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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
• • 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
  • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
  • C10M125/22—Compounds containing sulfur, selenium or tellurium
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
  • C10M135/04—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/02—Mixtures of base-materials and thickeners
• • 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
  • C10M2201/065—Sulfides; Selenides; Tellurides
• • 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
  • C10M2201/065—Sulfides; Selenides; Tellurides
  • C10M2201/066—Molybdenum sulfide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
  • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
  • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
• • 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

Definitions

• the present invention relates to a lubricating composition comprising a metal sulphide or a metal oxide, in particular to a grease.
• a problem of the above known grease is that it shows relatively poor load carrying properties as determined with the four-ball test according to ASTM D2596.
• a lubricating composition at least comprising:
• a metal sulphide or metal oxide preferably a metal sulphide
• lubricating compositions containing a metal sulphide or a metal oxide as well as an organosulphur compound exhibit an unexpected improvement in extreme pressure and anti-wear properties as measured by the four-ball test according to ASTM D2S96.
• An important advantage of the present invention is that improved extreme pressure properties may be obtained at the same total additive concentration, but also equivalent extreme pressure performance using lower concentrations of additives. This not only results in a reduction of costs (a smaller amount of relatively expensive additives is needed) , but also avoids or reduces some of the problems associated with typical extreme pressure additive concentrations such as corrosion, oxidation instability, and reduced product life at high temperature.
• the metal sulphide or metal oxide used in the lubricating composition according to the present invention and various conventional metal sulphides or metal oxides, alone or in combination, may be conveniently used. Examples of metal sulphides or metal oxides are Bi 2 Ss, ZnS f MS 2 , Sb 2 S 3 , MoS 2 , Fe 2 S 3 , ZnO, TiO 2 , MoO 3 , etc.
• a metal sulphide is used (rather than a metal oxide) , wherein the metal sulphide is preferably selected from the group consisting of Bi 2 S 3 , ZnS, WS 2 and MoS 2 . It is even more preferred that the metal sulphide is Bi ⁇ Ss.
• the organosulphur compound can be selected from a broad range of compounds.
• the organosulphur compound is a compound obtainable by sulphurisation of a compound containing unsaturated hydrocarbon moieties, the hydrocarbon moieties preferably containing only H and C atoms.
• Particularly preferred are sulphurised esters and fats and sulphurised polyalkenes (such as polybutenes) .
• suitable organosulphur compounds and the preparation thereof are disclosed in US 4 191 659, the teaching of which is herein incorporated by reference.
• Non-limiting examples of these organosulphur compounds may be obtained by sulphurising olefinic compounds ⁇ i.e. having at least one non-aromatic double bond), such as compounds having the general formula (1)
• Group I or II e.g., sodium, potassium, barium, calcium
• - X is halogen (e.g., chloro, bromo, or iodo)
• Y is oxygen or divalent sulphur
• Ar is an aryl or substituted aryl moiety of up to about 12 carbon atoms.
• R 3- -R 4 may also together form an alkylene or substituted alkylene group; i.e., the olefinic compound may be alicyclic.
• substituents in the substituted moieties described above are not normally a critical aspect of the invention. Typical examples of such substituents include any of the above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.
• the olefinic compound is usually one in which each R value which is not hydrogen is independently alkyl, alkenyl or aryl, or (less often) a corresponding substituted radical.
• Mono-olefinic and diolefinic compounds are preferred, and especially terminal mono-olefinic hydrocarbons; that is, those compounds in which R 3 and R 4 are hydrogen and R 1 and R 2 are alkyl or aryl, especially alkyl (that is, the olefin is aliphatic) .
• Olefinic compounds having about 3- 30 and especially about 3-16 ⁇ most often less than 9) carbon atoms are particularly desirable.
• Isobutene, propylene and their dimers, trimers and tetramers, and mixtures thereof are especially preferred olefinic compounds.
• isobutylene and diisobutylene are particularly desirable because of their availability and the particularly high sulphur-containing compositions which can be prepared therefrom.
• organosulphur compounds For the preparation of the above non-limiting examples of organosulphur compounds, specific reference is again made to US 4 191 659, the teaching of which is incorporated by reference.
• organosulphur compounds which can be suitably used according to the present invention are Roscan 144 available from PCAS ⁇ Longjumeau, France) and SVE 1OC available from Harrison Manufacturing Company Ltd. (Australia) .
• the organosulphur compound has a S content in the range of from 5 to 40 wt . % , preferably from 7 to 20, more preferably from 8 to 12 wt.%, based on the weight of the organosulphur compound.
• the lubricating composition has a S content in the range of from 0.1 to 10 wt.%, preferably from 1 to 8 wt.%, based on the finished lubricating composition.
• the composition is in the form of a grease and contains one or more thickeners.
• base oil used in the method according to the present invention
• various conventional mineral oils and synthetic oils may be conveniently used.
• base oil is meant to also include a grease base stock.
• the base oil composition used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils.
• Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
• Suitable base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer- Tropsch derived base oils and mixtures thereof.
• Group I base oil By “Group I” base oil, “Group II” base oil and “Group III” base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III, Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
• API American Petroleum Institute
• Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating oil composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
• Synthetic oils include hydrocarbon oils such as olefin oligomers (PAOs) , dibasic acid esters, polyol esters, and dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the Shell Group under the designation "XHVI” (trade mark) may be conveniently used.
• PAOs olefin oligomers
• XHVI XHVI
• the total amount of base oil incorporated in the lubricating composition of the present invention is preferably present in an amount in the range of from 60 to 99 wt . % , more preferably in an amount in the range of from 75 to 99 wt . % and most preferably in an amount in the range of from 75 to 98 wt.%, with respect to the total weight of the lubricating composition.
• the total amount of the metal sulphide and/or metal oxide in the final lubricating composition is typically in the range of from 0.5 to 10.0 wt.%, preferably from 1.0 to 5.0 wt%, based on the total weight of the lubricating composition.
• the total amount of the organosulphur compound oxide in the final lubricating composition is typically in the range of from 0.5 to 10-0 wt.%, preferably from 1.0 to 5.0 wtl, based on the total weight of the lubricating composition.
• the final lubricating composition may further comprise one or more additives such as anti- oxidants, anti-wear agents, dispersants, detergents, friction modifiers, viscosity index improvers, pour point depressants, tackifying agents, corrosion inhibitors, demulsifiers, defoaming agents and seal compatibility agents, etc.
• additives such as anti- oxidants, anti-wear agents, dispersants, detergents, friction modifiers, viscosity index improvers, pour point depressants, tackifying agents, corrosion inhibitors, demulsifiers, defoaming agents and seal compatibility agents, etc.
• Said additives are typically present in an amount in the range of from 0.01 to 12.5 wt.%, based on the total weight of the lubricating composition, preferably in an amount in the range of from 0.05 to 10.0 wt.%, more preferably from 1.0 to 9.0 wt . % and most preferably in the range of from 2.0 to 5.0 wt.%, based on the total weight of the lubricating composition.
• the base oil as contained in the lubricating composition may contain or be compounded with one or more thickeners such as metallic soaps , organic substances or inorganic substances, for example, lithium soaps, lithium complex soaps, sodium terephthalate, urea/urethane compounds and clays.
• thickeners such as metallic soaps , organic substances or inorganic substances, for example, lithium soaps, lithium complex soaps, sodium terephthalate, urea/urethane compounds and clays.
• the lubricating composition has a kinematic viscosity at 100 0 C (ASTM D445) in the range of from 2 to 80 rn ⁇ rVs, more preferably in the range of from 3 to 70 rnmVs, most preferably in the range of from 4 to 50 mm 2 /s.
• the lubricating compositions of the present invention may be conveniently prepared by admixing the one or more base oils and, optionally, one or more additives that are usually present in lubricating compositions, for example as herein before described, with mineral and/or synthetic base oil.
• the metal sulphide (s) or metal oxide (s) used has (have) a sufficiently small particle size (e.g. below 50 ⁇ m, preferably below 20 ⁇ m) to allow easy dispersion thereof in the lubricating composition.
• the present invention provides a method for improving one or more of extreme pressure and anti-wear properties, which method comprises lubricating with a lubricating composition according to the invention. Also, the present invention provides the use of a lubricating composition according to the present invention for improving one or more of extreme pressure and anti-wear properties, in particular according to ASTM D2596.
• Table 1 indicates the composition of the lubricating oil compositions that were tested; the amounts of the components are given in wt.%, based on the total weight of the fully formulated formulations.
• the "grease base stock” as used in Example 1 and Comparative Examples 1-4 was a conventional grease base stock and contained about 10% m/m lithium 12- hydroxystearate thickener and about 90% m/m paraffinic mineral base oil blended from SN 500 and bright stock (viscosity at 40 0 C of 180 mmVs according to ASTM D445) .
• Bi 2 S 3 is available from e.g. Miracema-Kuodex (Brazil) .
• the ⁇ organosulphur compound" as used in Example 1 is a sulphurised ester available from PCAS (Longjumeau, France) under the trade designation M Roscan 144".
• Example 1 The compositions of Example 1 and Comparative Examples 2-4 were obtained by simply mixing the grease base stock, the Bi 2 S3 and the sulphurised ester, if present, using a laboratory paddle mixer. Table 1
• Table 2 The measured wear scars (in mm) are indicated in Table 2 below. Table 2 also shows the load at which the respective compositions failed, which loads were maintained for 1 minute or until failure occurred within 1 minute. Failure occurs when the upper ball as used in the test becomes intimately bonded, or welded to, the three lower balls. This is signified by a significant increase in noise and vibration from the test equipment and is often accompanied by smoke emanating from the contact between the balls. Table 2
• the lubricating composition according to the present invention provides an unexpected improvement in extreme pressure and anti- wear properties as measured according to ASTM D2596.
• Example 1 By using (a relatively high amount of) 8 wt.% sulphurised ester alone (Comparative Example 4 ⁇ a weld load of 315 kg was achieved, showing a degree of extreme pressure performance when compared with Comparative Example 1 (containing no sulphurised ester) .
• Example 1 according to the present invention (containing both sulphurised ester and bismuth sulphide) allows to achieve a weld load of well above 400 kg.
• the unexpectedly high weld load of 800 kg as achieved according to the present invention would be considered as a very high extreme pressure performance, suitable for greases in the highest loaded applications.
• An important advantage of the present invention is that improved extreme pressure properties may be obtained at the same total additive concentration, but also equivalent extreme pressure performance using lower concentrations of additives. This not only results in a reduction of costs (a smaller amount of relatively expensive additives is needed) , but also avoids or reduces some of the problems associated with typical extreme pressure additive concentrations such as corrosion, oxidation instability, and reduced product life at high temperature.
• the present invention shows also benefits in wear protection, as shown by the size of the wear scars shown above, from the tests which were run at loads less than the failure loads.
• Example 1 shows the smallest wear scar size compared with all Comparative Examples. Equally at 150 kg, a somewhat higher but still moderate load, the wear scar size from the test with Example 1 was equal lowest, together with Comparative Example 3, containing a large amount of bismuth sulphide. Such a large amount of bismuth sulphide as in Comparative Example 3 would represent a very considerable raw material cost to the lubricant producer and would probably not be considered in industrial practice.

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

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• 2009
  • 2009-08-10 EP EP09781658A patent/EP2331662A2/en not_active Withdrawn
  • 2009-08-10 BR BRPI0917016A patent/BRPI0917016A2/pt not_active IP Right Cessation
  • 2009-08-10 US US13/058,214 patent/US20110172133A1/en not_active Abandoned
  • 2009-08-10 WO PCT/EP2009/060328 patent/WO2010018148A2/en not_active Ceased
  • 2009-08-10 JP JP2011522494A patent/JP2011530638A/ja not_active Withdrawn
  • 2009-08-10 KR KR1020117005502A patent/KR20110053996A/ko not_active Withdrawn
  • 2009-08-10 RU RU2011109039/04A patent/RU2011109039A/ru not_active Application Discontinuation
  • 2009-08-10 CN CN2009801333451A patent/CN102137918A/zh active Pending

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