EP2373771B1 - Graisse industrielle et automobile et son procédé de fabrication - Google Patents

Graisse industrielle et automobile et son procédé de fabrication Download PDF

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Publication number
EP2373771B1
EP2373771B1 EP09830730.9A EP09830730A EP2373771B1 EP 2373771 B1 EP2373771 B1 EP 2373771B1 EP 09830730 A EP09830730 A EP 09830730A EP 2373771 B1 EP2373771 B1 EP 2373771B1
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European Patent Office
Prior art keywords
group
oil
iso
grease
obtaining
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EP09830730.9A
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German (de)
English (en)
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EP2373771A4 (fr
EP2373771A1 (fr
Inventor
Carol A. Barnes
Kamilah N. Smith
Alan G. Blahey
Douglas C. Maclaren
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Publication of EP2373771A4 publication Critical patent/EP2373771A4/fr
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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
    • 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
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
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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
    • 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
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C10M2207/1276—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/073—Star shaped polymers
    • C—CHEMISTRY; METALLURGY
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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
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
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    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This invention relates to a lubricating grease composition suitable for industrial and automotive uses, and a process for its manufacture.
  • the invention relates to a premium multipurpose grease composition exhibiting favorable water resistant properties, high and low temperature performance, and which is suitable for use in both industrial and automotive applications.
  • a lubricating grease In North America and other northern climates, it is desirable for a lubricating grease to exhibit good performance over a wide range of temperatures. In addition, industrial greases often require good performance in wet environments. Testing methods and performance criteria established by the National Lubricating Grease Institute (NLGI) have become industry-wide accepted standards. These standards include greases for use in automotive applications. It is therefore desirable for lubricating grease to meet NLGI grade classification. Preferably, such greases should be multipurpose, being suitable for industrial applications and meet NLGI grade classification for automotive application. For instance, WO 2005/090531 and EP 0 405 893 A2 disclose grease compositions having good water resistance.
  • NLGI National Lubricating Grease Institute
  • this invention relates to a premium multipurpose lubricating grease suitable for industrial and automotive uses, and a process for making the same.
  • a lubricating grease composition comprising, based on the overall grease composition:
  • a method for making a lubricating grease comprises: (a) obtaining at least one bright stock Group I oil, (b) obtaining at least one naphthenic Group V oil, (c) obtaining at least one ISO 68 Group I oil, (d) obtaining at least one ISO 100 Group II oil, (e) obtaining a hydrophilic copolymer containing a styrene and a carboxylic acid, an anhydride or an ester, (f) obtaining a soap thickener, (g) obtaining an antioxidant, and (h) mixing, based on the overall grease composition, 30 to 40 wt% of the at least one bright stock Group I oil (a), 5 to 15 wt% of the at least one naphthenic Group V oil (b), 5 to 10 wt% of the at least one ISO 68 Group I oil (c), 20 to 30 wt% of the least one ISO 100 Group II oil (d), 2 to 6 wt% of the polymer (e)
  • Various lubricating oils can be employed in preparing the grease compositions of the present invention. Applicants have found that using oils of a certain type during the cooking phase of the grease preparation, and oils of a different type during the finishing phase achieved a grease with favorable properties. Another embodiment of the present invention is the inclusion of a polymer that imparts excellent water resistance properties without compromising the low temperature performance of the grease. Applicants have found that using a hydrophilic polymer provided favorable properties.
  • Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks generally have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates.
  • Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
  • Group III stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stocks include base stocks not included in Groups I-IV. Table 1 summarizes properties of each of these five groups. Table 1: Base Stock Properties Saturates Sulfur Viscosity Index Group I ⁇ 90% and/or > 0.03% and ⁇ 80 and ⁇ 120 Group II ⁇ 90% and ⁇ 0.03% and ⁇ 80 and ⁇ 120 Group III ⁇ 90% and ⁇ 0.03% and ⁇ 120 Group IV Polyalphaolefins (PAO) Group V All other base oil stocks not included in Groups I, II, III, or IV
  • the base stocks include at least one base stock of synthetic oils.
  • Synthetic oil for purposes of this application shall include all oils that are not naturally occurring mineral oils.
  • lubricating oils will typically comprise between 50 - 90 wt% of the overall grease composition. These oils will typically combine to provide an overall viscosity of the grease in the range of ISO 100 to ISO 320.
  • the preferred viscosity for the present invention is between ISO 150 to ISO 275, with ISO 220 being the most preferred.
  • the lubricating oils used as the base stock in the cooking phase of the manufacturing process are at least one bright stock Group I oil and at least one naphthenic Group V oils. These oils will have a preferred viscosity in the range of 200 to 1400 cSt at 40°C, with a range of 200 to 500 cSt at 40°C being most preferred.
  • a combination of heavy naphthenic oil and a bright stock are used as the base stock during the cooking phase, with 5-15 wt% heavy naphthenic oil and 30 - 40 wt% bright stock.
  • the use of Group II oils during the cooking phase should be limited or avoided altogether.
  • a combination of 5 - 10 wt% of an ISO 68 Group I and 20 - 30 wt% of an ISO 100 Group II are used during the finishing phase.
  • Various other oils in smaller amounts may also be incorporated during the finishing phase.
  • the grease composition will also contain a soap thickener dispersed in the lubricating oil during the cooking phase to form a base grease.
  • the soap thickener will comprise between 5% and 15% of the overall grease composition weight.
  • the particular thickener employed is not critical and can vary broadly provided that it is effectively water insoluble.
  • the thickener may be based on aluminum, barium, calcium or lithium soaps, or their complexes.
  • Soap thickeners may be derived from a wide range of animal oils, vegetable oils and greases, as well as the fatty acids derived therefrom. Carbon black, silica, and clays may be used as well as dyes, polyureas and other organic thickeners. Pyrrolidone-based thickeners can also be used.
  • Preferred thickeners are based on lithium soap, calcium soap, their complexes, or mixtures thereof. Particularly preferred is a lithium or lithium complex thickener derived from reacting a C-18 fatty acid (12-hydroxy stearic acid) and a C-9 dicarboxylic acid (azelaic acid) with lithium hydroxide monohydrate.
  • Canadian Patent 996537 provides a process for making this preferred thickener.
  • a mixture of Group I and Group V oils and a lithium soap of a C 12 to C 24 hydroxy fatty acid is first prepared. Then a C 2 to C 12 aliphatic carboxylic acid is added to that mixture and converted to its dilithium soap under conditions that are suitable for the formation of a complex between the lithium soap of the dicarboxylic acid and the lithium soap of the hydroxy fatty acid. While the lithium soap of the hydroxy fatty acid could be preformed and then dispersed in the lubricating oil medium, it is generally more expedient to prepare that soap in situ in the lubricating oil by neutralizing the hydroxy fatty acid with lithium base.
  • the usual procedure during the cooking phase is to charge into the grease kettle the Group I and Group V oils and to then add the hydroxy fatty acid.
  • the mixture of fatty acid and oil is heated sufficiently to bring about the dissolving action, e.g. at 82 to 93°C (180 to 200°F ) .
  • a concentrated aqueous solution of the lithium base is added, usually in an amount slightly in excess of that required to neutralize the acid.
  • the temperature at this stage of the cooking phase is usually between 93 to 99°C (200 and 210°F ) .
  • the rate of addition of the lithium base may be varied.
  • the temperature of the mixture of the Group I and Group V oils and lithium soap of the hydroxy fatty acid be raised to between 121 to 149°C (250 and 300°F ) . This is done in order to bring about a substantial dehydration of the mixture, such as, the removal of 70 to 100% of the water.
  • the temperature of the grease mixture is once again raised in order to bring about dehydration. Preferably this will take place at 138 to 149°C (280 to 300°F ) .
  • the temperature of the mixture should further be raised to preferably between 193 to 204°C (380 and 400°F ) .
  • the soap stock is then cooled during the finishing phase of the grease preparation. Finishing oils, including Group II oils and various other lubricating oils, may be added into the mixture at this point. Mixing may continue until the grease has reached ambient temperatures. When the temperature has been lowered to about 65°C (150°F), other grease additives can be introduced as would be understood by persons skilled in the art.
  • one embodiment contemplates the inclusion of a polymer.
  • Various polymers may be used in greases, although the precise impact of any given polymer on a given grease cannot be predicted. Applicants have found that the use of a hydrophilic copolymer was important in achieving excellent water resistance properties.
  • maleic anhydride styrene esterified copolymer is used, with the preferred amount being between 2 and 6 wt% of the overall grease.
  • the polymer may be incorporated during either the cooking phase or finishing phase of the grease preparation.
  • the preferred styrene maleic anhydride ester (SMAE) copolymer is unique from other polymer examples because it contains oxygen groups.
  • the structure of the SMAE copolymer (shown below) has exposed hydroxyl and carbonyl groups that can act as hydrogen bond donors (former) and acceptors (latter).
  • the SMAE copolymer is more hydrophilic than strictly hydrocarbon-based copolymers such as styrene isoprene and styrene isobutylene.
  • Equation 1 shows the chemical structure of the SMA ester and the esterification of styrene maleic anhydride copolymer to form a SMA ester and the resulting chemical structure of the SMA ester.
  • the grease structure is a type of soap. The ability of the soap to dissolve in waters varies. Preferably, the grease soap should not readily dissociate in contact with water.
  • the grease soap structure is held together with a variety of bonds, including ionic bonds with the metal, hydrogen bonds within the oxygen-rich triglyceride and the ester function of 12-hydroxy stearic acid (once incorporated into the structure) and van der Waals interactions between the C-C side chains.
  • bonds including ionic bonds with the metal, hydrogen bonds within the oxygen-rich triglyceride and the ester function of 12-hydroxy stearic acid (once incorporated into the structure) and van der Waals interactions between the C-C side chains.
  • a polymer that incorporates or binds water molecules into its structure may enhance the water resistance performance of a grease.
  • Hydrogen bonding capability present in certain copolymers can improve their ability to incorporate or bind water molecules into their respective structures.
  • the water resistance performance of a grease may be improved where the copolymer provides preferential binding of the water, such as, the attraction of water to the copolymer, through hydrogen bonding, is stronger than the attraction of water to the grease structure.
  • the grease may also contain small amounts of supplemental additives, which include antioxidants, anti-wear agents and other additives.
  • supplemental additives include antioxidants, anti-wear agents and other additives.
  • Specific antioxidants employed are not critical and can vary broadly to achieve favorable properties. A combination of a Group II oil and diphenylamine antioxidant was found to enhance the oxidation life of the grease, while achieving good high temperature performance.
  • Antioxidants will typically comprise less than 5 wt% of the overall grease composition.
  • the total amount of all additives, including the antioxidant will typically be between 2 - 10wt% of the overall grease.
  • a person skilled in the art will recognize the benefits of adding specific additives to the grease disclosed herein to achieve favorable properties.
  • the examples in table 2 below disclose various screening tests for the influence of the base oils and thickener on overall grease performance.
  • the grease performance tests include water spray-off, low temperature torque, fretting wear and wheel bearing life.
  • Table 3 below discloses screening test for the influence of the polymer selection and concentration on overall grease performance. These tests includes water spray-off, wet roll, water washout, low temperature torque, fretting wear, wheel bearing life and apparent viscosity.
  • Table 4 discloses screening tests for the influence of various antioxidants on grease performance for wheel bearing life. The results of Table 4 demonstrate that a combination of an ISO 100 Group II base oil and a diphenylamine antioxidant achieved good high temperature performance and oxidation life.
  • Table 4 EXAMPLE # 1 * 19 * 20 * 21 22 BATCH # Invention 12-52-07 GR1004-156-2 GR1004-156-3 GR1004-156-1 Batch 8 GR1004-152 BASE OILS ISO 100 Group II 24 24 24 24 24 0 Heavy Naphthenic 10.2 10.2 10.2 10.2 11.7 ISO 68 Group I 8.7 8.7 8.7 16.6 Bright Stock 35.6 35.6 35.6 35.6 47.5 ISO 22 Naphthenic 0 0 0 0 4.1 ADDITIVES Polymer A 3 3 3 3 3 3 3 3 3 Antioxidant (diphenylamine) 1.5 0.76 0.30 0 1.5 PERFORMANCE Wheel Bearing Life, D3527, hr (125 min.) 153 134 130 80 47 LEGEND Base Oil

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (6)

  1. Composition de graisse lubrifiante comprenant, par rapport à la composition de graisse dans son ensemble :
    (a) 30 à 40 % en poids d'au moins une huile de base lubrifiante de haute viscosité du Groupe I ;
    (b) 5 à 15 % en poids d'au moins une huile naphténique du Groupe V,
    (c) 5 à 10 % en poids d'au moins une huile ISO 68 du Groupe I ;
    (d) 20 à 30 % en poids d'au moins une huile ISO 100 du Groupe II ;
    (e) 2 à 6 % en poids d'un copolymère hydrophile contenant un styrène et un acide carboxylique, un anhydride ou un ester ;
    (f) 5 à 15 % en poids d'un épaississant de type savon, et
    (g) un antioxydant,
    dans laquelle
    l'épaississant de type savon (f) est dispersé dans la au moins une huile de base lubrifiante de haute viscosité du Groupe I (a) et la au moins une huile naphténique du Groupe V (b) pendant une phase de cuisson et la au moins une huile ISO 68 du Groupe I (c) et la au moins une huile ISO 100 du Groupe II (d) sont introduites pendant une phase de finition.
  2. Graisse selon la revendication 1, dans laquelle le copolymère est un ester de styrène-anhydride maléique.
  3. Graisse selon l'une quelconque des revendications précédentes, dans laquelle l'épaississant est obtenu par réaction d'un mélange d'un hydroxyacide gras en C12 à C24 et d'un diacide carboxylique en C2 à C12 avec une base au lithium.
  4. Graisse selon la revendication 1, dans laquelle l'antioxydant est un antioxydant à base d'amine.
  5. Graisse selon la revendication 1, dans laquelle l'antioxydant est la diphénylamine.
  6. Procédé de fabrication d'une graisse lubrifiante, ledit procédé comprenant les étapes consistant à :
    (a) obtenir au moins une huile de base lubrifiante de haute viscosité du Groupe I ;
    (b) obtenir au moins une huile naphténique du Groupe V ;
    (c) obtenir au moins une huile ISO 68 du Groupe I ;
    (d) obtenir au moins une huile ISO 100 du Groupe II ;
    (e) obtenir un copolymère hydrophile contenant un styrène et un acide carboxylique, un anhydride ou un ester ;
    (f) obtenir un épaississant de type savon ;
    (g) obtenir un antioxydant ; et
    (h) mélanger, par rapport à la composition de graisse dans son ensemble, 30 à 40 % en poids de la au moins une base lubrifiante de haute viscosité (a), 5 à 15 % en poids de la au moins une huile naphténique (b), 5 à 10 % en poids de la au moins une huile ISO 68 du Groupe I (c), 20 à 30 % en poids de la au moins une huile ISO 100 du Groupe II (d), 2 à 6 % en poids du polymère (e), 5 à 15 % en poids de l'épaississant de type savon (f), et l'antioxydant (g) pour former un graisse, dans lequel
    l'épaississant (f) est dispersé dans la au moins une huile de base lubrifiante de haute viscosité du Groupe I (a) et la au moins une huile naphténique du Groupe V (b) pendant une phase de cuisson et
    la au moins une huile ISO 68 du Groupe I (c) et la au moins une huile ISO 100 du Groupe II (d) sont introduites pendant une phase de finition.
EP09830730.9A 2008-12-05 2009-12-04 Graisse industrielle et automobile et son procédé de fabrication Not-in-force EP2373771B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20096508P 2008-12-05 2008-12-05
PCT/US2009/006387 WO2010065130A1 (fr) 2008-12-05 2009-12-04 Graisse industrielle et automobile et son procédé de fabrication

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EP2373771A1 EP2373771A1 (fr) 2011-10-12
EP2373771A4 EP2373771A4 (fr) 2012-07-04
EP2373771B1 true EP2373771B1 (fr) 2014-02-12

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EP (1) EP2373771B1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106047458A (zh) * 2016-05-31 2016-10-26 安徽潜山轴承制造有限公司 一种环保型轴承润滑脂组合物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6841547B2 (ja) * 2017-01-18 2021-03-10 出光興産株式会社 グリース組成物及びその製造方法

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Publication number Priority date Publication date Assignee Title
US3791973A (en) * 1971-02-24 1974-02-12 Exxon Research Engineering Co Grease thickened with lithium soap of hydroxy fatty acid and lithium salt of aliphatic dicarboxylic acid
JPS59204695A (ja) * 1983-05-10 1984-11-20 Idemitsu Kosan Co Ltd リチウム系グリ−スおよびその製造方法
US5110490A (en) * 1989-06-27 1992-05-05 Exxon Research And Engineering Company Water resistant grease composition
US6300288B1 (en) * 1994-03-31 2001-10-09 The Lubrizol Corporation Functionalized polymer as grease additive
US5707943A (en) * 1996-12-16 1998-01-13 The Lubrizol Corporation Mixtures of esterified carboxy-containing interpolymers and lubricants containing them
US5880074A (en) * 1997-01-09 1999-03-09 Dishong; Dennis M. Additive concentrates containing mixtures of organic diluents and esterified carboxy-containing interpolymers and lubricants containing them
US20040018946A1 (en) * 2002-07-26 2004-01-29 Aoyagi Edward I. Method of improving the frictional properties of functional fluids
US7691795B2 (en) * 2002-10-01 2010-04-06 The Lubrizol Corporation Metal hydroxide desiccated emulsions used to prepare grease
US7141157B2 (en) * 2003-03-11 2006-11-28 Chevron U.S.A. Inc. Blending of low viscosity Fischer-Tropsch base oils and Fischer-Tropsch derived bottoms or bright stock
US20050209114A1 (en) * 2004-03-19 2005-09-22 The Lubrizol Corporation, A Corporation Of The State Of Ohio Functionalized polymer composition for grease
EP2082406A1 (fr) * 2006-10-19 2009-07-29 Shell Internationale Research Maatschappij B.V. Composition d'huile électrique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106047458A (zh) * 2016-05-31 2016-10-26 安徽潜山轴承制造有限公司 一种环保型轴承润滑脂组合物

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US20110059879A1 (en) 2011-03-10
CA2743826C (fr) 2016-12-20
EP2373771A4 (fr) 2012-07-04
EP2373771A1 (fr) 2011-10-12
CA2743826A1 (fr) 2010-06-10

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