Classifications

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  • 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
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  • 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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  • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
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  • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
  • C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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  • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
  • C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
  • C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
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  • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
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  • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
  • C10M123/04—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a macromolecular compound
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  • 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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  • 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
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  • 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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  • 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
  • C10M2205/022—Ethene
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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
  • C10M2205/024—Propene
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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
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  • 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
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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
  • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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  • 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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  • 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
  • C10M2207/126—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 monocarboxylic
  • C10M2207/1265—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 monocarboxylic used as thickening agent
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  • 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
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  • 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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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/16—Naphthenic acids
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  • 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
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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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  • 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
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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/02—Bearings
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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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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 present invention relates to a lithium complex grease having improved thickener yield. More particularly, a more economical yet effective lithium complex grease is provided having a higher weight of base oil incorporated into the grease matrix.
• Lithium complex greases have been known and manufactured for quite some time. Such greases can be made from any of a wide number of different base stocks of lubricating oil viscosity, and combination and mixtures of such stocks. The resulting greases are all marked by varying levels of desirable grease characteristics including dropping point, penetration, mechanical and/or shear stability, oxidation resistance, etc., all of which in combination are taken into account when describing the lubricating life of the grease.
• Lithium complex greases comprising a lithium complex thickener and a lubricating base oil are well known.
• a grease composition comprising a major amount of a base oil of lubricating viscosity, and a minor amount of a lithium complex thickener.
• the grease composition can further comprise a copolymer, for example, of styrene and butadiene.
• the composition will comprise less than 25 wt % of the thickener in combination with the copolymer.
• the present grease composition exhibits a higher thickener yield, believed due to the combination of the lithium complex thickener and the copolymer, which in one embodiment is comprised of styrene and butadiene.
• a grease composition has been discovered which provides good mechanical properties, but also good economics.
• the thickener yield for the grease is much higher due to the presence of the copolymer of styrene and butadiene.
• the thickener yield can be at least 25% higher, 35% higher or even 50% higher than that of a composition without the copolymer.
• the lubricant base oil used in the present invention can be selected from Group I, II, III, IV, and V lubricant base oils, and mixtures thereof.
• the lubricant base oils of the present invention include synthetic lubricant base oils, such as Fischer-Tropsch derived lubricant base oils, and mixtures of lubricant base oils that are not synthetics and synthetics.
• the specifications for Lubricant Base Oils defined in the API Interchange Guidelines (API Publication 1509) using sulfur content, saturates content, and viscosity index, are shown below in Table I:
• Facilities that make Group I lubricant base oils typically use solvents to extract the lower viscosity index (VI) components and increase the VI of the crude to the specifications desired. These solvents are typically phenol or furfural. Solvent extraction gives a product with less than 90% saturates and more than 300 ppm sulfur. The majority of the lubricant production in the world is in the Group I category.
• VI viscosity index
• Facilities that make Group II lubricant base oils typically employ hydroprocessing such as hydrocracking or severe hydrotreating to increase the VI of the crude oil to the specification value.
• hydroprocessing typically increases the saturate content above 90 and reduces the sulfur below 300 ppm.
• Approximately 10% of the lubricant base oil production in the world is in the Group II category, and about 30% of U.S. production is Group II.
• VGO waxy vacuum gas oil
• SOG waxy vacuum gas oil
• Fischer-Tropsch wax is an ideal feed for a wax isomerization process to make Group III lubricant base oils. Only a small fraction of the world's lubricant supply is in the Group III category.
• Group IV lubricant base oils are derived by oligomerization of normal alpha olefins and are called poly alpha olefin (PAO) lubricant base oils.
• PAO poly alpha olefin
• Group V lubricant base oils are all others. This group includes synthetic esters, silicon lubricants, halogenated lubricant base oils and lubricant base oils with VI values below 80. For purposes of this application, Group V lubricant base oils exclude synthetic esters and silicon lubricants. Group V lubricant base oils typically are prepared from petroleum by the same processes used to make Group I and II lubricant base oils, but under less severe conditions.
• Synthetic lubricant base oils meet API Interchange Guidelines but are prepared by Fisher-Tropsch synthesis, ethylene oligomerization, normal alpha olefin oligomerization, or oligomerization of olefins boiling below C 10 .
• the lithium complex thickener used in the present grease composition can be any known lithium complex thickener.
• the lithium complex thickener can comprise a lithium soap derived from a fatty acid containing an epoxy group and/or ethylenic unsaturation and a dilithium salt derived from a straight chain dicarboxylic acid and/or, in one embodiment, a lithium salt derived from a hydroxy-substituted carboxylic acid such as salicylic acid.
• the thickener can be a complex of a lithium soap of a C 12 to C 24 hydroxy fatty acid and a monolithium salt of boric acid and can include a lithium salt of a second hydroxy carboxylic acid such as salicylic acid.
• the complex can comprise a lithium soap of a C 12 to C 24 hydroxy fatty acid thickener antioxidant comprising an alkali metal salt of hydroxy benzoic acid and a diozime compound.
• the alkali metal salt of hydroxy benzoic acid include dilithium salicylate.
• the complex can be a lithium soap which is a combination of a dilithium salt of a C 4 to C 12 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12-hydroxy C 12 to C 24 fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formed in-situ in the grease from a second hydroxy carboxylic acid wherein the —OH group is attached to a carbon atom not more than 6 carbons removed from the carboxyl group and wherein either of those groups may be attached to either aliphatic or aromatic portions of the materials.
• a lithium soap which is a combination of a dilithium salt of a C 4 to C 12 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12-hydroxy C 12 to C 24 fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formed in-s
• the lithium complex can comprise a combination of a complex lithium soap thickener, a lithium salt of a C 3 to C 14 hydroxycarboxylic acid and a thiadiazole.
• the grease may also optionally and preferably contain additional antioxidants, preferably amine type or phenol type anti-oxidants, most preferably amine type antioxidants.
• the lithium complex thickener is simply a lithium salt of a carboxylic acid, and in particular a hydroxycarboxylic acid, such as hydroxystearic acid.
• a thickener can be prepared, for example, by reacting lithium hydroxyl monohydrate with the hydroxystearic acid.
• the greases will comprise a major amount, e.g., greater than 50% by weight of the base oil, and a minor amount of the thickener and any other additives, i.e., less than 50% by weight.
• the greases of the present invention may, of course, contain any of the other, typical grease additives such as rust inhibitors, barium dinonyl naphtheline fulfonate, order modifiers, tackiness agents, extreme pressure agents, water shedding agents, dyes, etc.
• typical additives and their function are described in Modem Lubricating Greases by C. J. Boner, Scientific Publication (G.B.) Ltd. 1976.
• a copolymer is of particular significance as an additive.
• the copolymer can be a hydrocarbon based copolymer such as a copolymer of styrene and butadiene or ethylene and propylene.
• the copolymer additive is a copolymer of styrene and butadiene. It has been found that use of a small amount of such a copolymer, e.g. from 2-6 weight percent, or from 2-5 weight percent, or in another embodiment, from 3-4 weight percent, in combination with a lithium complex thickener, results in a 25-50% increase in thickener yield.
• Grease thickener yield defined as the weight of base oil incorporated into the grease matrix per unit of weight of thickener, is a key determinant of grease mechanical properties, such as penetration, shear stability and water resistance as well as formula cost.
• the incorporation of the copolymer of styrene and butadiene with the lithium complex thickener permits the use of a greater amount of base oil, thereby raising the grease thickener yield, while maintaining good mechanical properties. The result is a more economical yet still effective grease.
• Such copolymers of styrene and butadiene are commercially available.
• V-211 is a copolymer of styrene and butadiene available from Functional Products, Inc. of Cincinnati, Ohio.
• the copolymer is a white-yellow rubber powder which is quick dissolving.
• These copolymers of styrene and butadiene can be used in conjunction with other polymers, but they must be present in the grease compositions of the present invention.
• the yield relating to the amount of base oil one incorporates into the grease matrix while still realizing good mechanical properties, can increase by at least about 25 weight percent, about 35 weight percent, or at least about 50 weight percent.
• Such grease compositions have been shown to exhibit worked penetration properties of at least about 290, at least about 300, and even at least about 310.
• the compositions can be used in any automotive grease or industrial grease application.
• the grease compositions can be used for wheel bearings, an automotive chassis or for lubricating gears.
• 1-50 wt % of formula amount of base oil(s) were mixed in an open kettle at room temperature.
• Formula amount of mono and di-acids, emulsifier(s) are added with water [at 50% base oil amount] and stirred while heating to 200° F.
• lithium hydroxide is added slowly. Once the lithium hydroxide had been added, the mixture was heated to 400° F. It was held at 400° F. while stirring for 20 minutes.
• the grease is then cooled to 175° F. while stirring.
• performance additives e.g., rust inhibitor, extreme-pressure and anti-wear agents and polymers, tackifiers are added.
• the grease penetration was adjusted by adding base oil slowly while stirring. When penetration range was achieved, the grease was cooled to room temperature and stored suitably.
• Lubrizol 528C, EC5426A rust inhibitor
• glycerin, Lubrizol 5200 extreme-pressure, anti-wear agents
• Lubrizol 2002D functionalized olefin polymer
• V-2II copolymer of styrene-butadiene
• V-207 copolymer of ethylene and propylene
• Runs A and B are considered as base cases using a PIB polymer or a functionalized olefin polymer. In both cases, the base oil amount used is 80% of formula amount. In runs C and D, when these polymers are replaced with styrene-butadiene or ethylene-propylene copolymers, the used base oil amount increases to 157 and 132% of formula amount respectively. With an increasing amount of base oil in the formula, thickener yield increases accordingly. Runs E, F, G, and H show increased thickener yield with styrene-butadiene copolymer use in conjunction with PIB and functionalized polymers.

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