WO2014023707A1 - Composition de graisse - Google Patents

Composition de graisse Download PDF

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Publication number
WO2014023707A1
WO2014023707A1 PCT/EP2013/066429 EP2013066429W WO2014023707A1 WO 2014023707 A1 WO2014023707 A1 WO 2014023707A1 EP 2013066429 W EP2013066429 W EP 2013066429W WO 2014023707 A1 WO2014023707 A1 WO 2014023707A1
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WO
WIPO (PCT)
Prior art keywords
grease composition
composition according
abrasive particles
thickener
grease
Prior art date
Application number
PCT/EP2013/066429
Other languages
English (en)
Inventor
Eduard Albrecht
Sergey M. Mamykin
Original Assignee
Ab Nanol Technologies Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ab Nanol Technologies Oy filed Critical Ab Nanol Technologies Oy
Priority to EP13745665.3A priority Critical patent/EP2882833A1/fr
Publication of WO2014023707A1 publication Critical patent/WO2014023707A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • 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
    • 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
    • C10M2207/106—Carboxylix acids; Neutral salts thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—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
    • 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
    • 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
    • C10N2020/055—Particles related characteristics
    • 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
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to a grease composition. Furthermore, the present invention relates to a method for producing the grease composition.
  • Lubricants in roller bearings and friction bearings ensure that a film of lubricant, which transfers loads and separates different parts is established between parts that rub or slide against one another. This achieves the result that metallic surfaces do not come in contact with one another and therefore there is no wear.
  • the lubricants must therefore meet high demands. These includes extreme operating conditions such as very high or very low rotational speeds, high temperatures caused by high rotational speeds or by long-distance heating, very low temperatures, e.g., in bearings that operate in a cold environment or which occur with use in aviation and space travel.
  • modern lubricants should be suitable for use under so-called clean room conditions in order to avoid soiling of the room due to abrasion and/or the consumption of lubricants.
  • Metal-coating compositions were developed especially for exploitation in harsh environments featuring high temperatures and pressures.
  • Metal- coating lubricants are materials that form a non-oxidising thin metal film, such as a few micrometers thick copper film on the friction surfaces also on those surfaces not containing the film- forming metals.
  • the protective thin metal film provides significant reduction of the friction coefficient even in marginal lubrication conditions and when friction surfaces are under high pressure.
  • Russian patents RU 231 1447 and RU 2338777 discloses a metal- containing oil- soluble composition for lubricant greases.
  • Said composition comprises metal salt of inorganic acid, metal salt of organic acid, aliphatic alcohol, aromatic amine, epoxy resin, succinimide polymer and 2-imine-substituted derivative of indoline.
  • a known disadvantage of said composition is ineffective formation of the protective thin metal film on friction surfaces, thus making such a lubricant useless in applications where it is crucial to achieve a maximum degree of protection as soon as possible.
  • the purpose of the present invention is to eliminate the drawbacks mentioned above.
  • the purpose of the present invention is to prolong the lifespan of moving parts such as parts of bearings, machines and vehicles by reducing temperatures of friction surfaces and improving abrasive resistance, thus reducing wear of their moving parts. This is achieved by protecting friction surfaces with a novel grease composition providing a fast formation of the protective thin metal film on friction surfaces.
  • a further purpose of the grease composition according to the present invention is to provide an environmentally friendly lubricant comprising significantly less toxic and environmentally harmful chemicals or components than the lubricants and lubricant additives currently available on the market. Furthermore, it was thus an object of the present invention to provide a grease composition which leads to a reduction in the fuel consumption. Furthermore, the grease composition should enable a longer grease change intervals and improved operational lifetime.
  • a further objective of the present invention is development of a lubricant for application on the railway transport that can sustain high unit loads; provide long-lasting operation life of conjugated pairs protecting them from contact fatigue damages, decreasing the wear of the friction pairs wheel-rail and traction units of traction vehicles, providing protection of the friction surfaces from hydrogen wear and implementing the auto-compensation of wear and damages.
  • the present grease composition should enable a higher blocking efficiency regarding lubricant losses to the road bed.
  • An additional technical task of the present invention is development of a lubricant that can provide long-lasting operation time of roller bearings of axle boxes with a low friction coefficient and eliminate overheating of roller bearings in long-term operation as well as reduce damages through hydrogen wear.
  • the present invention provides a grease composition
  • a grease composition comprising a base oil component, at least one thickener and at least one metal salt, wherein the grease composition comprises at least one metal salt of an organic acid and at least one metal salt of an inorganic acid and from 0.00005 wt% to 0.01 wt%, preferably from 0.0001 wt% to 0.005wt%, most preferably from 0.0001 wt% to 0.003wt% abrasive particles.
  • the grease composition comprises at most 0.2 wt%, especially at most 0.1 wt%, preferably at most 0.05 wt%, more preferably at most 0.03 wt%, more preferably at most 0.02 wt% and most preferably at most 0.01 wt% of sulfur.
  • the grease composition comprises at least one viscosity index improver.
  • the average diameter size of abrasive particles ranges from 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ .
  • the abrasive particles have a hardness of at least 7 on the Mohs scale.
  • the abrasive particles comprise carbonates, nitrides, carbides and/ or oxides of elements of boron, carbon and/ or alkaline earth metal groups.
  • the grease composition comprises a NLGI consistency number according to DIN 51818 from 00 to 6, preferably from 0 to 6 and more preferably from 1 to 5.
  • the grease composition comprises a thickener on the basis of soap, a thickener on the basis of a polymer and/or an inorganic thickener.
  • the grease composition comprises particles having a size of less than 0.1 micron.
  • the grease composition comprises a drop point of at least 180°C according to DIN ISO 2176.
  • the present invention provides a method for producing a grease composition in accordance with the definitions provided above and below comprising mix- ing a base oil with at least one metal salt of an organic acid and at least one metal salt of an inorganic acid and from 0.00005 wt% to 0.01 wt%, preferably from
  • 0.0001 wt% to 0.005wt% most preferably from 0.0001 wt% to 0.003wt% abrasive particles and a thickener.
  • the present invention provides a bearing, preferably a wheel bearing or a roller bearing, comprising a grease composition in accordance with the definitions provided above and below.
  • a chassis comprising a grease composition in accordance with the definitions provided above and below.
  • the present invention provides a grease composition which leads to a reduction in the fuel consumption.
  • the grease composition according to the present invention does not comprise essential amounts of phosphorus- nor sulfur -based compounds.
  • the grease composition enables a longer grease change intervals and improved operational lifetime.
  • the present grease composition enables a higher blocking efficiency regarding lubricant losses to the road bed.
  • the invention is based on research work, the aim of which was to show that a certain concentration of abrasive particles accelerate formation of the protective thin metal film. According to the studies, abrasive particles enhance diffusion of metal ions, which are present in lubricant in the form of metal salts, into the crystal lattice of friction surfaces.
  • a grease composition means a substance introduced between moving surfaces to reduce the friction between them, i.e. a grease composition is any kind of a natural or a synthetic lubricating substance having a semisolid or plastic consistency.
  • the compounds of the grease composition of the present invention react on frictions surfaces and form a non-oxidising thin metal film on said surfaces, thus reducing mechanical wear and tear of the surfaces the grease composition has been applied on. Therefore, the grease composition can be classified as a metal-coating composition.
  • the grease composition of the present invention comprises a base oil component, at least one thickener and at least one metal salt.
  • Base oils that are useful in the practice of the present invention may be selected from natural oils, synthetic oils and mixtures thereof.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydro-refined, solvent-treated or acid-treated mineral oils of the par- affinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypro- pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1 - hexenes), poly(l -octenes), poly(l -decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof.
  • Preferred base oils include those obtained by producing heavy linear chain paraffins in the Fischer- Tropsch process where hydrogen and carbon monoxide obtained by the gasification process (partial oxidation) of natural gas (methane etc.) are used and then subjecting this material to a catalytic cracking and isomerisation process.
  • Fischer-Tropsch derived base oils may conveniently be any Fischer-Tropsch derived base oil as disclosed in for example EP-A-776959, EP-A-668342,
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and d 3 Oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500
  • Another suitable class of synthetic oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, ma- leic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, ma- leic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linole
  • esters examples include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C12 monocarbox- ylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4- methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2- ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4- methyl-2-ethyl
  • the oil of lubricating viscosity useful in the practice of the present invention may comprise one or more of a Group I Group II, Group III, Group IV or Group V oil or blends of the aforementioned oils.
  • Definitions for the oils as used herein are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996 , Addendum 1 , December 1998. Said publication categorizes oils as follows:
  • Group I oils contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1 .
  • Group II oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1 . Although not a separate Group recognized by the API, Group II oils having a viscosity index greater than about 1 10 are often referred to as "Group II+" oils.
  • Group III oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table 1 .
  • Group IV oils are polyalphaolefins (PAO).
  • Group V oils are all other base stocks not included in Group I, II, III, or IV.
  • the volatility of the base oil as measured by the Noack test (ASTM)
  • the viscosity index (VI) of the base oil is at least 100, preferably at least 1 10, more preferably greater than 120.
  • Base oils also referred to as oils of lubricating viscosity useful in the context of the present invention may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils.
  • the viscosity of the oil ranges from about 2 mm 2 s “1 (cen- tistokes) to about 200 mm 2 s “1 , especially from about 4 mm 2 s “1 to about 40 mm 2 s “1 as measured at 100 °C (ASTM 445).
  • a base oil or a base oil mixture will be preferred, for which the kinematic viscosity at 40 °C according to ASTM D445 is comprised between 10 and 80 mm 2 s “1 (centistokes), preferentially between 10 and 50 mm 2 s “1 (centistokes), preferentially between 20 and 40 mm 2 s “1 (centistokes), so as to guarantee good operability, good pumpability, and good cold properties, allowing use down to -20 °C, or even down to -40 °C.
  • a base oil or a base oil mixture will be preferred, the kinematic viscosity of which at 40 °C according to ASTM D445 is comprised between 70 and 1 10 mm 2 s “1 (centistokes), preferentially between 30 and 40 mm 2 s “1 (centistokes), preferentially between 35 and 37 mm 2 s “1 (centistokes), so as to guarantee an adequate oil film under higher loads.
  • the present grease composition comprises a thickener.
  • thickeners include thickeners on the basis of soap, thickeners on the basis of a polymer and/or inorganic thickeners.
  • the thickeners are known per se in the technical field and can be obtained commercially. These are, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 20, 2003, Wiley, ISBN 3-527-30385-5, in T. Mang and W. Dresel, Lubricants and Lubrication, 2001 , Wiley, ISBN 3-527-29536-4, and Wilfried J. Bartz et al., Schmierfette, expert- Verl., 2000, ISBN 3-8169-1533-7.
  • the greases according to the invention are preferably thickened with soaps, preferably metal soaps of fatty acids, which may be prepared separately or in situ during the making of the grease (in the latter case, the fatty acid is dissolved in the base oil and the suitable metal hydroxide is then added).
  • soaps preferably metal soaps of fatty acids
  • These thickeners are easily available and inexpensive products currently used in the field of greases.
  • Long chain fatty acids are preferentially used, typically comprising from 10 to 28 carbon atoms, either saturated or unsaturated, optionally hydroxylated.
  • the long chain fatty acids are for example, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, oleic, linoleic, erucic acids and their hydroxylated derivatives. 12-hydroxystearic acid is the most well-known derivative of this category, and preferred.
  • These long chain fatty acids generally derive from vegetable oils, for example palm, castor, rapeseed, sunflower oil or from animal fats (tallow, whale oil).
  • So-called simple soaps may be formed by using one or more long chain fatty acids. It is also possible to form so-called complex soaps by using one or more long chain fatty acids in combination with one or more carboxylic acids with a short hydrocarbon chain comprising at most 8 carbon atoms.
  • the saponification agent used for making the soap may be a metal compound of lithium, sodium, calcium, barium, titanium, aluminum, preferentially lithium and calcium, and preferably a hydroxide, oxide or carbonate of these metals.
  • One or more metal compounds may be used, either having the same metal cation or not, in the greases according to the invention. It is thereby possible to associate lithium soaps combined with calcium soaps in a lesser proportion.
  • the lithium complex thickener can comprise a lithium soap derived from a fatty acid containing an epoxy group and/or ethylenic unsaturation and a dilith- ium 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 lithium soap or a lithium complex soap prepared from hydroxy fatty acid having from 12 to 24 carbon atoms.
  • the thickener can be a complex of a lithium soap of a C-
  • the complex can comprise a lithium soap of a d 2 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-I2 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12- hydroxy C12 to C24 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 car- boxyl 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-I2 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12- hydroxy C12 to C24 fatty acid, e.g., lithium 12-hydroxy stearate; and
  • the lithium complex can comprise a combination of a complex lithium soap thickener, a lithium salt of a C 3 to d 4 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, such as stearic acid and oleic 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, stearic acid and/or oleic acid.
  • the thickener preferably include a lithium soap of 12-oxystearic acid and a lithium soap of oleic acid. More preferably, the weight ratio of the lithium soap of 12-oxystearic acid to the lithium soap of oleic is in the range of 10:1 to 1 :2, more preferably 5:1 to 1 :1 and most preferably 4:1 to 2:1 .
  • Thickeners based on polymers include polycarbamides (polyureas) and polytetrafluo- roethylene. Thickeners based on urea compounds are disclosed in
  • WO 2012/076025 A1 are expressly incorporated herein by reference for their disclosure regarding thickeners based on polymers.
  • inorganic thickeners can be applied such as bentonite, amorphous hy- drophilic silicon oxide particles and silica gel.
  • silica particles having a mean particle size in the range of 5 to 50 nm can be used as described in
  • the thickener mentioned above can be used as a single compound or as a mixture of different compounds being classified in the same class or as mixtures of thickeners being classified in different classes.
  • thickeners being based on soaps are preferred over thickeners based on polymers or inorganic thickeners.
  • the weight ratio of base oil to thickener in the grease composition is known per se and is described in the literature mentioned above and below. In general, this ratio depends on the NLGI consistency number according to DIN 51818 and is in the range from 100:1 to 100:30, preferably 100:2 to 100:25, in particular 100:5 to 100:15.
  • metal soaps are preferably used at contents of the order of 1 to 60% by weight, preferentially from 2 to 50% or further from 4 to 40% or from 4.5 to 30% by weight in the greases according to the invention.
  • applications such as lubricated bearings or centralized greasing for automobiles are targeted, the use of 1 to 6%, preferentially 2 to 5% of metal soap(s) will be preferred, so as to obtain fluid or semifluid greases of grade 000 or 00 according to the NLGI classification.
  • applications such as transmissions are targeted, the use of 6.5% to 15%, preferentially 7 to 13% or 8 to 12% of metal soap(s) will be preferred, so as to obtain greases of grade 0, grade 1 or grade 2 according to the NLGI classification.
  • the grease composition may preferably comprise about 8-12 weight percent (wt. %) lithium soap of 12-oxystearic acid and 1 ,5-3,0 wt. % lithium soap of oleic acid 1 ,5-3,0.
  • the thickening activity of some thickeners can be increase by using of copolymer as an additive.
  • copolymers are commonly used as viscosity index improvers and are described below.
  • 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.
  • 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 di- nonyl 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 grease composition of the present invention includes at least one metal salt.
  • the grease in order to form a metal film on the metal friction surfaces, the grease shall comprise metal ions.
  • said ions preferably have higher ionization energy than that of the surface metal ions; i.e. if a friction surface is made of steel, the grease preferably comprise ions of metals having higher ionization energy than Fe.
  • the ionization energy refers to the stable ionization state of the surface metal ions and the ions used in the grease.
  • the grease may comprise copper ions.
  • the metal ions are selected such that the metal ions present in the lubricant fulfill the vacancies and diffuse inside the frictional surface removing dislocations caused by friction and forming crystals of protective thin metal film on the surface. Ionization energy is an approximation in order to achieve a deposition of metal ions of the grease.
  • the ions of Cu, Co, Pb, Sn, Ni are useful for surfaces comprising iron such as steel.
  • Addition of oil soluble metal salts of inorganic and organic acids to grease is crucial for formation of a protective thin metal film on friction surfaces where grease was applied.
  • Said metal salts provide metal ions which fulfil the open vacancies and diffuse inside the frictional surface forming a thin metal film.
  • This is a known practise in the art, with a composition disclosed in RU2277579, RU231 1447, RU2338777 and WO 2012/076025 A1 being examples.
  • the documents RU2277579, RU231 1447, RU2338777 and WO 2012/076025 A1 are expressly incorporated herein by reference for their disclosure regarding metal salts.
  • an additive comprising metal salts useful for the present invention is commercially available under the trademark VALENA®.
  • the lubricant composition according to the present invention comprises abrasive particles which enhance diffusion of metal ions, present in the composition in the form of metal salts, into friction surfaces and thus accelerate formation of protective metal film.
  • the grease composition according to the present invention comprises oil soluble metal salts of inorganic and organic acids and further comprises from 0.00005 wt% to 0.01 wt%, preferably from 0.0001 wt% to 0.005wt%, most preferably from 0.0001 wt% to 0.003wt% abrasive particles.
  • the grease composition according to the present invention forms a protective layer at the friction surfaces through physical bonding between the metal ions of the salt and the friction surfaces.
  • the abrasive particles enhance diffusion of metal ions into friction surfaces and thus accelerate formation of protective metal film, as they remove oxide films from the friction surfaces.
  • abrasive particles by removing oxidized films from the friction surface, they catalyse the build-up of the protective metal film through physical bonding between the metal ions of the salts and the friction surfaces.
  • Oxide films which typically form on metal surfaces due to air exposure, make the metal more resistant to chemical reactions. With no oxide films on the surfaces the protective metal film forms faster. In addition thereto, the prevention of oxide films improves the wear resistance and lowers the scuffing of the metal surface.
  • abrasive particles it is meant here either naturally occurring or fabricated granular material composed of finely divided hard particles, such as mineral or metal particles. These particles are useful for removing oxide films from the friction surfaces and, hence should have an appropriate hardness. It shall be noted that the exact chemical composition of abrasive particles is of secondary importance; however, the crucial matter is the concentration of abrasive particles in an composition. According to the extensive studies, the optimal concentration of abrasive particles in the composition varies from about 0.00005wt% to about 0.01 wt%, where wt% is mass percentage. The optimal concentration depends on factors such as the composition of the lubricant and the additives, the size of abrasive particles, etc.
  • the composition comprises from about 0.0001 wt% to about 0.005wt% of abrasive particles
  • the protective metal film forms within about 30 seconds from the start of the friction between the lubricated surfaces (i.e. from the moment the lubricated engine or motor starts running). Measurements preformed for similar lubricant compositions without abrasive particles indicate that in these cases the protective metal film forms in about five minutes, which is a considerably longer period.
  • the average diameter size of abrasive particles ranges from 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ .
  • the exact chemical composition of abrasive particles may vary, however the average diameter size of the abrasive particles ranges approximately from 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ . This means that statistically the majority of the abrasive particles has said diameter, however, variations around these values are possible.
  • abrasive particles having a diameter of about 1 ⁇ may as well comprise abrasive particles having a diameter of about 5 ⁇ or 20 ⁇ .
  • the majority of abrasive particles found in another grease composition may have a diameter of about 10 ⁇ ; however, the same grease composition may also comprise abrasive particles having a diameter of about 3 ⁇ .
  • the average particle size as mentioned above refers to the number average as can be determined by optical methods such as microscopy.
  • the diameter size of abrasive particles ranges from 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ . That is the composition preferably comprises
  • abrasive particles having a particle diameter in the range of 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ .
  • the composition of the present invention comprises a low content of abrasive particles having a particle diameter of more than 100 ⁇ , more preferably more than 50 ⁇ , especially preferably more than 30 ⁇ .
  • the amount of abrasive particles having a particle diameter of more than 100 ⁇ , more preferably more than 50 ⁇ , especially preferably more than 30 ⁇ is preferably less than 0.005wt%, more preferably less than 0.001 wt%, more preferably less than 0.0001 wt%, especially preferably less than 0.00001 wt%.
  • the weight ratio of abrasive particles having a particle diameter of more than 100 ⁇ , more preferably more than 50 ⁇ , especially preferably more than 30 ⁇ to the abrasive particles having a particle diameter in the range from 0.5 ⁇ to 20 ⁇ is preferably below 1 :3, more preferably below 1 :10.
  • particles having a very small diameter do not act as abrasive particles and should not be considered as abrasive particles.
  • the median (number median) diameter of the abrasive particles is generally in the range from 0.5 ⁇ to 20 ⁇ , preferably from 1 ⁇ to 10 ⁇ , most preferably from 1 ⁇ to 3 ⁇ .
  • the median particle size V50 is the number median, where the value for 50% by weight of particles is smaller than or identical with this value and that for 50% by weight of these particles is greater than or identical with this value.
  • the abrasive particles are spherical.
  • the term spherical means that the particles preferably have a spherical shape, but it is clear to the person skilled in the art that, as a consequence of the methods of production, it is also possible that particles with some other shape may be present, or that the shape of the particles may deviate from the ideal spherical shape.
  • spherical therefore means that the ratio of the largest dimension of the particles to the smallest dimension is not more than 4, preferably not more than 2, each of these dimensions being measured through the centre of gravity of the particles. At least 70% of the particles are preferably spherical, particularly preferably at least 90%, based on the number of particles.
  • abrasive particles have a hardness of at least 6, more preferably at least 6.5 and especially preferably of at least 7 on the Mohs scale. Therefore, abrasive particles comprise finely divided particles of ceramic materials, minerals, metals and/ or other compounds having a hardness of at least 6, more preferably at least 6.5 and especially preferably of at least 7 7 or more on the Mohs scale.
  • the following minerals have a hardness of at least 7 on the Mohs scale, thus being suitable for use as abrasive particles: quartz, garner, beryl, chrysoberyl, topaz, emerald, spinel, corundum, boron and diamond.
  • abrasive particles comprise any of the above mentioned ceramic materials, minerals or metals, or mixtures thereof, in a form of a fine powder or a granular mixture.
  • abrasive particles comprise carbonates, nitrides, carbides and/ or oxides of elements of boron, carbon and/ or alkaline earth metal groups.
  • the boron group is a periodic table group consisting of boron (B), aluminium (Al), gallium (Ga), indium (In), thallium (Tl), and ununtri- um (Uut);
  • the carbon group is a periodic table group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), and ununquadium (Uuq); and alkaline earth metals consist of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
  • abrasive particles comprise any of the above compounds separately, or a mixture thereof, in a form of a fine powder or a granular mixture.
  • the oil soluble metal salts of inorganic acid comprise oil soluble metal salts, i. e. chlorides, bromides and/ or iodides of at least one of the following metals: Cu, Co, Pb, Sn, Ni. More preferably, the oil soluble metal salts of inorganic acid comprise CuCI, CuBr, CuJ, CuCI 2 , CuBr 2 , CoCI 2 , CoBr 2 , CoJ 2 , PbCI 2 , PbBr 2 , PbJ 2 , SnCI 2 , SnBr 2 , SnJ 2 , NiCI 2 , NiBr 2 and/or NiJ 2 . Copper salts are especially preferred.
  • the oil soluble metal salts of organic acid comprises acids comprising carbon atoms and oxygen atoms.
  • the organic acid salts copper salts are especially preferred.
  • the organic metal salt preferably the organic copper salt may be blended into the oil as any suitable oil soluble metal compound, preferably copper compound.
  • oil soluble we mean the compound is oil soluble under normal blending conditions in the oil or additive package.
  • the copper compound may be in the cuprous or cupric form.
  • the organic metal salt, preferably the organic copper salt may be added as the metal salt, preferably copper salt of a synthetic or natural carboxylic acid.
  • Examples include C-io to C-is fatty acids such as stearic or palmitic, but unsaturated acids such as oleic or branched carboxylic acids such as napthenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting metal carboxylates, preferably copper car- boxylates.
  • Exemplary of useful copper compounds are copper (Cu 1 and/or Cu”) salts of alkenyl succinic acids or anhydrides.
  • the salts themselves may be basic, neutral or acidic.
  • Examples of the metal salts of this invention are Cu salts of polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA), and Cu salts of polyisobutenyl succinic acid.
  • the selected metal employed is its divalent form, e.g., Cu 2+ .
  • the preferred substrates are polyalkenyl succinic acids in which the alkenyl group has a number average molecular weight (Mn) greater than 700.
  • the alkenyl group desirably has a Mn from 900 to 1400, and up to 2500, with a Mn of about 950 being most preferred.
  • PIBSA polyisobutylene succinic acid
  • These materials may desirably be dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) of the metal bearing material. Heating may take place between 70 °C and 200 °C. Temperatures of 1 10°C to 140°C are entirely adequate. It may be necessary, depending upon the salt produced, not to allow the reaction to remain at a temperature above about 140°C for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.
  • a solvent such as a mineral oil
  • Preferred metal salts of organic acids comprising organic acids having from 15 to 18 carbon atoms in their molecular formula, such as metal salts of oleic acid
  • a metal salt of organic acids are tin oleate C 3 6H 6 60 4 Sn, copper oleate C 3 6H 6 60 4 Cu, nickel oleate C 3 6H 6 60 4 Ni, lead oleate C 36 H 6 60 4 Pb and cobalt oleate C 36 H 6 60 4 Co with copper oleate C 36 H 6 60 4 Cu being especially preferred. It shall be noted that said oil soluble metal salts of inorganic and organic acids are completely dissolved in the end product, i.e. in a grease composition according to the present invention.
  • the composition comprises, in addition to abrasive particles and oil soluble metal salts of inorganic and organic acids, at least one of the following: an aliphatic alcohol, a succinimide derivative, an aromatic amine, an epoxy resin and/ or a 2-iminosubstituted indoline.
  • the succinimide derivative comprises S-5A polyalkenyl succinimide
  • the aromatic amine comprises homotype diphenylamine
  • the epoxy resin comprises commercially available aliphatic epoxy resin ⁇ 3 ⁇ -1 , produced by condensation of epichlorohydrin with glycol.
  • the grease composition of the present invention comprises at least one viscosity index improver.
  • Polymers useful as viscosity index improver usually act as thickener and as structure improvers as mentioned in the documents US 5,1 16,522, US 2005/245406 A1 , US 2007/191238 A1 and US 2012/004153 A1 .
  • Preferred viscosity index improvers for grease compositions advantageously increase the viscosity of the lubricating oil being released by the grease composition at higher temperatures when used in relatively small amounts (have a high thickening efficiency (TE)), provide reduced lubricating oil resistance at low temperatures and be resistant to mechanical degradation and reduction in molecular weight in use (have a low shear stability index (SSI)).
  • TE thickening efficiency
  • SSI low shear stability index
  • Viscosity index (VI) improvers include polymers based on olefins, such as polyisobu- tylene, copolymers of ethylene and propylene (OCP) and other hydrogenated iso- prene/butadiene copolymers, as well as the partially hydrogenated homopolymers of butadiene and isoprene and star copolymers and hydrogenated isoprene star polymers, polyalkyl (meth)acrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and hydrogenated copolymers of styrene/isoprene and styrene/butadiene.
  • olefins such as polyisobu- tylene, copolymers of ethylene and propylene (OCP) and other hydrogenated iso- prene/butadiene copoly
  • the molecular weight of polymers useful as viscosity index improver in accordance with the present invention can vary over a wide range since polymers having number-average molecular weights (Mn) as low as about 2,000 can affect the viscosity properties of an oleaginous composition.
  • Mn number-average molecular weights
  • the preferred minimum Mn is about 10,000; the most preferred minimum is about 20,000.
  • the maximum Mn can be as high as about 12,000,000; the preferred maximum is about 1 ,000,000; the most preferred maximum is about 750,000.
  • An especially preferred range of number-average molecular weight for polymer useful as viscosity index improver in the present invention is from about 15,000 to about 500,000; preferably from about 20,000 to about
  • the number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such determination is by size exclusion chromatography (also known as gel permeation chromatography (GPC)) which additionally provides molecular weight distribution information, see W. W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
  • size exclusion chromatography also known as gel permeation chromatography (GPC)
  • the polydispersity index (Mw/Mn)of preferred polymers useful as viscosity index improver in accordance with the present invention is less than about 10, preferably less than about 5, more preferably less than about 4 and most preferably less than about 3 e.g., from 1 .05 to 3.5, most preferably from 1 .1 to 3.
  • Mw is the weight average molecular weight of the polymer as measured by Gel Permeation Chromatography ("GPC") with a polystyrene standard.
  • TE Thickening Efficiency
  • c polymer concentration (grams of polymer/100 grams solution)
  • kvoii+poiymer is kinematic viscosity of the polymer in the reference oil
  • kv oU is kinematic viscosity of the reference oil.
  • the TE is preferably measured at 100 °C.
  • the viscosity index improver useful for the present invention preferably has a TE of from about 1 .5 to about 4.0, preferably from about 1 .6 to about 3.3, more preferably from about 1 .7 to about 3.0.
  • "Shear Stability Index” measures the ability of polymers used as V.I. improvers in crankcase lubricants to maintain thickening power during use and is indicative of the resistance of a polymer to degradation under service conditions. The higher the SSI, the less stable the polymer, i.e., the more susceptible it is to degradation.
  • kv fresh ⁇ kv oil
  • kv fresh is the kinematic viscosity of the polymer-containing solution before degradation
  • kv after is the kinematic viscosity of the polymer-containing solution after degradation.
  • SSI is conventionally determined using ASTM D6278-98 (known as the Kurt-Orban (KO) or DIN bench test).
  • the polymer under test is dissolved in suitable base oil (for example, solvent extracted 150 neutral) to a relative viscosity of 9 to 15 mm 2 s "1 (centistokes) at 100 ° C and the resulting fluid is pumped through the testing apparatus specified in the ASTM D6278-98 protocol for 30 cycles.
  • suitable base oil for example, solvent extracted 150 neutral
  • the shear stability index (SSI, 30 cycles) according to ASTM D6278-98 of preferred polymers useful as viscosity index improver in accordance with the present invention is preferably less than about 60 %, more preferably less than about 50 %, more preferably less than about 40 %. Preferred ranges are e.g. from about 1 % to about 60 %, preferably from about 2 % to about 50%, more preferably from about 5% to about 40 %.
  • Polymers based on olefins include monomers consisting of carbon atoms and hydrogen atoms, such as ethylene, propylene, butylene and diene monomers, such as butadiene.
  • the polymers based on olefins comprise at least 30 wt%, more preferably at least 50 wt% and most preferably at least 80 wt% repeating units being derived from olefin monomers.
  • Preferred olefin copolymers (or OCP) useful as viscosity index improvers conventionally comprise copolymers of ethylene, propylene and, optionally, a diene. Small polymeric side chains do not exert a substantial vis- cosity modifying effect in oil.
  • Polymerized propylene has one methyl branch for every two backbone carbon atoms. Ethylene polymer is substantially straight chained.
  • VI improvers that are star polymers made by hy- drogenation of anionically polymerized isoprene are commercially available. Anionic polymerization results in a relatively low molecular weight distribution (Mw/Mn). Hy- drogenation results in alternating ethylene/propylene units having a composition comparable to a polymer derived from 40 wt.% ethylene and 60 wt.% propylene. These VI improvers provide excellent shear stability, good solubility and excellent cold temperature properties.
  • Preferred polymers based on olefins are disclosed in EP0440506, EP1493800 and EP1925657.
  • the documents EP0440506, EP1493800 and EP1925657 are expressly incorporated herein by reference for their disclosure regarding viscosity index improvers based on olefins.
  • PolyalkyI (meth)acrylates are based on alkyl (meth)acrylate monomers conventionally comprising 1 to 4000 carbon atoms in the alkyl group of the (meth)acrylates.
  • the polyalkyl (meth)acrylates are copolymers of alkyl (meth)acrylate monomers having 1 to 4 carbon atoms in the alkyl group, such as methyl methacrylate, ethyl methacrylate and propyl methacrylate and alkyl (meth)acrylate monomers having 8 to 4000 carbon atoms, preferably 10 to 400 carbon atoms and more preferably 12 to 30 carbon atoms in the alkyl group.
  • Preferred polyalkyl (meth)acrylates are described in the patents US 5,130,359 and US 6,746,993.
  • the documents US 5,130,359 and US 6,746,993 are expressly incorporated herein by reference for their disclosure regarding viscosity index improvers based on polyalkyl (meth)acrylates.
  • the viscosity index improver may comprise dispersing groups.
  • Dispersing groups including nitrogen-containing and/or oxygen-containing functional groups are well known in the art.
  • nitrogen-containing groups are preferred.
  • One trend in the industry has been to use such "multifunctional" VI improvers in lubricants to replace some or all of the dispersant.
  • Nitrogen-containing functional groups can be added to a polymeric VI improver by grafting a nitrogen- or hy- droxyl- containing moiety, preferably a nitrogen-containing moiety, onto the polymeric backbone of the VI improver (functionalizing).
  • Processes for the grafting of a nitrogen-containing moiety onto a polymer include, for example, contacting the polymer and nitrogen-containing moiety in the presence of a free radical initiator, either neat, or in the presence of a solvent.
  • the free radical initiator may be generated by shearing (as in an extruder) or heating a free radical initiator precursor, such as hydrogen peroxide.
  • polyalkyl (meth)acrylate polymers polymers having functional groups, preferably nitrogen-containing functional groups can be achieved by using comonomers comprising nitrogen-containing groups such as dimethylaminoethyl methacrylate (U.S. Pat. No. 2,737,496 to E. I.
  • the amount of nitrogen-containing monomer will depend, to some extent, on the nature of the substrate polymer and the level of dispersancy required of the polymer.
  • the amount of nitrogen-containing and/or oxygen-containing monomer is suitably between about 0.4 and about 10 wt. %, preferably from about 0.5 to about 5 wt. %, most preferably from about 0.6 to about 2.2 wt. %, based on the total weight of polymer.
  • the viscosity index improvers can be used as a single polymer or as a mixture of different polymers, for example, a combination of a polymer based on an olefin, such as polyisobutylene, copolymers of ethylene and propylene (OCP) and other hydrogen- ated isoprene/butadiene copolymers, as well as the partially hydrogenated homopol- ymers of butadiene and isoprene and/or star copolymers and hydrogenated isoprene star polymers, preferably a copolymer of ethylene and propylene (OCP) with an VI improver comprising polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and/or hydrogenated copolymers of styrene/isoprene and/or sty- rene/butadiene
  • the grease composition may preferably contain a VI improver useful for the invention in an amount of from about 0 wt. % to about 30 wt.%, preferably from about 0.3 wt. % to about 25 wt.%, more preferably from about 0.4 wt. % to about 15 wt.%, stated as mass percent active ingredient (Al) in the total lubricating oil composition.
  • a VI improver useful for the invention in an amount of from about 0 wt. % to about 30 wt.%, preferably from about 0.3 wt. % to about 25 wt.%, more preferably from about 0.4 wt. % to about 15 wt.%, stated as mass percent active ingredient (Al) in the total lubricating oil composition.
  • the viscosity index improvers are widely generally sold in the market as commercial products.
  • VISCOPLEX® by Evonik Rohmax GmbH
  • ACLUBE® by Sanyo Chemical
  • Infineum® V534 and Infineum® V501 available from Infineum USA L.P. and Infineum UK Ltd. are examples of commercially available amorphous OCP.
  • Other examples of commercially available amorphous OCP VI improvers include Lubrizol® 7065 and Lubrizol® 7075 , available from The Lubrizol Corporation; Jilin® 0010 , available from PetroChina Jilin Petrochemical Company; and NDR0135 , available from Dow Elastomers L.L.C.
  • An example of a commercially available star polymer VI improver having an SSI equal to or less than 35 is Infineum® SV200 , available from Infineum USA L.P. and Infineum UK Ltd.
  • Other examples of commercially available star polymer VI improver having an SSI equal to or less than 35 include Infineum® SV250, and Infineum® SV270 , also available from Infineum USA L.P. and Infineum UK Ltd.
  • Multifunctional viscosity index improvers are available from Evonik Rohmax GmbH under the trade designations "Acryloid 985", “Viscoplex 6-054”, “Viscoplex 6-954" and “Viscoplex 6-565" and from The Lubrizol Corporation under the trade designation "LZ 7720C”.
  • the present grease composition may comprise further additives with the provision that the content of sulfur or phosphorus should be as low as possible.
  • additives include friction modifiers, antioxidants demulsifiers, dispersants and pour point depressants.
  • antioxidants hindered phenols or amines, for example phenyl alpha naphthyla- mine are generally used.
  • Demulsifiers which are generally applied are polyalkylene glycol ethers.
  • Preferred friction modifiers are compounds based on
  • poly(meth)acrylates as described in WO-A-2004/087850, WO 2006/105926, WO 2006/007934 and WO 2005/097956.
  • the documents WO-A-2004/087850, WO 2006/105926, WO 2006/007934 and WO 2005/097956 are expressly incorporated herein by reference for their disclosure regarding poly(meth)acrylates useful as friction modifiers.
  • polymers such as nanoparticulate polytetrafluoroeth- ylene can be added as described e. g. in US 201 1 /306527 A1 .
  • the document US 201 1 /306527 A1 is expressly incorporated herein by reference for its disclosure regarding greases comprising nanoparticulate polytetrafluoroethylene.
  • Dispersants maintain oil insolubles, resulting from oxidation during use, in suspension in the fluid thus preventing slide glocculation and precipitation or deposition on metal parts.
  • Suitable dispersants include high molecular weight alkyl succinimides, the reaction product of oil-soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof.
  • the ashless dispersants include the polyalkenyl or borated polyalkenyl succinimide where the alkenyl groups is derived from a C 3 -C 4 olefin, especially polyisobutenyl having a number average molecular weight of 700 to 5,000.
  • Other well-known dispersants include ethylene-propylene oligomers with N/O functionalities and oil soluble polyol esters of hydrocarbon substituted succinic anhydride, e.g., polyisobutenyl succinic anhydride, and the oil soluble oxazoline and lactone oxazoline dispersants derived from hydrocarbon substituted succinic anhydride and disubstituted amino alcohols.
  • Lubricating oils preferably contain 0.5 to 5 wt. % of ashless dispersant.
  • the pour point improvers include especially polyalkyi (meth)acrylates (PAMA) having 1 to 30 carbon atoms in the alcohol group, C 8 to d 8 dialkyl fumarate/vinyl acetate copolymers and chlorinated paraffin-naphthalane condensation products.
  • Lubricating oils preferably contain up to 5 wt. %, more preferably 0.01 to 1 .5 wt of pour point improvers. These are widely generally sold in the market as commercial products.
  • Table 2 shows preferred compositions for lubricants according to the present invention. Table 2.
  • thickener 0.1 to 60 1 to 40
  • abrasive particles 0.00005 to 0.01 0.00005 to 0.01 metal salt of organic acid 0.1 to 9.0 0.1 to 9.0
  • metal salt of inorganic acid 0.01 to 2.5 0.01 to 2.5
  • aromatic amine 0.01 to 2.0 0.01 to 2.0
  • the grease composition preferably comprises a NLGI consistency number according to DIN 51818 from 000 to 6, especially from 00 to 6, preferably from 0 to 6 and more preferably from 1 to 5.
  • the grease composition comprises a drop point of at least 180°C, more preferably at least 190 °C according to DIN ISO 2176.
  • Preferred lubricating grease compositions are preferably suitable for applications for upper service temperatures of more than 120 °C up to 260 °C and for low service temperatures of -60 °C according to DIN 51285. They may also be used at upper service temperatures of more than 180 °C and for low service temperatures down to -60 °C according to DIN 51825.
  • the grease composition comprises at most 0.2 wt%, especially at most 0.1 wt%, preferably at most 0.05 wt%, more preferably at most 0.03 wt%, more preferably at most 0.02 wt% and most preferably at most 0.01 wt% of sulfur.
  • the amount of sulfur in the lubricant composition should be as low as possible in order to improve the environmental acceptability.
  • the amount of sulfur can be determined according to ASTM D4294.
  • the sulfur content of the grease composition is identical or smaller than the sulfur content of the base oil. No sulfur containing additives are needed or added.
  • the grease composition comprises at most 0.05 wt%, especially at most 0.03 wt%, preferably at most 0.01 wt%, more preferably at most 0.003 wt%, more preferably at most 0.002 wt% and most preferably at most 0.001 wt% of phosphorus.
  • the amount of phosphorus in the grease composition should be as low as possible in order to improve the environmental acceptability.
  • the amount of phosphorus can be determined according to ASTM D1091 .
  • the phosphorus content of the grease composition is identical or smaller than the phosphorus content of the base oil. No phosphorus containing additives are needed or added.
  • the grease composition comprises at most 0.2 wt%, especially at most 0.1 wt%, preferably at most 0.05 wt%, more preferably at most 0.03 wt%, more preferably at most 0.02 wt% and most preferably at most 0.01 wt% of sulfated ash.
  • the amount of sulfated ash in the grease composition should be as low as possible in order to improve the environmental acceptability.
  • the amount of sulfated ash can be determined according to ASTM D874.
  • the sulfated ash of the grease composition is identical or smaller than the sulfated ash of the base oil.
  • the low amount of sulfur, phosphorus and sulfated ash in the grease composition can be obtained by using base oils having low sulfur and low phosphorus content and by omitting sulfur and phosphorus containing additives. It should be noted that prolongation of the lifespan of moving parts, such as bearings, by reducing temperatures of friction surfaces and improving abrasive resistance, thus reducing wear of their moving parts by using the present lubricant composition as mentioned above can surprisingly be improved by omitting conventional sulfur and/or phosphorus containing anti-wear and extreme pressure additives.
  • compositions of this invention are used principally in the formulation of bearing greases and in the formulation of chassis greases, and comprise a major amount of an oil of lubricating viscosity, a thickener, the metal salts and the abrasive particles as described above, and optionally other additives as needed to provide the grease composition with the required properties.
  • a lubricating grease may stimulate vibrations in the roller bearing which are in the medium-frequency band from 300 to 1800 Hz and high-frequency band 1800 to 10,000 Hz in revolving participation (rolling over, milling) in comparison with the bearing noise in the low-frequency band at 50 to 300 Hz.
  • Superimposed on the lubricant noise are sound peaks occurring with rollover of hard particles by the roller bearing in the form of shock pulses on the bearing ring.
  • the sound performance is evaluated according to the SKF BeQuiet method based on a static analysis of the noise peaks and the assignment to the noise classes BQ1 to BQ4. With increasing values of the noise class, the noise behavior becomes worse and the lifetime of the roller bearing is shortened (H. Werries, E.
  • the grease composition according to the present invention can be manufactured by any techniques known in the field, such as conventional mixing techniques, the different variations thereof being well known for those skilled in the art.
  • Lubricating greases may be produced in batch processes or by continuous processes.
  • the metal salts and/or the abrasive particles can be mixed with the base oil before the thickener is added to the base oil in order to achieve a grease composi tion of the present invention.
  • the present grease composition can be prepared by first dispersing or mixing the thickener in the lubricating oil for from about 1 to about 8 hours or more (preferably from about 1 to about 4 hours) followed by heat ing at elevated temperature (e.g., from about 60 °C to about 260 C depending upon the particular thickener used) until the mixture thickens.
  • the present greases can be used especially as bearing grease and/or as chassis grease.
  • the mechanical component having a metal surface to be treated with the grease composition according to the present invention is preferably a bearing, bearing component or a bearing application system.
  • the bearing component may be inner rings, outer rings, cages, rollers, balls and seal-counter faces.
  • the bearing application system in accordance with the present invention comprises bearing housings, mounting axles, shafts, bearing joints and shields. Further uses of the lubricant grease compo- sitions according to the present invention are e.g. agricultural machinery, bearings in dam-gates, low noise electric motors, large size electric motors, fans for cooling units, machine tool spindles, screw conveyor, and offshore and wind turbine applications.
  • Comparative tribological tests were carried out comparing the efficiency of a metal plating grease composition (Metalplaks-Ps) as Comparative Example 1 .
  • the lubricating grease Metalplaks-Ps has as a basis a compound of mineral and synthetic oils thickened with lithium soaps of fatty acids and oxyacid and comprises an additive composition, which provides enhanced anti-friction and protective properties.
  • the lubricating grease Metalplaks-Ps is commercially available under the trade name Metalub SS EP2 (MeTanio6 SS EP2) from 000 Nanol Technologies, 1 1 1398 Mos- kau, ul. Kuskovskaya, 16A, Office 26.
  • Example 1 a composition comprising the prior art metal plating grease composition according to Comparative Example 1 (Metalplaks-Ps ) and an additional content of abrasive particles has been prepared (about 0.0006 wt. % having a hardness of at least 7 on the Mohs scale).
  • the abrasive particles comprise boron carbide particles having an average diameter size of the boron carbide particles varied from 1 ⁇ to 3 ⁇ .
  • the comparative tests were conducted by a special procedure by loads of 700 MPa and 2600 MPa.
  • the essence of the procedure is a tribological examination of the conjunction with a point contact provided by a sample (disc) rotating at a constant velocity and a stationary motionless counterbody (ball) at a constant load with heat emission registered during and at the end of the tests and it being an indicator of the heat emission rate.
  • the mass and linear wear of the friction pair depends on the type of the lubricant, the load (Pgenerai, kg; G ma x iS t art kg/sin 2 ), the contact load (P c , Kg/mm 2 ) and the material of the friction pair.
  • the heat emission in the friction area is dependent on the friction coefficient of the modified friction layer, heat conductivity and the thickness of the grease layer.
  • the measured temperature (or the changed values of it) of one of the conjugated friction bodies during the tests is used to evaluate the type of change of the friction coefficient (positive or negative growing tendency), a change in the thickness of the lubricating grease layer as a function of the friction path length, of the testing period, of the lubricating grease material and of the friction pair.
  • Testing samples are made in form of a flat disc from steel ShH 15 (a standard roller bearing steel having a chromium content of about 1 .5 wt.%) with the diameter of 24 ⁇ 0.5 mm, the height of 3.5 ⁇ 0.5 mm, the hardness of HRC 62-64, non-parallelity of the working surfaces of no more than 0.1 mm and the roughness of the working surfaces of the samples R a ⁇ 0.63 ⁇ .
  • ShH 15 a standard roller bearing steel having a chromium content of about 1 .5 wt.5%
  • the counterbody is a ball from steel ShH 15 with the diameter of 6.3
  • the friction machine for testing of wear resistance provides the following testing conditions:
  • Load Pgen contact tightness force
  • thermo- electromotive force E mV
  • the sample in test and the counterbody are washed in alcohol, dried in the air and weighed with a weighing inaccuracy of no more than ⁇ 0.00005 g (m-i ; m 2 , g). The weighing is conducted three times with the scales' null-position checking each time.
  • the testing sample is set in a holder (7) and fastened with hold-down screws.
  • the ball is fastened in the collet fixture (6) connected via thermocouple with the millivoltmeter.
  • the lubricating grease Prior to launching the test the lubricating grease is laid on the disc with a palette knife or a syringe. The thickness of the lubricating layer should be sufficient for a visual detection of it across the whole working surface of the sample. After that the ball is set on the sample in accordance with Par. 2.3.
  • the load and the time period of the testing are chosen in accordance with the working conditions of the parts in the friction units (the settled friction mode on the given friction machine comes up to 1 hour).
  • the driving gear of the apparatus is set on.
  • the mass attrition of the surfaces of the sample ⁇ - ⁇ , g, and of the counter- body ⁇ 1 ⁇ 2, g, are determined as a difference of the weights of the sample and the counterbody before and after the testing.
  • S is the area of the wear spot on the ball, mm 2 ,
  • the contact load allows evaluating the load capacity of the friction pair.
  • thermocouple XK 0,3 1 5.0777 ⁇ ( ⁇ ⁇ - ⁇ ), where 1 5.0777 is the constant coefficient of the thermocouple XK 0,3 determined by calibration.
  • At is an increment in the temperature
  • ⁇ is the time point at the given moment of time of the test according to Table 1 .
  • Figure 1 shows the total mass attrition of the friction pairs
  • Figure 2 shows the diameter of wear spot of the ball
  • Figure 3 shows the loading capacity of the friction pairs
  • Figure 4 shows the heat emission rate at 1600 MPa
  • Figure 5 shows the heat emission rate at 2600 MPa
  • Figure 6 shows the final heat emission rate

Abstract

La présente invention concerne une composition de graisse comprenant un composant d'huile de base, au moins un épaississant et au moins un sel métallique, la composition de graisse comprenant au moins un sel métallique d'un acide organique et au moins un sel métallique d'un acide inorganique et de 0,00005 % en poids à 0,01 % en poids, de préférence de 0,0001 % en poids à 0,005 % en poids, de façon la plus préférée de 0,0001 % en poids à 0,003 % en poids de particules abrasives.
PCT/EP2013/066429 2012-08-08 2013-08-05 Composition de graisse WO2014023707A1 (fr)

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EP3428250A1 (fr) * 2017-07-11 2019-01-16 Shell International Research Maatschappij B.V. Graisse et procédé de préparation d'une graisse
EP3428251A1 (fr) * 2017-07-11 2019-01-16 Shell International Research Maatschappij B.V. Graisse et procédé de préparation d'une graisse

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