schmierwirkung mehr zeigen. An Schmierstoffe werden auch besondere Anforderungen bei der Anwendung dahingehend gestellt, dass die Laufflächen der Lager durch geringe Reibung nicht angegriffen werden, die Lagerflächen geräuscharm laufen, sowie langen Laufzeiten ohne Nachschmierung erreicht werden. Auch müssen Schmierstoffe Krafteinwirkungen, wie Fliehkraft, Schwerkraft und Schwingungen widerstehen.In roller and plain bearings, lubricants ensure that a separating, load-transferring lubricating film is built up between parts sliding or rolling on each other. This ensures that the metallic surfaces do not touch each other and therefore no wear occurs. The lubricants must therefore meet high requirements. These include extreme operating conditions such as very high or very low speeds, high temperatures caused by high speeds or external heating, very low temperatures, for example with bearings that work in a cold environment or that are used in the air and Space travel occur. Modern lubricants should also be able to be used under so-called clean room conditions in order to avoid room pollution from abrasion or the consumption of lubricants. In addition, when using modern lubricants, it should be avoided that they evaporate and thus "clog", ie that they become solid after a short application and no longer show any lubricating effect. Special requirements are also placed on lubricants when they are used in such a way that the running surfaces of the bearings are not attacked by low friction, the bearing surfaces run quietly, and long running times are achieved without relubrication. Lubricants also have to withstand the effects of forces such as centrifugal force, gravity and vibrations.

Wichtige Kenngröße für eine lange Funktionsdauer eines fettgeschmierten Wälzlagers im Hochtemperaturbereich ist neben der oberen Gebrauchstemperatur das Geräuschverhalten des Schmierstoffes. Ein Schmierfett kann bei Umlaufteilnahme (Überrollung, Walkung) Schwingungen im Wälzlager anregen, die als "Schmierstoffgeräusche" in den Frequenzbändern Medium 300 bis 1.800 Hz und High 1.800 bis 10.000 Hz, gegenüber den Lagergeräuschen im Frequenzband Low bei 50 bis 300 Hz liegen. Das Schmierstoffgeräusch wird von den Geräuschspitzen überlagert, die bei der Überrollung von harten Partikeln durch die Wälzkörper in Form von Stoßimpulsen auf dem Lagerring entstehen. Die Bewertung des Geräuschverhaltens erfolgt nach der SKF-BeQuiet+ - Methode.An important parameter for a long service life of a grease-lubricated roller bearing in the high temperature range is, in addition to the upper service temperature, the noise behavior of the lubricant. A lubricating grease can stimulate vibrations in the rolling bearing when it participates in circulation (rolling over, flexing), which are "lubricant noises" in the medium 300 to 1,800 Hz and high 1,800 to 10,000 Hz frequency bands, compared to the bearing noise in the low frequency band at 50 to 300 Hz. The lubricant noise is superimposed by the noise peaks that occur when hard particles roll over the rolling elements in the form of shock pulses on the bearing ring. The evaluation of the noise behavior is based on the SKF BeQuiet + method.

Die Fettgeräuschklassen werden wie folgt eingeteilt:

  • GNX: etwas schlechter als GN1 (sehr schlechtes Geräuschverhalten)
  • GN1: >95% aller Peaks sind <=40 µm/s (schlechtes Geräuschverhalten)
  • GN2: >95% aller Peaks sind <=20 µm/s; > 98% aller Peaks sind <= 40 µm/s (mittleres Geräuschverhalten)
  • GN3: >95% aller Peaks sind <=10 µm/s; > 98% aller Peaks sind <= 20 µm/s; > 100% aller Peaks sind <= 40 µm/s (gutes Geräuschverhalten)
  • GN4: >95% aller Peaks sind <= 5 µm/s; > 98% aller Peaks sind <= 10 µm/s; > 100% aller Peaks sind <= 20 µm/s (sehr gutes Geräuschverhalten)
The fat noise classes are divided as follows:
  • GNX: slightly worse than GN1 (very poor noise behavior)
  • GN1: > 95% of all peaks are <= 40 µm / s (poor noise behavior)
  • GN2: > 95% of all peaks are <= 20 µm / s; > 98% of all peaks are <= 40 µm / s (average noise behavior)
  • GN3: > 95% of all peaks are <= 10 µm / s; > 98% of all peaks are <= 20 µm / s; > 100% of all peaks are <= 40 µm / s (good noise behavior)
  • GN4: > 95% of all peaks are <= 5 µm / s; > 98% of all peaks are <= 10 µm / s; > 100% of all peaks are <= 20 µm / s (very good noise behavior)

Je besser das Geräuschverhalten eines Schmierfettes, desto geringer sind die durch den Schmierstoff erzwungenen Schwingungen des Lagers. Dies ist gleichbedeutend mit einer geringen Belastung des Lagers und führt zu einer längeren Funktionsdauer der Lagerung.The better the noise behavior of a lubricating grease, the lower the vibrations of the bearing caused by the lubricant. This is synonymous with a low load on the bearing and leads to a longer functional life of the bearing.

Aus der US 4 075 112 A sind Fette bekannt, die in Gelform vorliegen, bei denen es Schwierigkeiten gibt, diese in homogener und stabiler Form herzustellen. Diese Schwierigkeiten können beispielsweise von dem verwendeten Verdickungsmittel oder dem Basisöl verursacht werden. Es wird ein Fett bereitgestellt, dass homogen, stabil und wirksam ist, und die gewünschten Eigenschaften dadurch erreicht werden, dass in dem Fett geringere Mengen an Verdickungsmittel und anderen Zusätzen vorhanden sind. Dazu wurde ein hydriertes Polymer aus Buten oder Isobutylen mit relativ niedrigem Molekulargewicht eingesetzt und es wurde eine geringe Menge Verdickungsmittel in Form von Al-Komplexseifen verwendet.From the U.S. 4,075,112 A fats are known which are in gel form, which are difficult to produce in a homogeneous and stable form. These difficulties can be caused, for example, by the thickening agent used or the base oil. A fat is provided that is homogeneous, stable and effective and that the desired properties are achieved by the fact that lesser amounts of thickening agents and other additives are present in the fat. For this purpose, a hydrogenated polymer of butene or isobutylene with a relatively low molecular weight was used and a small amount of thickener in the form of Al complex soaps was used.

Die Aufgabe der vorliegenden Erfindung besteht darin, ein Hochtemperaturfett bereitzustellen, das den oben genannten Anforderungen entspricht. Insbesondere soll das Schmierfett bei hoher Temperatur über einen langen Zeitraum eine gute Schmierwirkung zeigen. Des weiteren sollen die gebildeten Vercrackungsrückstände nicht verlacken, sondern durch Frischfett wieder anlösbar sein. Ferner soll der Hochtemperaturschmierstoff eine gute hydrolytische Stabilität aufweisen, korrosions- und verschleißresistent sein, sowie eine gute Oxidationsbeständigkeit und ein an die Anforderung angepasstes gutes Tieftemperaturverhalten besitzen. Dies wir bei Schmierölen durch den Pourpoint und bei Schmierfetten durch den Fließdruck bei tiefen Temperaturen definiert. Außerdem soll das Hochtemperaturfett ein gutes Geräuschverhalten zeigen, lange Laufzeiten aufweisen und im wesentlichen keine Verschleißerscheinungen der Vorrichtungen bewirken.The object of the present invention is to provide a high-temperature grease which meets the above-mentioned requirements. In particular, the lubricating grease should exhibit a good lubricating effect over a long period of time at a high temperature. Furthermore, the cracking residues formed should not be laked up, but should be able to be dissolved again by fresh fat. Furthermore, the high-temperature lubricant should have good hydrolytic stability, be corrosion- and wear-resistant, as well as good oxidation resistance and good low-temperature behavior adapted to the requirements. This is defined for lubricating oils by the pour point and for lubricating greases by the flow pressure at low temperatures. In addition, the high-temperature grease should exhibit good noise behavior, have long running times and essentially cause no signs of wear on the devices.

Diese Aufgabe wird erfindungsgemäß durch ein Hochtemperaturfett umfassend folgende Komponenten gelöst:

  1. a) 91,9 bis 25 Gew.-% mindestens eines Öls aus der Gruppe der Alkylaromaten, vorzugsweise einem aliphathisch substituierten Naphthalin, ,
  2. b) 6 bis 45 Gew.% eines Polymers, nämlich eines hydrierten oder vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen;
  3. c) 0,1 bis 10 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen und
  4. d) 2 bis 20 Gew.-% Verdickungsmittel.
According to the invention, this object is comprehensively achieved by a high temperature grease solved the following components:
  1. a) 91.9 to 25% by weight of at least one oil from the group of alkyl aromatics, preferably an aliphatic substituted naphthalene,
  2. b) 6 to 45% by weight of a polymer, namely a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene;
  3. c) 0.1 to 10% by weight of additives, individually or in combination, selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants and
  4. d) 2 to 20% by weight of thickener.

Überraschend wurde gefunden, dass sich das erfindungsgemäße Hochtemperaturfett durch eine hervorragende Leistungsfähigkeit auszeichnen. So zeigt das erfindungsgemäße Hochtemperaturfett eine hohe thermische Stabilität kombiniert mit einer hohen Lebensdauer und guten Schmiereigenschaften.It has surprisingly been found that the high-temperature grease according to the invention is distinguished by excellent performance. The high-temperature grease according to the invention shows high thermal stability combined with a long service life and good lubricating properties.

Die Viskosität, gemessen bei 40 °C, des aliphathisch substituierten Naphthalins beträgt vorzugsweise 30 bis 600 mm2/s, bevorzugter 30 bis 300 m2/s.The viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm 2 / s, more preferably from 30 to 300 m 2 / s.

Das erfindungsgemäße Hochtemperaturfett kann ein zweites Öl enthalten, das einen Alkylaromaten umfasst. Bevorzugt wird ein Aromat eingesetzt. Unter einem Aromaten wird erfindungsgemäß ein monocyclisches, bicyclisches oder tricyclisches Ringsystem mit vier bis fünfzehn Kohlenstoffatomen verstanden, wobei das monocyclische Ringsystem aromatisch ist oder zumindest einer der Ringe in einem bi- oder tricylischen Ringsystem aromatisch ist. Bevorzugt wird ein bicyclisches Ringsystem, das vorzugsweise 10 Kohlenstoffatome aufweist, eingesetzt.The high temperature grease according to the invention can contain a second oil which comprises an alkyl aromatic. An aromatic is preferably used. According to the invention, an aromatic is understood to mean a monocyclic, bicyclic or tricyclic ring system with four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings in a bicyclic or tricyclic ring system being aromatic. A bicyclic ring system, which preferably has 10 carbon atoms, is preferably used.

Bevorzugt ist der Aromat mit einem oder mehreren aliphatischen Substituenten substituiert. Besonders bevorzugt ist der Aromat mit ein bis vier aliphatischen Substituenten und insbesondere mit zwei oder drei aliphatischen Substituenten substituiert.The aromatic is preferably substituted by one or more aliphatic substituents. The aromatic is particularly preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.

Eine Alkylgruppe ist erfindungsgemäß eine gesättigte aliphatische Kohlenwasserstoffgruppe mit 1 bis 30, vorzugsweise 3 bis 20, noch bevorzugter 4 bis 17 und insbesondere 6 bis 15 Kohlenstoffatomen. Eine Alkylgruppe kann linear oder verzweigt sein und ist wahlweise mit einem oder mehreren der oben genannten Substituenten substituiert.According to the invention, an alkyl group is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 to 17 and in particular 6 to 15 carbon atoms. An alkyl group can be linear or branched and is optionally substituted with one or more of the above-mentioned substituents.

Erfindungsgemäß besonders bevorzugt enthält das Schmierfett mindestens ein aliphatisch substituiertes Naphthalin, insbesondere mindestens ein alkylsubstituiertes Naphthalin. Bevorzugt ist das Naphthalin mit ein bis vier aliphatischen Substituenten substituiert und insbesondere mit zwei oder drei aliphatischen Substituenten.According to the invention, the lubricating grease particularly preferably contains at least one aliphatically substituted naphthalene, in particular at least one alkyl-substituted naphthalene. The naphthalene is preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.

Praktische Versuche haben gezeigt, dass Gemische unterschiedlich substituierter Naphthaline, das heißt Gemische aus Naphthalinen, die einen unterschiedlichen Substitutionsgrad und unterschiedliche aliphatische Substituenten aufweisen, besonders geeignet sind. Durch Variation der Mischungszusammensetzung können in diesem Fall die Eigenschaften, wie beispielsweise die Viskosität, des Hochtemperaturschmierstoffs besonders einfach eingestellt werden. Aliphatisch substituierte Naphthaline zeichnen sich ferner durch hervorragende Lösungseigenschaften und hohe thermo-oxidative Stabilität aus.Practical tests have shown that mixtures of differently substituted naphthalenes, that is to say mixtures of naphthalenes which have different degrees of substitution and different aliphatic substituents, are particularly suitable. In this case, by varying the composition of the mixture, the properties, such as the viscosity, of the high-temperature lubricant can be set particularly easily. Aliphatically substituted naphthalenes are also distinguished by excellent solution properties and high thermo-oxidative stability.

Die Viskosität, gemessen bei 40 °C, des aliphathisch substituierten Naphthalins beträgt vorzugsweise 30 bis 600 mm2/s, bevorzugter 30 bis 300 m2/s.The viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm 2 / s, more preferably from 30 to 300 m 2 / s.

Das erfindungsgemäße Hochtemperaturfett umfasst des weiteren ein Polyisobutylen. 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 hydrierter oder vollhydrierter Form eingesetzt werden, ebenso kann eine Mischung aus hydriertem und vollhydriertem Polyisobutylen verwendet werden. Bevorzugt werden vollhydrierte Polyisobutylene eingesetzt. Das Polyisobutylen ist in einer Menge von 6 bis 45 Gew.-% in der Zusammensetzung vorhanden, bevorzugt werden 10 bis 45 Gew.-%, insbesondere 15 bis 45 Gew.-% eingesetzt.The high-temperature grease according to the invention further comprises a polyisobutylene. A suitable choice of polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, can influence the properties of the fat according to the invention, for example its kinematic viscosity, in the desired manner. The polyisobutylene can be used in hydrogenated or fully hydrogenated form, and a mixture of hydrogenated and fully hydrogenated polyisobutylene can also be used. Fully hydrogenated polyisobutylenes are preferably used. The polyisobutylene is present in the composition in an amount of 6 to 45 percent by weight, preferably 10 to 45 percent % By weight, in particular 15 to 45% by weight, are used.

Gemäß einer weiteren bevorzugten Ausführungsform weist das Polyisobutylen ein zahlenmittleres Molekulargewicht von 115 bis 10.000 g/mol, vorzugsweise von 160 bis 5000 g/mol auf.According to a further preferred embodiment, the polyisobutylene has a number average molecular weight of 115 to 10,000 g / mol, preferably 160 to 5000 g / mol.

Das erfindungsgemäße Hochtemperaturfett umfasst des weiteren von 0,1 bis 10 Gew.-%, Additive, die einzeln oder in Kombination eingesetzt werden und aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen, ausgewählt werden.The high-temperature grease according to the invention also comprises from 0.1 to 10% by weight, additives, which are used individually or in combination and are selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants.

Das erfindungsgemäße Hochtemperaturfett umfasst außerdem ein Verdickungsmittel. Das Verdickungsmittel in dem erfindungsgemäßen Hochtemperaturfett der Schmierstoffzusammensetzung ist entweder ein Reaktionsprodukt aus einem Diisocyanat, vorzugsweise 2,4-Diisocyanatotoluol, 2,6-Diisocyanatotoluol, 4,4'-Diisocyanatodiphenylmethan, 2,4'-Diisocyanatophenylmethan, 4,4'-Diisocyanatodi-phenyl, 4,4'-Diisocyanato-3-3'-dimethylphenyl, 4,4'-Diisocyanato-3,3'-dimethylphenylmethan, die einzeln oder in Kombination verwendet werden können, mit einem Amin der allgemeinen Formel R'2-N-R, oder einem Diamin der allgemeinen Formel R'2-N-R-NR'2, wobei R ein Aryl-, Alkyl- oder Alkylenrest mit 2 bis 22 Kohlenstoffatomen ist und R' identisch oder verschieden ein Wasserstoff, ein Alkyl-, Alkylen- oder Arylrest ist, oder mit Gemischen aus Aminen und Diaminen oder
wird aus gewählt aus Al-Komplexseifen, Metall-Einfachseifen der Elemente der ersten und zweiten Hauptgruppe des Perriodensystems, Metall-Komplexseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems, Bentonite, Sulfonate, Silikate, Aerosil, Polyimide oder PTFE oder einer Mischung der vorgenannten Verdickungsmittel.
The high-temperature grease according to the invention also comprises a thickening agent. The thickener in the high-temperature grease of the lubricant composition according to the invention is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatophenylmethane, 4,4'-diisocyanatodi- phenyl, 4,4'-diisocyanato-3-3'-dimethylphenyl, 4,4'-diisocyanato-3,3'-dimethylphenylmethane, which can be used individually or in combination, with an amine of the general formula R ' 2 -NR , or a diamine of the general formula R ' 2 -NR-NR' 2 , where R is an aryl, alkyl or alkylene radical having 2 to 22 carbon atoms and R ', identically or differently, is a hydrogen, an alkyl, alkylene or aryl radical is, or with mixtures of amines and diamines or
is selected from Al complex soaps, metal single soaps of the elements of the first and second main group of the periodic table, metal complex soaps of the elements of the first and second main group of the periodic table, bentonites, sulfonates, silicates, Aerosil, polyimides or PTFE or a mixture of the above Thickener.

Als Additive für Hochtemperaturöle und -fette haben die nachfolgend genannten Additive besonders gute physikalische und chemische Eigenschaften:As additives for high-temperature oils and greases, the following additives have particularly good physical and chemical properties:

Der Zusatz von Antioxidantien kann die Oxidation des erfindungsgemäßen Öls oder Fetts, insbesondere bei seinem Einsatz, verringern oder gar verhindern. Bei einer Oxidation können unerwünschte freie Radikale entstehen und infolgedessen vermehrt Zersetzungsreaktionen des Hochtemperaturschmierstoffes auftreten. Durch die Zugabe von Antioxidantien wird das Hochtemperaturfett stabilisiert.The addition of antioxidants can reduce or even prevent the oxidation of the oil or fat according to the invention, especially when it is used. In the event of oxidation, undesirable free radicals can arise and, as a result, more decomposition reactions of the high-temperature lubricant occur. The high temperature fat is stabilized by adding antioxidants.

Erfindungsgemäß besonders geeignete Antioxidantien sind die folgenden Verbindungen:
Styrolisierte Diphenylamine, diaromatische Amine, Phenolharze, Thiophenolharze, Phosphite, butyliertes Hydroxytoluol, butyliertes Hydroxyanisol, Phenyl-alphanaphthylamin, Phenyl-beta-naphthylamin, octyliertes/butyliertes Diphenylamin, dialpha-Tocopherol, di-tert.-butyl-Phenyl, Benzolpropansäure, schwefelhaltige Phenolverbindungen, Phenolverbindungen und Mischungen dieser Komponenten.
Antioxidants particularly suitable according to the invention are the following compounds:
Styrenated diphenylamines, diaromatic amines, phenolic resins, thiophenolic resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alphanaphthylamine, phenyl-beta-naphthylamine, octylated / butylated diphenylamine, dialpha-tocopherol, phenyl-phenyl-phenol, sulfur-propane, phenyl-tert-butyl-phenyl compounds , Phenolic compounds and mixtures of these components.

Weiterhin kann das Hochtemperaturfett Korrosionsschutzadditive, Metalldesaktivatoren oder Ionen-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 (C11-14)-Alkylaminen, Gemisch aus Phosphorsäure und Mono-und Diisooctylester umgesetzt mit tert.-Alkylamin und primären (C12-14)-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.The high-temperature grease can also contain corrosion protection 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 (C 11-14 ) -alkylamines, mixture of phosphoric acid and mono- and diisooctyl esters reacted with tert-alkylamine and primary (C 12-14 ) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates. Commercially available additives are the following: IRGAMET® 39, IRGACOR® DSS G, amine O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 and CI-498.

Weitere Verschleißschutzadditive sind Amine, Aminphosphate, Phosphate, Thiophosphate, Phosphorthionate und Mischungen dieser Komponenten. 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, phosphorothionates and mixtures of these components. 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 .®, FLUORBOND ® FG, SYNALOX® 40-D, ACHESON® FGA 1820 and ACHESON® FGA 1810.

Des weiteren kann das Fett Festschmierstoffe wie PTFE, 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, SiO2-Modifikationen oder eine Mischung daraus enthalten.Furthermore, the grease can contain solid lubricants such as PTFE, 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, SiO 2 modifications or a mixture thereof.

Praktische Versuche haben gezeigt, dass das erfindungsgemäße Hochtemperaturfett bis zu einer Temperatur von 250°C keine oder zu vernachlässigende Zersetzungserscheinungen aufweist. Hierunter wird verstanden, dass sich weniger als 10% des Schmierstoffs zersetzen.Practical tests have shown that the high-temperature grease according to the invention shows no or negligible decomposition phenomena up to a temperature of 250 ° C. This means that less than 10% of the lubricant decomposes.

Das erfindungsgemäße Hochtemperaturfett kann als ein weiteres Grundöl ein Öl, vorzugsweise ausgewählt aus der Gruppe bestehend aus Mineralöl, aliphatischen Carbonsäure- und Dicarbonsäureestern, Fettsäuretriglyceriden, Pyromellitsäureester, Diphenylether, Phloroglucinester und/oder Poly-alpha-olefinen, alpha-Olefinen-Copolymere enthalten.The high-temperature grease according to the invention can contain, as a further base oil, an oil, preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, pyromellitic acid esters, diphenyl ethers, phloroglucinic esters and / or poly-alpha-olefins, alpha-olefin copolymers.

Praktische Versuche haben gezeigt, dass das erfindungsgemäße Hochtemperaturfett aufgrund seiner physikalischen und chemischen Eigenschaften hervorragend bei der Verwendung in Ketten, Wälz- und Gleitlagern, in der Fahrzeugtechnik, der Fördertechnik, dem Maschinenbau, der Bürotechnik sowie in industriellen Anlagen und Maschinen, aber auch in den Bereichen der Haushaltsmaschinen und der Unterhaltungselektronik ist. Aufgrund seiner guten Temperaturbeständigkeit kann er auch bei hohen Einsatztemperaturen bis 260°C, vorzugsweise bei Temperaturen von 150 bis 250°C eingesetzt werden.Practical tests have shown that the high-temperature grease according to the invention, due to its physical and chemical properties, is excellent for use in chains, roller and plain bearings, in vehicle technology, conveyor technology, mechanical engineering, office technology and in industrial systems and machines, but also in the Areas of household machines and consumer electronics. Due to its good temperature resistance, it can also be used at high operating temperatures of up to 260 ° C, preferably at temperatures of 150 to 250 ° C.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung des oben beschriebenen Hochtemperaturfetts, bei dem die Grundöle und die Additive miteinander vermischt werden.The invention also relates to a method for producing the above-described high-temperature grease, in which the base oils and the additives are mixed with one another.

Die Erfindung wird nun anhand der nachfolgenden Beispiele näher erläutert.The invention will now be explained in more detail with the aid of the following examples.

Referenzbeispiele 1 bis 2Reference examples 1 to 2

Herstellung eines HochtemperaturölsProduction of a high temperature oil

Es werden Estolide oder aliphatisch substituierte Naphthaline in einem Rührkessel vorgelegt. Bei 100°C wird unter Rühren das Polyisobutylen und ggf. ein weiteres Öl hinzugegeben. Anschließend wird das Gemisch 1 h gerührt, um eine homogene Mischung zu erhalten. Die Verschleißschutzmittel und das Antioxidationsmittel werden bei 60°C unter Rühren in den Kessel zugegeben. Nach ca. 1 Stunde kann das fertige Öl in die vorgesehenen Gebinde abgefüllt werden.Estolides or aliphatically substituted naphthalenes are placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil are added with stirring. Then the mixture is stirred for 1 hour to obtain a homogeneous mixture. The anti-wear agents and the antioxidant are added to the kettle at 60 ° C. while stirring. After approx. 1 hour, the finished oil can be filled into the containers provided.

Zusammensetzung der Hochtemperaturöle:Composition of high temperature oils: Tabelle 1Table 1 Beispiel 1example 1 Vergleichsbeispiel 1Comparative example 1 TrimellitatTrimellitate 0,00.0 63,063.0 Estolid 1Estolide 1 44,044.0 0,00.0 Estolid 2Estolide 2 19,019.0 0,00.0 hydriertes PIBhydrogenated PIB 30,430.4 30,430.4 aminisches Antioxidantamine antioxidant 2,02.0 2,02.0 phenolisches Antioxidantphenolic antioxidant 1,01.0 1,01.0 Verschleißschutz EP/WAWear protection EP / WA 3,53.5 3,53.5 KorrosionsschutzCorrosion protection 0,10.1 0,10.1 Anlösbarkeit der RückständeSolubility of the residues sehr gut (4)very good (4) sehr gut (4)very good (4) Tabelle 2Table 2 Referenzbeispiel 2Reference example 2 Vergleichsbeispiel 2Comparative example 2 Trimellitat 1Trimellitate 1 00 76,076.0 alkyliertes Naphthalinalkylated naphthalene 76,076.0 0,00.0 hydriertes PIBhydrogenated PIB 20,020.0 20,020.0 aminisches Antioxidantamine antioxidant 4,04.0 4,04.0 Anlösbarkeit der RückständeSolubility of the residues sehr gut (4)very good (4) sehr gut (4)very good (4)

Die Basisdaten der Ölbeispiele können aus Tabelle 3 entnommen werden. Tabelle 3 Rezeptur Referenz-beispiel 1 Vergleichs-beispiel 1 Referenz-beispiel 2 Vergleichsbeispiel 2 Eisenmann-Test [250°C, 72h] Anlösbarkeit 4 4 4 4 Basisdaten Flammpunkt (°C) > 250 > 250 > 250 > 250 kin. V40 280,0 270,0 300,0 140,5 kin. V100 29,00 25,0 25,00 16,13 VI 137 120,0 105 121 The basic data of the oil examples can be found in Table 3. <u> Table 3 </u> Recipe Reference example 1 Comparative example 1 Reference example 2 Comparative example 2 Eisenmann test [250 ° C, 72h] Solvability 4th 4th 4th 4th Basic data Flash point (° C) > 250 > 250 > 250 > 250 kin. V40 280.0 270.0 300.0 140.5 kin. V100 29.00 25.0 25.00 16.13 VI 137 120.0 105 121

Des weiteren wurde das Reibverhalten der Öle im SRV in Anlehnung an DIN 51834-2 und der Verdampfungsverlust im dynamischen TGA gemessen. Die Ergebnisse werden in den Tabellen 4 und 5 gezeigt und sind graphisch in den Figuren 1 und 2 wiedergegeben. Hier entsprechen die Beispiele 1 und 2 den Referenzbeispielen 1 und 2. Tabelle 4 Referenz-beispiel 1 Vergleichs-beispiel 1 Referenz-beispiel 2 Vergleichs-beispiel 2 SRV TST (250 N) 50 - 120°C 0,116 0,112 0,156 0,091 120 - 140°C 0,111 0,127 0,155 0,091 140 - 160°C 0,105 0,141 0,158 0,128 160 - 180°C 0,1 0,145 0,163 0,139 180 - 200°C 0,095 0,143 0,171 0,165 200 - 210°C 0,08 0,137 0,177 0,194 210 - 220°C 0,086 0,132 0,175 0,206 220 - 230°C 0,085 0,129 0,179 0,208 230 - 240°C 0,087 0,126 0,185 0,208 240 - 250°C 0,091 0,121 0,189 0,206 250°C isotherm 0,093 0,118 0,186 0,201 Tabelle 5 Referenz-beispiel 1 Vergleichs-beispiel 1 Referenz-beispiel 2 Vergleichs-beispiel 2 TGA dynamisch 120°C 0,1 0,1 0,1 0,1 140°C 0,3 0,2 0,3 0,2 160°C 0,6 0,5 0,4 0,4 180°C 1 0,9 0,9 0,7 200°C 1,7 1,4 1,8 1,2 220°C 2,8 2,3 3,6 2,2 240°C 4,6 3,7 6,6 3,7 260°C 7,7 5,9 11,7 6,3 Furthermore, the friction behavior of the oils in the SRV was measured based on DIN 51834-2 and the evaporation loss in the dynamic TGA. The results are shown in Tables 4 and 5 and are graphed in FIG Figures 1 and 2 reproduced. Here, Examples 1 and 2 correspond to Reference Examples 1 and 2. <u> Table 4 </u> Reference example 1 Comparative example 1 Reference example 2 Comparative example 2 SRV TST (250 N) 50 - 120 ° C 0.116 0.112 0.156 0.091 120-140 ° C 0.111 0.127 0.155 0.091 140-160 ° C 0.105 0.141 0.158 0.128 160-180 ° C 0.1 0.145 0.163 0.139 180-200 ° C 0.095 0.143 0.171 0.165 200-210 ° C 0.08 0.137 0.177 0.194 210-220 ° C 0.086 0.132 0.175 0.206 220-230 ° C 0.085 0.129 0.179 0.208 230-240 ° C 0.087 0.126 0.185 0.208 240-250 ° C 0.091 0.121 0.189 0.206 250 ° C isothermal 0.093 0.118 0.186 0,201 Reference example 1 Comparative example 1 Reference example 2 Comparative example 2 TGA dynamic 120 ° C 0.1 0.1 0.1 0.1 140 ° C 0.3 0.2 0.3 0.2 160 ° C 0.6 0.5 0.4 0.4 180 ° C 1 0.9 0.9 0.7 200 ° C 1.7 1.4 1.8 1.2 220 ° C 2.8 2.3 3.6 2.2 240 ° C 4.6 3.7 6.6 3.7 260 ° C 7.7 5.9 11.7 6.3

Beispiele 4 und 7Examples 4 and 7 Referenzbeispiele 3, 5, 6 und 8Reference examples 3, 5, 6 and 8 Herstellung eines erfindungsgemäßen HochtemperaturfettsProduction of a high temperature grease according to the invention

Das Grundöl wird in einem Rührkessel vorgelegt. Bei 100°C wird unter Rühren das Polyisobutylen und ggf. ein weiteres Öl und das Verdickungsmittel hinzugegeben. Das Verdickungsmittel entsteht durch eine in situ-Reaktion der eingesetzten Reaktanten im Grundöl. Anschließend wird das Gemisch auf 150°C bis 210°C erhitzt, mehrere Stunden gerührt und wieder abgekühlt. Im Abkühlprozeß bei ca. 60°C werden die notwendigen Verschleißschutzmittel, Antioxidationsmittel und Korrosionsschutzmittel hinzugegeben. Eine homogene Mischung des Fettes erhält man durch den abschließenden Homogenisierungsschritt über Walze, Kolloidmühle oder die Gaulin.The base oil is placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil and the thickener are added with stirring. The thickener results from an in situ reaction of the reactants used in the base oil. The mixture is then heated to 150 ° C. to 210 ° C., stirred for several hours and cooled again. In the cooling process at approx. 60 ° C, the necessary wear protection agents, antioxidants and corrosion protection agents are added. A homogeneous mixture of the fat is obtained by the final homogenization step using a roller, colloid mill or the Gaulin.

Die Zusammensetzungen der Hochtemperaturfette sind in Tabelle 6 gezeigt. Tabelle 6 Typ Li-Komplex Li-Komplex Li-Komplex Di-Harnstoff Di-Harnstoff Di-Harnstoff Referenz-beispiel 3 Beispiel 4 Referenz-beispiel 5 Referenz-beispiel 6 Beispiel 7 Referenz-beispiel 8 Trimellitsäureester [Gew.%] 60 0 0 65,2 0 0 Estolid [Gew.%] 0 0 56 0 0 65,2 alkyliertes Naphtalin [Gew.%] 0 64 0 0 65,2 0 voll hydriertes Polyisobutylen [Gew.%] 26 25 25 25 25 25 Additiv-Package [Gew.%] 4 1 4 1 1 1 Verdicker-Konzentration [Gew.%] 10 10 15,0 8,8 8,8 8,8 The compositions of the high temperature greases are shown in Table 6. <u> Table 6 </u> Type Li complex Li complex Li complex Di-urea Di-urea Di-urea Reference example 3 Example 4 Reference example 5 Reference example 6 Example 7 Reference example 8 Trimellitic acid ester [% by weight] 60 0 0 65.2 0 0 Estolide [wt.%] 0 0 56 0 0 65.2 alkylated naphthalene [wt.%] 0 64 0 0 65.2 0 fully hydrogenated polyisobutylene [% by weight] 26th 25th 25th 25th 25th 25th Additive package [wt.%] 4th 1 4th 1 1 1 Thickener concentration [wt.%] 10 10 15.0 8.8 8.8 8.8

Bei den in den Beispielen 3 bis 8 verwendeten Verdickungsmitteln handelt es sich um: Referenz-Beispiel 3: LiOH, 12-Hydroxystearinsäure, Azelainsäure, Beispiel 4: LiOH, 12-Hydroxystearinsäure, Azelainsäure, Referenz-Beispiel 5: LiOH, 12-Hydroxystearinsäure, Azelainsäure, Referenz-Beispiel 6: Di-Harnstoff; Methylen-Di-phenyl-diisocyanat (MDI), Octylamin, Oleylamin Beispiel 7: Di-Harnstoff; MDI, Octylamin, Oleylamin Referenz-Beispiel 8: Di-Harnstoff; MDI, Octylamin, Oleylamin The thickeners used in Examples 3 to 8 are: Reference example 3: LiOH, 12-hydroxystearic acid, azelaic acid, Example 4: LiOH, 12-hydroxystearic acid, azelaic acid, Reference example 5: LiOH, 12-hydroxystearic acid, azelaic acid, Reference example 6: Di-urea; Methylene-diphenyl-diisocyanate (MDI), octylamine, oleylamine Example 7: Di-urea; MDI, octylamine, oleylamine Reference example 8: Di-urea; MDI, octylamine, oleylamine

Die allgemeinen Kenndaten der Fettmuster 3 bis 8 werden in Tabelle 7 gezeigt. Tabelle 7 Kenndaten Referenz-Beispiel 3 Beispiel 4 Referenz-Beispiel 5 Referenz-Beispiel 6 Beispiel 7 Referenz-Beispiel 8 Walpenentration nach 60 DT [DIN ISO 2137] 284 283 278 232 232 300 Walpenentration nach 100000 DT [DIN ISO 2137] 324 319 319 254 254 338 Tropfpunkt [C°] ISO >300 >300 >300 >300 280 292 Fließdruck -20°C; [mbar] [DIN 51805] >2000 275 284 575 525 <1400 Fließdruck -30°C; [mbar] [DIN 51805] >2000 425 675 <1400 <1400 <1400 Ölabsch 40°C/168h; [Gew.%] [DIN 51817] 3,80 3 1,70 1,2 0,10 5,60 Ölabsch 150°C/30h; [Gew.%] [FTMS 761 C] 7,4 7,5 2,50 0,20 0,30 5,00 Verdampfungsverlust 150°C/24°C [DIN 58397 Teil 1] 2 5,3 2,50 1,6 3,5 2,1 Wasserbeständigkeit statisch [DIN 51807] 1 2 1,00 0 1 1 The general characteristics of the fat samples 3 to 8 are shown in Table 7. <u> Table 7 </u> Characteristics Reference example 3 Example 4 Reference example 5 Reference example 6 Example 7 Reference example 8 Walpenentration according to 60 DT [DIN ISO 2137] 284 283 278 232 232 300 Walpenentration according to 100000 DT [DIN ISO 2137] 324 319 319 254 254 338 Drop point [C °] ISO > 300 > 300 > 300 > 300 280 292 Flow pressure -20 ° C; [mbar] [DIN 51805] > 2000 275 284 575 525 <1400 Flow pressure -30 ° C; [mbar] [DIN 51805] > 2000 425 675 <1400 <1400 <1400 Oil cut-off 40 ° C / 168h; [% By weight] [DIN 51817] 3.80 3 1.70 1.2 0.10 5.60 Oil cut-off 150 ° C / 30h; [% By weight] [FTMS 761 C] 7.4 7.5 2.50 0.20 0.30 5.00 Evaporation loss 150 ° C / 24 ° C [DIN 58397 part 1] 2 5.3 2.50 1.6 3.5 2.1 Static water resistance [DIN 51807] 1 2 1.00 0 1 1

Die Verdampfungsverluste der verschiedenen Fettmuster bei 150°C nach 30 h liegen zwischen 2% und 5%, was die sehr gute thermische Stabilität dieser Fettkonzepte unterstreicht.The evaporation losses of the various fat samples at 150 ° C after 30 hours are between 2% and 5%, which underlines the very good thermal stability of these fat concepts.

Einen entscheidenden Einfluss auf die Schmierwirkung eines Fettes hat die Ölabscheidung. Dabei ist darauf zu achten, dass einerseits die Ölabscheidung nicht zu hoch ist und das Öl aus dem Lager läuft und somit dem Tribo-System nicht mehr zur Verfügung steht und anderseits keine Ölabscheidung zu beobachten ist und die Schmierwirkung des Fettes verloren geht. Die Ölabscheidung sollte idealerweise zwischen 0,5 und 8 Gew.-% liegen, damit sich ein optimaler Schmierfilm im Lager ausbilden kann.Oil separation has a decisive influence on the lubricating effect of a grease. It must be ensured that, on the one hand, the oil separation is not too high and the oil runs out of the bearing and is therefore no longer available to the tribo-system and, on the other hand, no oil separation can be observed and the lubricating effect of the grease is lost. The oil separation should ideally be between 0.5 and 8 wt .-%, so that an optimal Can form a lubricating film in the bearing.

Die Fette der Beispiele wurden einem FE 9 Wälzlagertest nach DIN 51 821 unterzogen, bei dem die Lebensdauer der untersuchten Fette ermittelt wird und die obere Gebrauchstemperatur von Schmierfetten in Wälzlagern bei mittleren Drehzahlen und mittleren axialen Belastungen bestimmt wird.The greases in the examples were subjected to an FE 9 roller bearing test according to DIN 51 821, in which the service life of the greases examined is determined and the upper service temperature of lubricating greases in roller bearings at medium speeds and medium axial loads is determined.

Die untersuchten Fette und die Ergebnisse der L10 und L50-Werte sind in Tabelle 8 gezeigt. Tabelle 8 Referenz-Beispiel 3 Beispiel 4 Referenz-Beispiel 5 Referenz-Beispiel 6 Beispiel 7 Referenz-Beispiel 8 FE 9 [180°C,6000 1/min, 1500N] L 50 (h) 249 >100 207 146 >100 >100 L 10 (h) 169 >50 138 72 >50 >50 The fats tested and the results of the L10 and L50 values are shown in Table 8. <u> Table 8 </u> Reference example 3 Example 4 Reference example 5 Reference example 6 Example 7 Reference example 8 FE 9 [180 ° C, 6000 rpm, 1500N] L 50 (h) 249 > 100 207 146 > 100 > 100 L 10 (h) 169 > 50 138 72 > 50 > 50

Die Tabelle 8 zeigt, dass die Laufzeiten durch die Verwendung von PIB in Verbindung mit verschiedenen Grundölen lange Laufzeiten aufweisen und somit für hohe Anwendungstemperaturen im Dauerbetrieb geeignet sind.Table 8 shows that the running times due to the use of PIB in conjunction with various base oils have long running times and are therefore suitable for high application temperatures in continuous operation.

Des weiteren wurde das Geräuschverhalten nach der Fette nach SKF Be Quiet + gemäß den Beispielen 3 bis 8 gemessen. Die Ergebnisse sind in Tabelle 9 angegeben. Tabelle 9 Referenz-Beispiel 3 Beispiel 4 Referenz-Beispiel 5 Referenz-Beispiel 6 Beispiel 7 Referenz-Beispiel 8 Geräuschprüfung [BeQuiet+ SKF] GN4 GN3 GN3 GN2 GN3 GN4 In addition, the noise behavior after the SKF Be Quiet + fats according to Examples 3 to 8 was measured. The results are given in Table 9. <u> Table 9 </u> Reference example 3 Example 4 Reference example 5 Reference example 6 Example 7 Reference example 8 Noise test [BeQuiet + SKF] GN4 GN3 GN3 GN2 GN3 GN4

Das Geräuschverhalten der verschiedenen Fettformulierungen wird durch die Verwendung des vollhydierten Polyisobutylens sehr positiv beeinflußt. Es können mit Ausnahme von Beispiel 6 gute bis sehr gute Geräuscheigenschaften erzielt werden.The use of fully hydrogenated polyisobutylene has a very positive effect on the noise behavior of the various fat formulations. With the exception of Example 6, good to very good noise properties can be achieved.

Die Eigenschaftes des Fetts gemäß Beispiel 3, bei dem vollhydriertes PIB verwendet wurde, wurde nun mit einem Fett (Vergleichsbeispiel 3) verglichen, dass ein PIB enthielt, bei dem noch Doppelbindungen vorhanden waren, also ein nicht vollhydriertes PIB.The properties of the fat according to Example 3, in which fully hydrogenated PIB was used, was now compared with a fat (comparative example 3) that contained a PIB in which double bonds were still present, that is to say a not fully hydrogenated PIB.

Die sonstige Zusammensetzung des Fetts gemäß Vergleichsbeispiel 3 entsprach der des Beispiels 3. Tabelle 10 Beispiel 3 Vergleichsbeisp. 3 FE 9 [180°C,6000 1/min, 1500N] L 50 (h) 249 126 L 10 (h) 169 72 Geräuschprüfung [BeQuiet+ SKF] GN4 GN1 Verdampfungsverlust [DIN ISO 58397] 170°C/24h 4,3 5,1 Verdampfungsverlust [DIN ISO 58397] 180°C/24h 6,9 7,4 Walpenentration nach 60 DT [DIN ISO 2137] 284 301 Walpenentration nach 100000 DT [DIN ISO 2137] 324 356 Korrosionswirkung von Schmierstoffen auf Kupfer [DIN ISO 51811] 150°C/24h 1a n.A. Ölabsch 150°C/30h; [Gew.%] [ASTM D 6184] 7,4 8,4 Ölabsch 150°C/30h; [Gew.%] [ASTM D 6184 17,9 14,7 Ölabsch 168°C/40h; [Gew.%] [DIN 51817] 3,8 6,5 Prüfung von Schmerfetten auf korrosionsverhindernde Eigenschaften [DIN 51801/ISO 11007] 0 n.A. Tropfpunkt [C°] [DIN ISO 2176] >300 295,0 Verdampfungsverlust 150°C/24°C [DIN 58397 Teil 1] 2 2,4 Wasserbeständigkeit statisch [DIN 51807] 90°C 0 n.A. The other composition of the fat according to comparative example 3 corresponded to that of example 3. <u> Table 10 </u> Example 3 Comparative example 3 FE 9 [180 ° C, 6000 rpm, 1500N] L 50 (h) 249 126 L 10 (h) 169 72 Noise test [BeQuiet + SKF] GN4 GN1 Loss of evaporation [DIN ISO 58397] 170 ° C / 24h 4.3 5.1 Evaporation loss [DIN ISO 58397] 180 ° C / 24h 6.9 7.4 Walpenentration according to 60 DT [DIN ISO 2137] 284 301 Walpenentration according to 100000 DT [DIN ISO 2137] 324 356 Corrosion effect of lubricants on copper [DIN ISO 51811] 150 ° C / 24h 1a n / A Oil cut-off 150 ° C / 30h; [% By weight] [ASTM D 6184] 7.4 8.4 Oil cut-off 150 ° C / 30h; [% By weight] [ASTM D 6184 17.9 14.7 Oil cut-off 168 ° C / 40h; [% By weight] [DIN 51817] 3.8 6.5 Testing of fat greases for corrosion-preventing properties [DIN 51801 / ISO 11007] 0 n / A Drop point [C °] [DIN ISO 2176] > 300 295.0 Evaporation loss 150 ° C / 24 ° C [DIN 58397 part 1] 2 2.4 Static water resistance [DIN 51807] 90 ° C 0 n / A

Der Vergleich der Fette mit vollhydriertem PIB und nicht vollhydriertem PIB in Tabelle 10 zeigt, dass das Fett des Beispiels 3 eine verdoppelte Laufzeit bei der FE9 Prüfung zeigt, geringere Verdampfungsverluste und ein signifikant besseres Geräuschverhalten aufweist.The comparison of the fats with fully hydrogenated PIB and not fully hydrogenated PIB in Table 10 shows that the fat of Example 3 shows a doubled running time in the FE9 test, lower evaporation losses and a significantly better one Has noise behavior.

Zum Nachweis der vorteilhaften Eigenschaften eines Öls, das vollhydriertes PIB enthält, wurde dies mit einem Öl verglichen, dass ein teilweise hydriertes PIB enthält. Tabelle 11 zeigt die Ergebnisse. Tabelle 11 Muster Öl 1 Öl 2 Estolid 1 32,966 Gew.-% 32,966 Gew.-% Estolid 2 26,874 Gew.-% 26,874 Gew.-% voll hydriertes PIB 33,65 Gew.-% ----- teil hydrietes PIB ----- 33,65 Gew.-% Antioxidant 3 Gew.-% 3 Gew.-% AW 3,5 Gew.-% 3,5 Gew.-% Korrosionsschutz 0,01 Gew.-% 0,01 Gew.-% Prüfmethoden V40 (mm2/s) 277,8 277,6 V100 (mm2/s) 28,28 27,90 Viskositätsindex 136 134 Eisenmanntest 72h/250°C Rückstand (%) 6,6 8,0 Eisenmanntest 72h/250°C Anlösbarkeit 4 1 Eisenmanntest 120h/220°C Rückstand (%) 13,8 19,2 Eisenmanntest 120h/220°C Anlösbarkeit 3 1 HTG Kettenprüfstand 220°C/2600N/2m/s (h) 15 13 4 = Rückstand nach vollständiger Verdampfung sehr gut anlösbar
3 = Rückstand nach vollständiger Verdampfung gut anlösbar
2 = Rückstand nach vollständiger Verdampfung partiell anlösbar
1 = Rückstand nach vollständiger Verdampfung nicht anlösbar
To demonstrate the advantageous properties of an oil that contains fully hydrogenated PIB, this was compared with an oil that contains a partially hydrogenated PIB. Table 11 shows the results. <u> Table 11 </u> template Oil 1 Oil 2 Estolide 1 32.966 wt% 32.966 wt% Estolide 2 26.874 wt% 26.874 wt% fully hydrogenated PIB 33.65% by weight ----- part hydrietes PIB ----- 33.65% by weight Antioxidant 3% by weight 3% by weight AW 3.5 wt% 3.5 wt% Corrosion protection 0.01 wt% 0.01 wt% Test methods V40 (mm 2 / s) 277.8 277.6 V100 (mm 2 / s) 28.28 27.90 Viscosity index 136 134 Eisenmann test 72h / 250 ° C residue (%) 6.6 8.0 Eisenmann test 72h / 250 ° C solvability 4th 1 Eisenmann test 120h / 220 ° C residue (%) 13.8 19.2 Eisenmann test 120h / 220 ° C solvability 3 1 HTG chain test bench 220 ° C / 2600N / 2 m / s (h) 15th 13th 4 = residue can be dissolved very well after complete evaporation
3 = residue easily dissolvable after complete evaporation
2 = residue partially dissolvable after complete evaporation
1 = residue cannot be dissolved after complete evaporation

Tabelle 11 zeigt, dass deutliche Unterschiede bei der Verwendung von vollhydriertem und teilweise hydriertem PIB vorhanden sind. So ist das Anlösen des Rückstandes auf Basis des teilweise hydrierten PIB nicht mehr möglich, während des Öl mit dem vollhydriertem PIB sehr gute Wiederanlösungseigenschaften aufweist.Table 11 shows that there are significant differences when using fully hydrogenated and partially hydrogenated PIB. For example, it is no longer possible to partially dissolve the residue on the basis of the partially hydrogenated PIB, while the oil with the fully hydrogenated PIB has very good redissolving properties.

Claims (5)

  1. A high-temperature grease, comprising
    a) 91.9 to 25 wt.-% of at least one oil from the group of alkylaromatics;
    b) 6 to 45 wt.-% of a polymer, selected from the group consisting of a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene;
    c) 0.1 to 10 wt.-% of additives, alone or in combination, selected from the group consisting of corrosion-protection additives, antioxidants, wear-protection additives, UV stabilisers, inorganic or organic solid lubricants and
    d) 2 to 20 wt.-% of thickener.
  2. The high-temperature grease according to claim 1, in which the oil component comprises, as further oil, a compound selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, pyromellitic acid esters, diphenyl ethers, phloroglucinol esters and/or polyalphaolefins, alpha olefin copolymers.
  3. The high-temperature grease according to claim 1, in which the thickener is selected from the group consisting of urea, aluminium complex soaps, metal simple soaps of the elements of the first and second main group of the periodic table, metal complex soaps of the elements of the first and second main group of the periodic table, bentonites, sulfonates, silicates, aerosil, polyimides, PTFE or a mixture of the aforementioned thickeners.
  4. The high-temperature grease according to claim 1, in which the alkylaromatic compound is an aliphatically substituted naphthalene.
  5. A use of the high-temperature grease according to one of the preceding claims for lubricating rolling contact bearings and friction bearings in automotive engineering, materials handling technology, manufacturing systems engineering, office technology and in industrial installations and machines, but also in the fields of domestic machines, consumer electronics and for lubricating chains, chain rollers and belts of continuous presses.
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