EP2205707A1 - Lubricating grease composition and preparation - Google Patents
Lubricating grease composition and preparationInfo
- Publication number
- EP2205707A1 EP2205707A1 EP08832979A EP08832979A EP2205707A1 EP 2205707 A1 EP2205707 A1 EP 2205707A1 EP 08832979 A EP08832979 A EP 08832979A EP 08832979 A EP08832979 A EP 08832979A EP 2205707 A1 EP2205707 A1 EP 2205707A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oil
- grease composition
- less
- molecules
- kinematic viscosity
- 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.)
- Withdrawn
Links
Classifications
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- 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
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
- C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
- C10M2205/0265—Butene used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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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
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/046—Hydroxy ethers
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/006—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions used as thickening agents
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/102—Ureas; Semicarbazides; Allophanates
- C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
- C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/015—Distillation range
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- 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
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- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- 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
- C10N2030/74—Noack Volatility
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy
Definitions
- the invention relates generally to lubricating grease compositions having improved service life.
- Lubrication of moving parts with grease is necessary to for efficient motion of these parts.
- a necessary property of the lubricating grease is extended life, i.e., the grease must protect the bearings for long periods of time under severe conditions.
- One measure of this performance in wheel bearing applications is ASTM D3527-02 Life Performance test, which employs severe conditions of 25 lbs force (11 IN) thrust load, 1000 rpm, and 16O 0 C spindle temperature to induce grease deterioration and failure. The test is performed in a 20/4 hour on/off cycle until the grease breaks down, causing measured drive motor torque to increase past an established end point. The number of hours to failure is the test result.
- Grease compositions in the prior art typically employ a Group I, II, III, a synthetic PAO (for poly ⁇ -olefin) or mixtures thereof as a base oil stock.
- the groups are broad categories of base stocks developed by the American Petroleum
- Fischer Tropsch base oil FTBO
- Crude product prepared from the Fischer-Tropsch process comprises a mixture of various solid, liquid, and gaseous hydrocarbons, which can be refined into products such as diesel oil, naphtha, wax, and other liquid petroleum or specialty products.
- Fischer-Tropsch synthesis products can be obtained by known processes such as, for example, the commercial SASOL® Slurry Phase Fischer-Tropsch technology, the commercial SHELL® Middle Distillate Synthesis (SMDS) Process, or by the non-commercial EXXON® Advanced Gas Conversion (AGC-21) process. Details of these processes and others are described in, for example, WO-9934917, WO- 9920720 and WO- -05107935, EP-776959, EP- 668342; U.S. Patent Nos. 4,943,672, 5,059,299, 5,733,839, and RE39073 ; US Published Application No.
- the Fischer-Tropsch synthesis product usually comprises hydrocarbons having 1 to 100, or even more than 100 carbon atoms, and typically includes paraffins, olefins and oxygenated products.
- EP1630221 Al discloses a grease composition
- a grease composition comprising a base oil prepared from a Fischer-Tropsch product wherein the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms is at least 0.2 in the Fischer-Tropsch product, and with at least 30% of the compounds having at least 30 carbon atoms, for the grease composition to have an enhanced exhibited oxidational stability while allowing more soap thickeners to be used.
- the Fischer-Tropsch base oil used in the grease of EP 163022 IAl is produced from a process in which dewaxing is a separate step from hydroisomerizing.
- the invention relates to a grease composition having extended service life compared to the grease compositions of the prior art, the composition is made from Fischer-Tropsch base oils produced from processes having a combined hydroisomerization dewaxing step.
- a grease composition comprising (i) a lubricating base oil; (ii) from 2 to 50 wt % of a thickener selected from a simple soap, a complex soap, polyurea, diurea, triurea, fluorocarbon resin, and mixtures thereof; and (iii) 0-30 wt % of at least an additive selected from the group of preservatives, colorants, anti-weld agents, extreme pressure agents, flame retardants, rust inhibitors, corrosion inhibitors, oil bleed inhibitors, metal deactivators, viscosity modifiers, pour point depressants, and mixtures thereof; the lubricating base oil comprises at least 50 wt.
- the Fischer-Tropsch base oil is a Fischer-Tropsch derived base oil.
- the Fischer-Tropsch base oil is a base oil made from a waxy feed.
- a method to make a grease composition comprises blending a composition comprising a lubricating base oil with: 2 to 50 wt % of a thickener selected from a simple soap, a complex soap, polyurea, diurea, triurea, fluorocarbon resin, and mixtures thereof; and 0-10 wt % of at least an additive selected from the group of preservatives, colorants, anti-weld agents, extreme pressure agents, flame retardants, rust inhibitors, corrosion inhibitors, oil bleed inhibitors, metal deactivators, viscosity modifiers, pour point depressants, and mixtures thereof; the lubricating base oil comprises at least 50 wt.
- % of a Fischer- Tropsch base oil having a total weight percent of molecules with cycloparaffmic functionality of greater than 10, and a ratio of weight percent molecules with monocycloparaff ⁇ nic functionality to weight percent molecules with multicycloparaffinic functionality of greater than 15.
- an article having components lubricated by composition comprising (i) a lubricating base oil; (ii) from 2 to 30 wt % of a thickener selected from a simple soap, a complex soap, polyurea, diurea, triurea, fluorocarbon resin, and mixtures thereof; and (iii) 0-10 wt % of at least an additive selected from the group of preservatives, colorants, anti-weld agents, extreme pressure agents, flame retardants, rust inhibitors, corrosion inhibitors, oil bleed inhibitors, metal deactivators, viscosity modifiers, pour point depressants, and mixtures thereof; the lubricating base oil comprises at least 50 wt.
- % of a Fischer-Tropsch base oil having a total weight percent of molecules with cycloparaffinic functionality of greater than 10, and a ratio of weight percent molecules with monocycloparaff ⁇ nic functionality to weight percent molecules with multicycloparaffinic functionality of greater than 15.
- Fischer-Tropsch derived means that the product, fraction, or feed originates from or is produced at some stage by a Fischer-Tropsch process.
- Fischer-Tropsch base oil may be used interchangeably with “FT base oil,” “FTBO,” “GTL base oil” (GTL: gas-to-liquid), or “Fischer-Tropsch derived base oil.”
- isomerized base oil refers to a base oil made by isomerization of a waxy feed, which may be derived from a Fischer-Tropsch process or a mineral oil.
- a "waxy feed" comprises at least 40 wt% n-paraffins. In one embodiment, the waxy feed comprises greater than 50 wt% n-paraffins. In another embodiment, greater than 75 wt% n-paraffins. In one embodiment, the waxy feed also has very low levels of nitrogen and sulphur, e.g., less than 25 ppm total combined nitrogen and sulfur, or in other embodiments less than 20 ppm.
- waxy feeds examples include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof.
- the waxy feeds have a pour point of greater than 50°C. In another embodiment, greater than 60°C.
- Kinematic viscosity is a measurement in mm 2 /s of the resistance to flow of a fluid under gravity, determined by ASTM D445-06.
- Viscosity index (VI) is an empirical, unit-less number indicating the effect of temperature change on the kinematic viscosity of the oil. The higher the VI of an oil, the lower its tendency to change viscosity with temperature. Viscosity index is measured according to ASTM D 2270-04.
- CCS VIS Cold-cranking simulator apparent viscosity
- Brookfield viscosity is used to determine the internal fluid-friction of a lubricant during cold temperature operation, which can be measured by ASTM D 2983-04.
- Pul point is a measurement of the temperature at which a sample of base oil will begin to flow under certain carefully controlled conditions, which can be determined as described in ASTM D 5950-02.
- Auto ignition temperature is the temperature at which a fluid will ignite spontaneously in contact with air, which can be determined according to ASTM 659-78.
- consecutive numbers of carbon atoms means that the base oil has a distribution of hydrocarbon molecules over a range of carbon numbers, with every number of carbon numbers in-between.
- the base oil may have hydrocarbon molecules ranging from C22 to C36 or from C30 to C60 with every carbon number in-between.
- the hydrocarbon molecules of the base oil differ from each other by consecutive numbers of carbon atoms, as a consequence of the waxy feed also having consecutive numbers of carbon atoms.
- the source of carbon atoms is CO and the hydrocarbon molecules are built up one carbon atom at a time. Petroleum-derived waxy feeds have consecutive numbers of carbon atoms.
- PAO poly-alpha-olefin
- the molecules of an isomerized base oil have a more linear structure, comprising a relatively long backbone with short branches.
- the classic textbook description of a PAO is a star-shaped molecule, and in particular tridecane, which is illustrated as three decane molecules attached at a central point. While a star-shaped molecules is theoretical, nevertheless PAO molecules have fewer and longer branches that the hydrocarbon molecules that make up the isomerized base oil disclosed herein.
- Molecules with cycloparaffinic functionality mean any molecule that is, or contains as one or more substituents, a monocyclic or a fused multicyclic saturated hydrocarbon group.
- “Molecules with monocycloparaff ⁇ nic functionality” mean any molecule that is a monocyclic saturated hydrocarbon group of three to seven ring carbons or any molecule that is substituted with a single monocyclic saturated hydrocarbon group of three to seven ring carbons.
- “Molecules with multicycloparaff ⁇ nic functionality” mean any molecule that is a fused multicyclic saturated hydrocarbon ring group of two or more fused rings, any molecule that is substituted with one or more fused multicyclic saturated hydrocarbon ring groups of two or more fused rings, or any molecule that is substituted with more than one monocyclic saturated hydrocarbon group of three to seven ring carbons.
- Oxidator BN measures the response of a lubricating oil in a simulated application. High values, or long times to adsorb one liter of oxygen, indicate good stability. Oxidator BN can be measured via a Dornte-type oxygen absorption apparatus (R. W. Dornte "Oxidation of White Oils," Industrial and Engineering Chemistry, Vol. 28, page 26, 1936), under 1 atmosphere of pure oxygen at 34O 0 F., time to absorb 1000 ml of O 2 by 100 g. of oil is reported. In the Oxidator BN test, 0.8 ml of catalyst is used per 100 grams of oil. The catalyst is a mixture of soluble metal- naphthenates simulating the average metal analysis of used crankcase oil.
- the additive package is 80 millimoles of zinc bispolypropylenephenyldithiophosphate per 100 grams of oil.
- Molecular characterizations can be performed by methods known in the art, including Field Ionization Mass Spectroscopy (FIMS) and n-d-M analysis (ASTM D 3238-95 (Re-approved 2005) with normalization).
- FIMS Field Ionization Mass Spectroscopy
- ASTM D 3238-95 Re-approved 2005
- the base oil is characterized as alkanes and molecules with different numbers of unsaturations.
- the molecules with different numbers of unsaturations may be comprised of cycloparaffins, olefins, and aromatics. If aromatics are present in significant amount, they would be identified as 4-unsaturations.
- olefins When olefins are present in significant amounts, they would be identified as 1 -unsaturations.
- the total of the 1 -unsaturations, 2-unsaturations, 3 -unsaturations, 4-unsaturations, 5-unsaturations, and 6-unsaturations from the FIMS analysis, minus the wt % olefins by proton NMR, and minus the wt % aromatics by HPLC-UV is the total weight percent of molecules with cycloparaffinic functionality. If the aromatics content was not measured, it was assumed to be less than 0.1 wt % and not included in the calculation for total weight percent of molecules with cycloparaffinic functionality.
- the total weight percent of molecules with cycloparaffinic functionality is the sum of the weight percent of molecules with monocyclopraff ⁇ nic functionality and the weight percent of molecules with multicycloparaffinic functionality.
- Molecular weights are determined by ASTM D2503-92 (Reapproved 2002). The method uses thermoelectric measurement of vapour pressure (VPO). In circumstances where there is insufficient sample volume, an alternative method of ASTM D2502-94 may be used; and where this has been used it is indicated.
- VPO vapour pressure
- Density is determined by ASTM D4052-96 (Reapproved 2002). The sample is introduced into an oscillating sample tube and the change in oscillating frequency caused by the change in the mass of the tube is used in conjunction with calibration data to determine the density of the sample.
- Weight percent olefins can be determined by proton-NMR according to the steps specified herein.
- the olefins are conventional olefins, i.e. a distributed mixture of those olefin types having hydrogens attached to the double bond carbons such as: alpha, vinylidene, cis, trans, and trisubstituted, with a detectable allylic to olefin integral ratio between 1 and 2.5. When this ratio exceeds 3, it indicates a higher percentage of tri or tetra substituted olefins being present, thus other assumptions known in the analytical art can be made to calculate the number of double bonds in the sample.
- the steps are as follows: A) Prepare a solution of 5- 10% of the test hydrocarbon in deuterochloroform. B) Acquire a normal proton spectrum of at least 12 ppm spectral width and accurately reference the chemical shift (ppm) axis, with the instrument having sufficient gain range to acquire a signal without overloading the receiver/ ADC, e.g., when a 30 degree pulse is applied, the instrument having a minimum signal digitization dynamic range of 65,000. In one embodiment, the instrument has a dynamic range of at least 260,000. C) Measure the integral intensities between: 6.0-4.5 ppm (olefin); 2.2-1.9 ppm (allylic); and 1.9-0.5 ppm (saturate).
- the wt% olefins by proton NMR 100 times the number of double bonds times the number of hydrogens in a typical olefin molecule divided by the number of hydrogens in a typical test substance molecule.
- the wt% olefins by proton NMR calculation procedure, D works particularly well when the percent olefins result is low, less than 15 wt%.
- Weight percent aromatics in one embodiment can be measured by HPLC-UV.
- the test is conducted using a Hewlett Packard 1050 Series Quaternary Gradient High Performance Liquid Chromatography (HPLC) system, coupled with a HP 1050 Diode- Array UV- Vis detector interfaced to an HP Chem-station.
- HPLC Hewlett Packard 1050 Series Quaternary Gradient High Performance Liquid Chromatography
- Identification of the individual aromatic classes in the highly saturated base oil can be made on the basis of the UV spectral pattern and the elution time.
- the amino column used for this analysis differentiates aromatic molecules largely on the basis of their ring- number (or double-bond number). Thus, the single ring aromatic containing molecules elute first, followed by the polycyclic aromatics in order of increasing double bond number per molecule.
- Retention time window limits for each aromatic class can be determined by manually evaluating the individual absorbance spectra of eluting compounds at different times and assigning them to the appropriate aromatic class based on their qualitative similarity to model compound absorption spectra.
- Weight percent aromatic carbon (“Ca”), weight percent naphthenic carbon (“Cn”) and weight percent paraffinic carbon (“Cp”) in one embodiment can be measured by ASTM D3238-95 (Reapproved 2005) with normalization.
- ASTM D3238-95 (Reapproved 2005) is the Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method.
- This method is for "olefin free" feedstocks which are assumed in this application to mean that that olefin content is 2 wt% or less.
- the normalization process consists of the following: A) If the Ca value is less than zero, Ca is set to zero, and Cn and Cp are increased proportionally so that the sum is 100%. B) If the Cn value is less than zero, Cn is set to zero, and Ca and Cp are increased proportionally so that the sum is 100%; and C) If both Cn and Ca are less than zero, Cn and Ca are set to zero, and Cp is set to 100%.
- HPLC-UV Calibration can be used for identifying classes of aromatic compounds even at very low levels, e.g., multi-ring aromatics typically absorb 10 to 200 times more strongly than single-ring aromatics. Alkyl-substitution affects absorption by 20%. Integration limits for the co-eluting 1- ring and 2-ring aromatics at 272nm can be made by the perpendicular drop method. Wavelength dependent response factors for each general aromatic class can be first determined by constructing Beer's Law plots from pure model compound mixtures based on the nearest spectral peak absorbances to the substituted aromatic analogs. Weight percent concentrations of aromatics can be calculated by assuming that the average molecular weight for each aromatic class was approximately equal to the average molecular weight for the whole base oil sample.
- the weight percent of all molecules with at least one aromatic function in the purified mono-aromatic standard can be confirmed via long-duration carbon 13 NMR analysis.
- the NMR results can be translated from % aromatic carbon to % aromatic molecules (to be consistent with HPLC-UV and D 2007) knowing that 95-99% of the aromatics in highly saturated base oils are single-ring aromatics.
- the standard D 5292-99 (Reapproved 2004) method can be modified to give a minimum carbon sensitivity of 500:1 (by ASTM standard practice E 386) with a 15-hour duration run on a 400-500 MHz NMR with a 10-12 mm Nalorac probe.
- Acorn PC integration software can be used to define the shape of the baseline and consistently integrate.
- Extent of branching refers to the number of alkyl branches in hydrocarbons.
- Branching and branching position can be determined using carbon- 13 ( 13 C) NMR according to the following nine-step process. 1) Identify the CH branch centers and the CH 3 branch termination points using the DEPT Pulse sequence (Doddrell, D.T.; D. T. Pegg; M.R. Bendall, Journal of Magnetic Resonance 1982, 48, 323ff.). 2) Verify the absence of carbons initiating multiple branches (quaternary carbons) using the APT pulse sequence (Part, S. L.; J. N. Shoolery, Journal of Magnetic Resonance 1982, 46, 535ff.).
- % in chloroform-dl are excited by 30 degrees pulses followed by a 1.3 sec acquisition time.
- the broadband proton inverse-gated decoupling is used during a 6 sec delay prior to the excitation pulse and on during acquisition.
- Samples are doped with 0.03 to 0.05 M Cr (acac) 3 (tris (acetylacetonato)-chromium (III)) as a relaxation agent to ensure full intensities are observed.
- the DEPT and APT sequences can be carried out according to literature descriptions with minor deviations described in the Varian or Bruker operating manuals.
- DEPT is Distortionless Enhancement by Polarization Transfer.
- the DEPT 45 sequence gives a signal all carbons bonded to protons.
- DEPT 90 shows CH carbons only.
- DEPT 135 shows CH and CH 3 up and CH 2 180 degrees out of phase (down).
- APT is attached proton test, known in the art. It allows all carbons to be seen, but if CH and CH 3 are up, then quaternaries and CH 2 are down.
- the branching properties of the sample can be determined by 13 C NMR using the assumption in the calculations that the entire sample was iso-paraffinic.
- the unsaturates content may be measured using Field Ionization Mass Spectroscopy (FIMS).
- the grease composition comprises a number of components, including optional additives, in a matrix of base oil.
- Base Oil Matrix Component In one embodiment, the base oil or blends thereof comprises at least an isomerized base oil which the product itself, its fraction, or feed originates from or is produced at some stage by isomerization of a waxy feed from a Fischer-Tropsch process ("Fischer-Tropsch derived base oils"). In another embodiment, the base oil comprises at least an isomerized base oil made from a substantially paraffmic wax feed ("waxy feed"). In a third embodiment, the base oil consists essentially of at least an isomerized base oil.
- Fischer-Tropsch derived base oils are disclosed in a number of patent publications, including for example U.S. Pat. Nos. 6080301, 6090989, and 6165949, and US Patent Publication No. US2004/0079678A1, US20050133409, US20060289337.
- Fischer-Tropsch process is a catalyzed chemical reaction in which carbon monoxide and hydrogen are converted into liquid hydrocarbons of various forms including a light reaction product and a waxy reaction product, with both being substantially paraffmic.
- the isomerized base oil has consecutive numbers of carbon atoms and has less than 10 wt% naphthenic carbon by n-d-M.
- consecutive numbers of carbon atoms we mean that the hydrocarbon molecules of the base oil differ from each other by consecutive numbers of carbon atoms, as a consequence of the waxy feed also having sequential numbers of carbon atoms.
- the source of carbon atoms is CO and the hydrocarbon molecules are built up one carbon atom at a time. Petroleum-derived waxy feeds also have sequential numbers of carbon numbers.
- the molecules of the base oil have a more linear structure, comprising a relatively long backbone with short branches.
- PAO PAO
- tridecane tridecane
- PAO molecules PAO molecules have fewer and longer branches that the hydrocarbon molecules that make up the base oil used in this disclosure.
- the isomerized base oil is made by a process in which the hydroisomerization dewaxing is at conditions sufficient for the base oil to have: a) a wt. % of all molecules with at least one aromatic function less than 0.30; b) a wt. % of all molecules with at least one cycloparaffin function greater than 10; c) a ratio of wt. % of molecules containing monocycloparaffins to wt. % of molecules containing multicycloparaffins greater than 20; and d) a viscosity index greater than 28 x Ln (Kinematic viscosity at 100 0 C.) + 80.
- the isomerized base oil is made from a process in which the highly paraffinic wax is hydroisomerized using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component, and under conditions of 600 0 F. to 75O 0 F.
- the conditions for hydroisomerization are controlled such that the conversion of the compounds boiling above 700 0 F in the wax feed to compounds boiling below 700 0 F is maintained between 10 wt % and 50 wt%.
- the resulting FT base oil has a kinematic viscosity of between 1.0 and 3.5 mm 2 /s at 100 0 C and a Noack volatility of less than 50 wt. % .
- the base oil comprises greater than 3 wt. % molecules with cycloparaffinic functionality and less than 0.30 weight percent aromatics.
- the FT base oil has a Noack volatility less than the Noack volatility calculated by the following equation: 160- 40 (Kinematic Viscosity at 100 0 C).
- the isomerized base oil is made from a process in which the highly paraffinic wax is hydroisomerized under conditions for the base oil to have a kinematic viscosity at 100°C. of 3.6 to 4.2 mm 2 /s, a viscosity index of greater than 130, a wt% Noack volatility less than 12, a pour point of less than -9 0 C.
- the base oil comprises greater than 10 wt. % and less than 70 wt. % total molecules with cycloparaffinic functionality, and a ratio of wt. % molecules with monocycloparaffinic functionality to wt. % molecules with multicycloparaffinic functionality greater than 15.
- the isomerized base oil has a Noack volatility less than an amount calculated by the following equation: 1000 x (Kinematic Viscosity at 100°C.) "2 7 .
- the isomerized base oil has a Noack volatility less than an amount calculated by the following equation: 900 x (Kinematic Vicosity at 100°C.) "2 8 .
- the isomerized base oil has a Kinematic Vicosity at 100°C.
- the isomerized base oil has a kinematic viscosity at 100 0 C. of less than 4.0 mm 2 /s, and a wt% Noack volatility between 0 and 100.
- the isomerized base oil has a kinematic viscosity between 1.5 and 4.0 mm 2 /s and a Noack volatility less than the Noack volatility calculated by the following equation: 160 - 40 (Kinematic Viscosity at 100 0 C).
- the isomerized base oil has a kinematic viscosity at 100°C in the range of 2.4 and 3.8 mm 2 /s and a Noack volatility less than an amount defined by the equation: 900 x (Kinematic Viscosity at 100 0 C) '2 8 -15).
- the isomerized base oil is made from a process in which the highly paraffinic wax is hydroisomerized under conditions for the base oil to have a kinematic viscosity at 100°C. of 3.6 to 4.2 mm /s, a viscosity index of greater than 130, a wt% Noack volatility less than 12, a pour point of less than -9 0 C.
- the isomerized base oil has an aniline point, in degrees F, greater than 200 and less than or equal to an amount defined by the equation: 36 x Ln(Kinematic Viscosity at 100 0 C, in mm 2 /s) + 200.
- AIT in 0 C 1.6 x (Kinematic Viscosity at 4O 0 C, in mm 2 /s) + 300.
- the base oil as an AIT of greater than 329 0 C. and a viscosity index greater than 28 x Ln (Kinematic Viscosity at 100 0 C, in mm 2 /s) + 100.
- the isomerized base oil has a traction coefficient of less than 0.023 when measured at a kinematic viscosity of 15 mm 2 /s and at a slide to roll ratio of 40%.
- the isomerized base oil has a traction coefficient of less than 0.017 when measured at a kinematic viscosity of 15 mm 2 /s and at a slide to roll ratio of 40%. In another embodiment the isomerized base oil has a viscosity index greater than 150 and a traction coefficient less than 0.015 when measured at a kinematic viscosity of 15 mm /s and at a slide to roll ratio of 40 %. [053] In some embodiments, the isomerized base oil having low traction coefficients also display a higher kinematic viscosity and higher boiling points.
- the base oil has a traction coefficient less than 0.015, and a 50 wt% boiling point greater than 565°C. (1050°F). In another embodiment, the base oil has a traction coefficient less than 0.011 and a 50 wt% boiling point by ASTM D 6352-04 greater than 582 0 C. (1080 0 F). [054] In some embodiments, the isomerized base oil having low traction coefficients also display unique branching properties by NMR, including a branching index less than or equal to 23.4, a branching proximity greater than or equal to 22.0, and a Free Carbon Index between 9 and 30. In one embodiment, the base oil has at least 4 wt% naphthenic carbon, in another embodiment, at least 5 wt% naphthenic carbon by n-d-M analysis by ASTM D 3238-95 (Reapproved 2005) with normalization.
- the isomerized base oil is produced in a process wherein the intermediate oil isomerate comprises paraff ⁇ nic hydrocarbon components, and in which the extent of branching is less than 7 alkyl branches per 100 carbons, and wherein the base oil comprises paraff ⁇ nic hydrocarbon components in which the extent of branching is less than 8 alkyl branches per 100 carbons and less than 20 wt % of the alkyl branches are at the 2 position.
- the isomerized base oil has an average molecular weight between 600 and 1100, and an average degree of branching in the molecules between 6.5 and 10 alkyl branches per 100 carbon atoms.
- the isomerized base oil is obtained from a process in which the highly paraffinic wax is hydroisomerized at a hydrogen to feed ratio from 712.4 to 3562 liter H 2 /liter oil, for the base oil to have a total weight percent (wt. %) of molecules with cycloparaffinic functionality of greater than 10, and a ratio of wt. % molecules with monocycloparaffinic functionality to wt. % molecules with multicycloparaffmic functionality of greater than 15.
- the base oil has a viscosity index greater than an amount defined by the equation: 28 x Ln (Kinematic viscosity at 100°C.) + 95.
- the base oil comprises a wt. % aromatics less than 0.30; a wt. % of molecules with cycloparaffinic functionality greater than 10; a ratio of wt. % of molecules with monocycloparaffinic functionality to wt. % of molecules with multicycloparaff ⁇ nic functionality greater than 20; and a viscosity index greater than 28 x Ln (Kinematic Viscosity at 100°C.) + 110.
- the base oil further has a kinematic viscosity at 100°C. greater than 6 mm 2 /s. In a fifth embodiment, the base oil has a kinematic viscosity at 100°C. of less than 10 mm 2 /s. In another embodiment, the base oil has a wt. % aromatics less than 0.05 and a viscosity index greater than 28 x Ln (Kinematic Viscosity at 100 0 C.) + 95. In yet another embodiment, the base oil has a wt. % aromatics less than 0.30, a wt.
- % molecules with cycloparaff ⁇ nic functionality greater than the kinematic viscosity at 100°C, in mm 2 /s, multiplied by three, and a ratio of molecules with monocycloparaffinic functionality to molecules with multicycloparaffinic functionality greater than 15.
- the isomerized base oil contains between 2 - 10 % naphthenic carbon as measured by n-d-M, with the lower viscosity base oil generally having a lower naphthenic carbon distribution.
- the base oil has a kinematic viscosity of 1.5 - 3.0 mm 2 /s at 100°C. and 2-3 % naphthenic carbon.
- the isomerized base oil has an average molecular weight greater than 475; a viscosity index greater than 140, and a wt. % olefins less than 10. The base oil improves the air release and low foaming characteristics of the mixture when incorporated into the power transmission fluid composition.
- the isomerized base oil has between 5 - 18 wt.
- the isomerized base oil has less than 1.2 wt. % molecules with multicycloparaffin functionality.
- the isomerized base oil is produced from a process wherein the waxy feed is hydroisomerization dewaxed over a highly selective and active wax hydroisomerization catalyst which has: 1) a 1-D 10-ring molecular sieve having channels with a minimum crystallographic free diameter of not less than 3.9 Angstrom and a maximum crystallographic free diameter of not more than 6.0 Angstrom, and no channels with a maximum crystallographic free diameter greater than 6.0 Angstrom; T) a noble metal hydrogenation component; and 3) a refractory oxide support. Additionally, the waxy feed has: 1) a T90 boiling point greater than 49O 0 C; 2) greater than 40 wt.
- the isomerized base oil has at least one of the following properties: a kinematic viscosity at 100 0 C. between 10 mm 2 /s and 20 mm 2 /s; a kinematic viscosity at 40°C. between 50 mm 2 /s and 120 mm 2 /s; a viscosity index between 140 and 170; cold cranking simulator viscosity in the range of 10,000 - 20,000 at -25°C.
- the isomerized base oil has an oxidator BN of 30 to 70 hours.
- a cloud point of less than 5°C a spread between pour point and cloud point of less than 25°C; molecular weight of 400 - 700; and density in the range of 0.810 to 0.830.
- the thickener is an alkyldiurea compound having an average molecular weight in the range of from 600 to 700, wherein in the range of from 25 to 60 mole % of the total alkyl groups is an unsaturated component, and the total amine value of the primary amine constituting the raw material is in the range of from 250 to 350.
- the thickener is a perfluorocarbon resins selected from the group of polytetrafluoroethylene (PTFE), tetrafluoroethylene- perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and combinations thereof.
- PTFE polytetrafluoroethylene
- PFA tetrafluoroethylene- perfluoroalkylvinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- the thickener is polytetrafluoroethylene (PTFE) due to its excellent stability at high temperatures and resistance to chemicals.
- the thickener is a lithium complex soap containing at least two lithium components.
- examples include a lithium soap of at least one, hydroxy fatty acid, e.g., C12 to C29.
- the lithium component is selected from a lithium compound of (i) a C2 to C 12 aliphatic or cycloaliphatic dicarboxylic acid (or Cl to ClO, e.g., Cl to C4, alkyl ester thereof); or (ii) of a C3 to C24 hydroxy carboxylic acid (or Cl to ClO, such as Cl to C4, alkyl ester thereof) which has the hydroxy group separated from the carboxyl group by six or less carbon atoms; or a mixture thereof.
- the lithium component is a lithium salt of boric acid.
- the amount of lithium complex thickeners ranges from 5 to 20 wt. % of the total grease composition.
- the thickener is a complex basic aluminum soap.
- complex basic aluminum soaps is meant that the aluminum soap molecule contains at least one hydroxy anion for each aluminum cation, and at least two dissimilar anions substantially hydrocarbonaceous in character.
- substantially hydrocarbonaceous anions is meant those anions which are composed mainly of hydrogen and carbon, and include such anions which contain, in addition, minor amounts of substituents such as oxygen, nitrogen, etc.
- thickeners for use in the grease composition include aluminum laurate, aluminum soap oleate, aluminum stearate, aluminum benzoate stearate, aluminum benzoate oleate, aluminum benzoate 12-hydroxy stearate, aluminum toluate stearate, aluminum benzoate naphthenate, aluminum benzoate hydrogenated rosin, aluminum benzoate sulfonate, aluminum azelate stearate, aluminum phosphate benzoate stearate, aluminum benzoate hydroxy stearate, etc.
- thickeners for use in the grease composition include aluminum laurate, aluminum soap oleate, aluminum stearate, aluminum benzoate stearate, aluminum benzoate oleate, aluminum benzoate 12-hydroxy stearate, aluminum toluate stearate, aluminum benzoate naphthenate, aluminum benzoate hydrogenated rosin, aluminum benzoate sulfonate, aluminum azelate stearate, aluminum phosphate benzoate stearate, aluminum benzo
- the thickener is a mixture of diureas and polyureas, and wherein the diureas and polyureas are formed by the reaction of oleylamine, ethylenediamine, cyclohexylamine, and toluene diisocyanate.
- the thickener is a mixture comprising as the thickener constituents, (a) one or more urea-type compounds; (b) one or more fatty acid metal salts; and (c) at least one type of amide compound selected from the group comprised of aliphatic amides and aliphatic bisamides shown by the general formulae (1) and (2) R 1 CONH 2 (1) RICONHR 2 NHCOR 1 (2), wherein R 1 denotes a saturated or unsaturated alkyl group having from 15 to 17 carbon atoms and R 2 denotes a methylene group or an ethylene group.
- the grease composition further comprises at least an antioxidant in the range of 0.1 to 10 wt %.
- antioxidants include at least an organic compound containing nitrogen and mixtures thereof, such as organic amines, sulfides, hydroxy sulfides, phenols, etc., alone or in combination with metals like zinc, tin, or barium, etc.
- Examples include phenyl-alpha-naphthyl amine and derivatives, bis(alkylphenyl)amine, N 5 N diphenyl-p- phenylenediamine, 2,2,4 trimethyldihydroquinoline oligomer, bis(4 isopropylaminophenyl)-ether, N-acyl-p-aminophenol, N-acylphenothiazines, N of ethylenediamine tetraacetic acid, alkylphenol-formaldehyde-amine polycondensates, and alkylated diphenyl amines where the alkyl group(s) contain(s) from 1 to 12 carbon atoms; unsubstituted phenothiazine; substituted and unsubstituted quinolines where the substituents are alkyl groups of 1 to 10 carbon atoms; and mixtures thereof.
- the grease composition further comprises a polyhydroxylated compound to improve the low shear stability of the grease.
- the polyhydroxylated compound is a polyhydroxylated ester.
- the polyhydroxylated compound is pentaerythritol monooleate.
- the improvement in low shear stability is demonstrated by a lower percent softening measured using the Shell Roll Test (ASTM D 1831-00 (Reapproved 2006)).
- the grease composition softens less than 10% in the Shell Roll Test.
- the grease composition further comprises preservatives including but not limited to fungicides and antibacterial agents; colorants; shear stability additives; anti-wear / anti-weld and / or extreme-pressure agents including but not limited to carbamates, esters, molybdenum complexes, alkali- metal borates, antimony dithiocarbamates having 1 to 50 carbon in the alkyl group, dihydrocarbyl polysulfide, phosphorus compounds, boron compounds, zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl, and aryl type), diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, fluoroalkylpolysiloxane, lead naphthenate, neutralized phosphates, dithiophosphates, sulfur-free phosphates, and mixtures thereof; flame retardants such as calcium oxide; oiliness agents; ferrous / rust
- oil bleed inhibitors such as polybutne
- foam inhibitors such as alkyl methacrylate polymers and dimethyl silicone polymers
- metal deactivators such as disalicylidene propylenediamine, triazole derivatives, thiadiazole derivatives, mercaptobenzimidazoles; complex organic nitrogen, and amines; friction modifiers; thermal conductive additives; electroconductive agents; elastomeric compatibilizers; viscosity modifiers such as polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity modifiers; pour point depressants such as polymethyl methacrylate; multifunctional additives such as sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphorodithioate, oxymol
- the grease composition comprises greater than 4.0 wt % of calcium oxide having a LOI value of less than 3.0.
- LOI is "Loss on Ignition” parameter measured according to ASTM C25-06. LOI is used to measure the loss of flame retardant activity due to recarbonation.
- the grease composition further comprises from 0.1 to 15 wt. % an nano-particle additive or mixture thereof.
- the nano-particle additive is selected from the group of: a carbonate of a Group Ia alkali metal; a carbonate of a Group 2a alkaline earth metal, a sulfate of a Group Ia alkali metal or a Group 2a alkaline earth metal; a phosphate of a Group Ia alkali metal or Group 2a alkaline earth metal; a carboxylate of a Group Ia alkali metal; a carbonate of a Group 2a alkaline earth metal, or mixtures thereof, having an average particle size of less than 100 nanometers.
- the grease composition further comprises 0.1 to 7 wt. % of at least one of an oil-soluble organic molybdenum complex, an oil- soluble organic zinc compound of dithiocarbamic acid, an oil-soluble organic zinc compound of dithiophosphoric acid, an inorganic sulphur compound, and mixtures thereof.
- the grease composition further comprises 0.1 to 10 wt. % of at least one or more metal salts of a fatty acid wherein the metal is selected from the group consisting of aluminium, magnesium, zinc, calcium and mixtures thereof.
- the grease composition further comprises at least an oil-soluble amine salt of a phosphorus compound, e.g., phosphate and/or monthiophosphate.
- the grease composition further comprises 0.25 to 10 wt. % of at least one of dibutylthiophosphate and dibutylphosphate salts, such as an oleylamine salt of a mixture of dibutylthiophosphate and dibutylphosphate.
- the grease composition further comprises 0.25 to 10 wt. % of an olefin or a sulfurized olefin, e.g., polybutene or sulfurized polybutene.
- the grease composition further comprises an inorganic filler selected from the group consisting of metal oxides, metal nitrides, metal carbides, clay minerals, diamond, and mixtures thereof.
- the inorganic filler has an average particle size of less than 2 ⁇ m.
- the grease composition further comprises at least a thermally conductive additive in an amount of is 0.1-10 wt.%.
- a thermally conductive additive examples include but are not limited to aluminum nitride, silica, alumina, metal silicon, boron nitride, zinc oxide, and mixtures thereof.
- the thermally conductive grease further comprises an electroconductive filler, e.g., graphite, carbon black, carbon nanotubes, metal powder, and mixtures thereof, in an amount of 0.1 - 10 wt.%.
- the grease composition is employed in a solid stick grease form, i.e., by admixing the grease composition within a resin with the resin comprising 20 to 80 by weight of the total weight of the stick grease.
- the resin is a thermosetting plasticizer selected from the group consisting of branched phthalate, linear phthalate, branched adipate, mixed dibasic acid polyester, trimellitate, polyester glutarate, polyester adipate, citrate, polymeric plasticizer, sebacates, adipic acid polyesters, dioctyl adipate, a soybean-based plasticizer, and combinations thereof.
- the grease composition is prepared by mixing the base oil matrix with the thickener and/or components of thickeners, optional components and / or additives in a vessel, such as a grease making kettle, an-inline mixing chamber, or a contactor kettle. The mixture is then agitated with heating from 25 0 C. to 25O 0 C. depending on the thickener(s) used. In yet another embodiment and after mixing, the mixture of the base oil, thickener, and optional components / additives is sheared for a time sufficient to reduce substantially all of the thickener particles to below 500 microns in size.
- the base oil / thickener mixture is further processed to form a grease.
- the mixture is heated to a temperature of 125 to 175 0 C, then subsequently milled to form a homogeneous grease.
- milling is conducted at temperatures ranging from 10 0 C. to 175 0 C.
- additional standard grease manufacturing procedures such as filtering and de-airating the grease may be employed.
- the grease composition has a maximum torque of 10 N-m at -40°C. In a third embodiment, the grease composition displays a maximum torque of 12 N-m at -40 0 C. [087] In one embodiment, the grease composition exhibits excellent bearing life, i.e., capable of performing for longer period of time of at least 50% at high temperatures/speeds and in an oxidizing environment as compared to greases containing Group II or PAO base oils in the prior art. In one embodiment simulating the high temperature stability of the grease in an automotive wheel bearing and in a modified automotive front wheel hub-spindle-bearings assembly (ASTM D3527-02 Life Performance test), the grease composition has a bearing life of at least 150 hours. In a second embodiment with additives such as antioxidant, extreme-pressure, etc. added to the grease, the composition has a bearing life of at least 200 hours.
- the grease composition has a bearing life of at least 600 hours when tested for use with ball bearings operating under light loads at high speeds and elevated temperatures (ASTM D3336-97 (E2006). When tested without the addition of additives such as polybutene, the composition still exhibits an extended life of at nearly 400 hours.
- the grease composition exhibits excellent extreme pressure properties as measured using ASTM D2596-97(Reapproved 2002), with a highest LWL (LWL: Load- Wear Index) of 73.05 Kg and a LNSL (LNSL: Last Non-Seizure Load) of 126Kg.
- LWL Load- Wear Index
- LNSL Last Non-Seizure Load
- the solid stick grease is used between two metal surfaces in sliding and rolling-sliding contact such as steel wheel-rail systems including mass transit and freight systems.
- the composition further contains a liquid crystalline compound for use as lubrication grease for machine components, such as precision equipment, mobile telephone and hard disk drive of computer.
- the grease composition is used in electroconductive applications wherein the grease further comprises an electroconductive filler material, the grease is used for roll bearing of electric motor, automobile electrical parts, an alternator / an intermediate pulley (engine accessories), or an electromagnetic clutch for a car air conditioner.
- Polybutene is commercially available from a number of sources, having a density of 7.48 and a kinematic viscosity of 630 mm 2 /s @100°C.
- FT base oils are from Chevron Corporation of San Ramon, CA.
- the properties of the FTBO base oils used in the examples are shown in Table 2.
- PAO is a mixture of two highly branched isoparaffinic polyalphaolef ⁇ n (to get the desired viscosity) from Chevron Corporation of San Ramon, CA.
- the first PAO has a kinematic viscosity of 39.72 mm 2 /s @100°C (405.30 mm 2 /s @40°C) and the second PAO has a kinematic viscosity of 7.771 mm 2 /s @100°C (46.55 mm 2 /s @40°C).
- Group II is a commercially available mineral oil with a density of 7.2910 and kinematic viscosity of 12.15 mm 2 /s @100°C (112.6 mm 2 /s @40°C).
- Bright stock base oil is commercially available from various sources, having a density of 7.467 and kinematic viscosity of 30.09 mm 2 /s @100°C (461 mm 2 /s @40°C).
- Example 1 A base oil blend comprising 85 wt. % of FTBO-I and 15 wt. % of FTBO-2 Fischer-Tropsch derived base oils is used as the base oil matrix for the grease composition.
- the grease composition also comprises a polyurea thicknener comprising a diisocyanate and an alkylamine in an approximate 1 :2 ( ⁇ 0.5) to 1 :3 ratio ( ⁇ 0.5), and 1.5 to 20 wt. % of one or more corrosion inhibitors and antioxidants known in the art, and optional carrier oil.
- Example 2 A base oil blend comprising 70 - 90 wt. % mixture of
- the grease composition further comprises 5-30 wt. % of a polyurea thicknener comprising MDI, TDI or other diisocyanate and an alkyl amine in an approximate 1 :1 ( ⁇ 0.) to 1 :3 ratio, 0.5-10 wt. % of one or more oxidation inhibitors known in the art, 1.5 to 20 wt. % of at least a corrosion inhibitor known in the art, and optional carrier oil.
- a polyurea thicknener comprising MDI, TDI or other diisocyanate and an alkyl amine in an approximate 1 :1 ( ⁇ 0.) to 1 :3 ratio
- 0.5-10 wt. % of one or more oxidation inhibitors known in the art 1.5 to 20 wt. % of at least a corrosion inhibitor known in the art, and optional carrier oil.
- Examples 1 and 2 can be prepared as follows: A large stainless steel mixing bowl is charged with base oil (or mixtures thereof depending on the example) and heated close to 16O 0 F. The mixer is started at a moderate rate setting, and calculated amounts of thickener additives are added and let melt first if necessary
- a grease composition according to Example 1 was prepared and run 3 times, with the tests running normally for 360-391 hours at 355 0 F., after which the bearing temperature rose to 385 0 F. (criteria for grease failure). Temperature continued rising until a torque shutdown occurred, at which point the bearing failed between 392-398 hours.
- a grease composition according to Example 2 grease with polybutene was prepared and tested 3 times. The tests ran normally for 600-640 hours at 355 0 F., after which the bearing temperature continued rising to 375-38O 0 F. Temperature continued rising to 450 - 500 0 F. until a torque shutdown occurred. The bearing failed between 631 to 744 hours.
- Examples 3-6 In these examples, the base oil is first measured and then blended in a large stainless steel mixing bowl. The oil is next heated to close to 16O 0 F. Between 0.25-3 wt.% of a surfactant or surfactant blend is added and the mixture is stirred for 5 minutes. Between 3-15 wt% 12-Hydroxystearic can be added next. Mixture is allowed to cool gradually, then 0.5-10 wt% lithium hydroxide mono hydrate can be slowly added until well blended. The mixture is next heated slowly to 390-400 0 F. Temperature is held constant for 20 minutes, then mixture is allowed to cool off gradually to 180-250 0 F. before milling.
- a surfactant or surfactant blend is added and the mixture is stirred for 5 minutes. Between 3-15 wt% 12-Hydroxystearic can be added next. Mixture is allowed to cool gradually, then 0.5-10 wt% lithium hydroxide mono hydrate can be slowly added until well blended. The mixture is next heated slowly to 390-400 0
- additives can be added last after milling, then the mixture is allowed to cool off to 18O 0 F.
- Additives or additive packages used in this example may include 0.5-10 wt% extreme pressure agent(s), 0.1-5 wt% of at least a water resistance agent, 1-10 wt% of at least a viscosity modifier, 0.1-2 wt% of at least a rust inhibitor, 0-5 wt% of at least an antioxidant.
- Examples 3 and 5 employ base oils commonly used in the prior art, i.e., a mixture of Group II and bright stock base oils for Example 3 and PAO base oils for Example 5.
- Example 4 employs FTBO-I and Example 6 employs FTBO-3 as the base oil.
- Examples 11-12 In order to formulate the grease compositions in these examples, 1 kg. of the base oil is first measured and then blended in a large stainless steel mixing bowl. 5 to 17wt.% of 12-hydroxy stearic acid, 1-6 wt.% of an additive such as Synative FA, 0.3 to 8 wt% of an additive such as an overbased calcium sulfonate extreme pressure additive, and 0.25-3 wt% of an additive such as nonyl phenol 4 mole ethoxylate can be added next. The mixture is next stirred and heated to approximately 22O 0 F. The heating continued while 0.5-7% LiOH monohydrate is added slowly. The heating of the mixture continues to approximately 36O 0 F. and held at that temperature for 20 minutes.
- an additive such as Synative FA
- an additive such as an overbased calcium sulfonate extreme pressure additive
- an additive such as nonyl phenol 4 mole ethoxylate
- the mixture is next cooled slowly with the addition of another 0.40 - 0.70 kg. of the base oil. Temperature is held constant for 10 - 30 minutes, then mixture is allowed to cool off gradually to approximately 24O 0 F.
- about 0.25 - 2.0 wt% of at least a metal passivants, 1.0-6 wt% of at least an extreme pressure agent, 0.1-2.0 wt% of at least a rust inhibitor, 0 - 1 wt% of a tackifier, and 0.1-5 wt% of at least an antioxidant are incorporated before milling.
- a grease composition according to Example 11 grease was prepared employing a base oil commonly used in the prior art, i.e., PAO base oil and without polybutene as a viscosity modifier .
- a grease composition according to Example 12 grease was prepared employing a medium viscosity grade FT base oil, FTBO-I.
- Examples 13-14 Examples 11-12 were duplicated, except performance additives beyond a thickener system, e.g., LiOH monohydrate or a similar thickener, was incorporated, with Example 13 employing the PAO in Example 11, and Example 14 employing the medium viscosity FT base oil FTBO-I of Example
- Examples 15-17 In order to formulate the grease compositions in these examples, 1.5 kg. of the base oil is first measured, blended, and heated to 22O 0 F. While blending, 2 - 8 wt% of tallowalkylamine is added. Approximately 0.1-1.0 wt. % of a sulfinate detergent and H 2 O are added next. The mixture is mixed for 15 minutes at approximately 16O 0 F. In the next step, 2-10 wt% of MDI is added and the mixture is continuously mixed for an additional 30 minutes. The mixture is heated up slowly in stages to approximately 37O 0 F. and held steady for 30 minutes. The mixture is next cooled slowly with the addition of another 0.53 kg. of the base oil.
- Example 15 A grease composition according to Examples 15 and 16 employing base oils commonly used in the prior art were prepared with Example 15 incorporating a Group II base oil and Example 16 employing a PAO with a viscosity of about 4 mm 2 /s at 100 0 C.
- Example 17 employs a light viscosity grade FT base oil, FTBO-4.
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- General Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97570807P | 2007-09-27 | 2007-09-27 | |
| US97572807P | 2007-09-27 | 2007-09-27 | |
| US12/031,853 US20090088354A1 (en) | 2007-09-27 | 2008-02-15 | Lubricating grease composition and preparation |
| US12/031,830 US20090088353A1 (en) | 2007-09-27 | 2008-02-15 | Lubricating grease composition and preparation |
| PCT/US2008/076945 WO2009042507A1 (en) | 2007-09-27 | 2008-09-19 | Lubricating grease composition and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2205707A1 true EP2205707A1 (en) | 2010-07-14 |
| EP2205707A4 EP2205707A4 (en) | 2011-11-09 |
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ID=40511810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08832979A Withdrawn EP2205707A4 (en) | 2007-09-27 | 2008-09-19 | Lubricating grease composition and preparation |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2205707A4 (en) |
| JP (1) | JP2010540719A (en) |
| CN (1) | CN101855329A (en) |
| BR (1) | BRPI0817727A2 (en) |
| CA (1) | CA2700637A1 (en) |
| MX (1) | MX2010003303A (en) |
| WO (1) | WO2009042507A1 (en) |
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| EP2075314A1 (en) * | 2007-12-11 | 2009-07-01 | Shell Internationale Research Maatschappij B.V. | Grease formulations |
| WO2012017023A1 (en) * | 2010-08-03 | 2012-02-09 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| US8969269B2 (en) * | 2011-06-24 | 2015-03-03 | Chevron U.S.A. Inc. | Lubricating grease composition |
| US20130029888A1 (en) * | 2011-07-27 | 2013-01-31 | Chevron U.S.A. Inc. | Lubricating grease composition |
| CN102604723B (en) * | 2012-02-09 | 2013-09-25 | 中山大学 | Lubricating grease composition and preparation method thereof |
| US9187707B2 (en) * | 2013-01-18 | 2015-11-17 | Sal A Randisi, Sr. | Lubricating composition and method for preparing same |
| CN104513688B (en) * | 2013-09-30 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of polyurea grease of composite calcium zirconium base six and preparation method thereof |
| CN103666657B (en) * | 2013-11-22 | 2015-04-29 | 广西大学 | Heavy-load vehicle hub bearing grease |
| CN104140862B (en) * | 2014-07-10 | 2016-03-30 | 新乡市恒星科技有限责任公司 | A kind of extreme pressure compound lithium base grease additive and preparation method thereof |
| CN105018208A (en) * | 2015-07-20 | 2015-11-04 | 广西大学 | High temperature-resistant water spraying-resistant radiation-resistant wear-resistant lubricating grease composition |
| JP2017043745A (en) * | 2015-08-28 | 2017-03-02 | コスモ石油ルブリカンツ株式会社 | Grease composition |
| CN105296061A (en) * | 2015-11-24 | 2016-02-03 | 杭州力特油剂有限公司 | Lubricating grease |
| US10392577B2 (en) * | 2016-05-18 | 2019-08-27 | Nch Corporation | Composition and method of manufacturing overbased sulfonate modified lithium carboxylate grease |
| JP2018053942A (en) * | 2016-09-26 | 2018-04-05 | セイコーエプソン株式会社 | Robot and gear device |
| JP2018090783A (en) * | 2016-11-30 | 2018-06-14 | ミネベアミツミ株式会社 | Grease composition and rolling bearing |
| US11078438B2 (en) | 2017-07-24 | 2021-08-03 | Chemtool Incorporated | Extreme pressure metal sulfonate grease |
| CN108192713A (en) * | 2017-12-28 | 2018-06-22 | 山东国大黄金股份有限公司 | A kind of mine lubricating oil |
| CN109536249A (en) * | 2018-10-30 | 2019-03-29 | 新疆金雪驰科技股份有限公司 | A kind of lubricating grease and preparation method thereof applied to wind power plant yaw system gear |
| JP7220076B2 (en) | 2018-12-27 | 2023-02-09 | シェルルブリカンツジャパン株式会社 | Lubricant composition for ball joints |
| CN110982583A (en) * | 2019-11-07 | 2020-04-10 | 江苏澳润新材料有限公司 | Low-temperature composite calcium sulfonate-based lubricating grease and preparation method thereof |
| CN112048354A (en) * | 2020-09-23 | 2020-12-08 | 上海虎头化工有限公司 | Long-acting high-temperature lubricating grease and preparation method thereof |
| CN121039260A (en) * | 2023-03-29 | 2025-11-28 | 胜牌全球产品知识产权有限公司 | Electric vehicle lubricants and additives |
| JP2024170999A (en) * | 2023-05-29 | 2024-12-11 | 協同油脂株式会社 | Grease composition |
| CN116716087B (en) * | 2023-08-10 | 2023-11-03 | 南方电网调峰调频(广东)储能科技有限公司 | White oil-based immersion coolant for electronic components |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362409A (en) * | 1992-07-10 | 1994-11-08 | The Lubrizol Corporation | Grease compositions |
| US5851969A (en) * | 1997-03-14 | 1998-12-22 | Exxon Research And Engineering Company | Grease containing diamine corrosion inhibitors |
| US7111989B1 (en) * | 2002-10-01 | 2006-09-26 | Emerson Power Transmission Manufacturing, L.P. | Bearing assembly and lubricating grease |
| GB2408749B (en) * | 2003-02-20 | 2005-10-05 | Chevron Usa Inc | New low noise grease gelling agents |
| US6916768B2 (en) * | 2003-02-20 | 2005-07-12 | Chevron U.S.A. Inc. | Low noise grease gelling agents |
| JP5108200B2 (en) * | 2003-11-04 | 2012-12-26 | 出光興産株式会社 | Lubricating oil base oil, method for producing the same, and lubricating oil composition containing the base oil |
| US7214307B2 (en) | 2004-07-22 | 2007-05-08 | Chevron U.S.A. Inc. | White oil from waxy feed using highly selective and active wax hydroisomerization catalyst |
| US7402236B2 (en) | 2004-07-22 | 2008-07-22 | Chevron Usa | Process to make white oil from waxy feed using highly selective and active wax hydroisomerization catalyst |
| US7407920B2 (en) * | 2004-07-29 | 2008-08-05 | Crompton Corporation | Overbased calcium salicylate greases |
| JP5180437B2 (en) * | 2005-01-07 | 2013-04-10 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
| US7465696B2 (en) * | 2005-01-31 | 2008-12-16 | Chevron Oronite Company, Llc | Lubricating base oil compositions and methods for improving fuel economy in an internal combustion engine using same |
| US7547666B2 (en) * | 2005-12-21 | 2009-06-16 | Chevron U.S.A. Inc. | Ashless lubricating oil with high oxidation stability |
| JP4809626B2 (en) * | 2005-04-28 | 2011-11-09 | 昭和シェル石油株式会社 | Urea-based lubricating grease composition |
| US20070066495A1 (en) * | 2005-09-21 | 2007-03-22 | Ian Macpherson | Lubricant compositions including gas to liquid base oils |
| EP2075314A1 (en) * | 2007-12-11 | 2009-07-01 | Shell Internationale Research Maatschappij B.V. | Grease formulations |
-
2008
- 2008-09-19 MX MX2010003303A patent/MX2010003303A/en unknown
- 2008-09-19 EP EP08832979A patent/EP2205707A4/en not_active Withdrawn
- 2008-09-19 WO PCT/US2008/076945 patent/WO2009042507A1/en not_active Ceased
- 2008-09-19 CN CN200880115873A patent/CN101855329A/en active Pending
- 2008-09-19 JP JP2010527043A patent/JP2010540719A/en active Pending
- 2008-09-19 CA CA2700637A patent/CA2700637A1/en not_active Abandoned
- 2008-09-19 BR BRPI0817727A patent/BRPI0817727A2/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
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| CA2700637A1 (en) | 2009-04-02 |
| EP2205707A4 (en) | 2011-11-09 |
| JP2010540719A (en) | 2010-12-24 |
| CN101855329A (en) | 2010-10-06 |
| MX2010003303A (en) | 2010-08-31 |
| WO2009042507A1 (en) | 2009-04-02 |
| BRPI0817727A2 (en) | 2017-05-16 |
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