WO2013093103A1 - Lubricating composition - Google Patents
Lubricating composition Download PDFInfo
- Publication number
- WO2013093103A1 WO2013093103A1 PCT/EP2012/076850 EP2012076850W WO2013093103A1 WO 2013093103 A1 WO2013093103 A1 WO 2013093103A1 EP 2012076850 W EP2012076850 W EP 2012076850W WO 2013093103 A1 WO2013093103 A1 WO 2013093103A1
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- WIPO (PCT)
- Prior art keywords
- lubricating oil
- oil composition
- base oil
- composition according
- fischer
- Prior art date
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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- 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
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/104—Aromatic fractions
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/104—Aromatic fractions
- C10M2203/1045—Aromatic fractions used as base material
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
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- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
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- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/1256—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as thickening agent
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- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10N2030/04—Detergent property or dispersant property
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Definitions
- the present invention relates to a lubricating composition, in particular a lubricating composition having improved oxidation stability and deposit
- Fischer-Tropsch derived base oils in lubricating compositions such as engine oils, transmission fluids, and industrial lubricants results in various performance benefits.
- performance benefits by the use of Fischer-Tropsch derived base oils mentioned in the above article are: improved oxidation properties, improved engine cleanliness, improved wear protection, improved emissions and improved after- treatment device compatibility. Also the Fischer-Tropsch base oils allow to formulate low-viscosity energy
- Fischer-Tropsch base oils have relatively low solvency.
- solvent in relation to a base oil means the ability of that base oil to dissolve performance additives. It would be desirable to develop lubricating compositions having acceptable solvency at the same time as exhibiting the other
- a lubricating oil composition comprising:
- base oil selected from Group III base oils, Group IV polyalphaolefins, or a combination thereof;
- antioxidant selected from aminic antioxidants, phenolic antioxidants, and mixtures thereof;
- detergent comprising (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM D2896) in the range of from 50 to 150;
- an alkaline earth metal salicylate having a TBN in the range of from 150 to 250 (ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400.
- the base oil used in the lubricating composition according to the present invention is selected from a Group III base oil, a polyalphaolefin and mixtures thereof.
- the base oil used in the present invention may conveniently comprise mixtures of one or more Group III base oils and/or polyalphaolefins, thus, according to the present invention, the term "base oil” may refer to a mixture containing more than one base oil.
- Suitable base oils for use in the lubricating oil composition of the present invention are Group III mineral base oils, Group IV poly-alpha olefins (PAOs) , Group III Fischer-Tropsch derived base oils and mixtures thereof .
- Group III and “Group IV” base oils in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum
- API API for category III and IV. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
- Fischer-Tropsch derived base oils are known in the art.
- Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
- a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To- Liquids ⁇ base oil.
- Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating 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
- the aromatics content of a Fischer- Tropsch derived base oil will typically be below 1 wt . % , preferably below 0.5 wt . % and more preferably below 0.1 wt.%.
- the base oil has a total paraffin content of at least 80 wt.%, preferably at least 85, more preferably at least 90, yet more preferably at least 95 and most preferably at least 99 wt.%. It suitably has a saturates content (as measured by IP-368) of greater than 98 wt.%.
- the saturates content of the base oil is greater than 99 wt.%, more preferably greater than 99.5 wt.%. It further preferably has a maximum n-paraffin content of 0.5 wt.%.
- the base oil preferably also has a content of naphthenic compounds of from 0 to less than 20 wt.%, more preferably of from 0.5 to 10 wt.%.
- the Fischer-Tropsch derived base oil or base oil blend has a kinematic viscosity at 100°C ⁇ as measured by AST D 7042) in the range of from 1 to 35 irattVs (cSt), preferably from 1 to 25 mm 2 /s (cSt) , more preferably from 2 mm 2 /s to 12 mmVs.
- the Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C ⁇ as measured by AST D 7042) in the range of from 1 to 35 irattVs (cSt), preferably from 1 to 25 mm 2 /s (cSt) , more preferably from 2 mm 2 /s to 12 mmVs.
- the Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C ⁇ as measured by AST D 7042
- the Fischer- Tropsch derived base oil has a kinematic viscosity at 100 °C of at most 5.0 mm 2 /s, preferably at most 4.5 mm 2 /s, more preferably at most 4.2 mm 2 /s (e.g. "GTL 4").
- the Fischer- Tropsch derived base oil has a kinematic viscosity at 100 °C of at most 8.5 mm 2 /s, preferably at most 8 mm 2 /s (e.g. "GTL 8") .
- the Fischer-Tropsch derived base oil typically has a kinematic viscosity at 40 °C (as measured by ASTM D 7042) of from 10 to 100 mm 2 /s (cSt), preferably from 15 to 50 ram 2 /s.
- preferably has a pour point (as measured according to ASTM D 5950) of below -30°C, more preferably below ⁇ 40°C, and most preferably below -45 °C.
- the flash point ⁇ as measured by ASTM D92) of the Fischer-Tropsch derived base oil is preferably greater than 120°C, more preferably even greater than 140°C.
- the Fischer-Tropsch derived base oil preferably has a viscosity index (according to ASTM D 2270) in the range of from 100 to 200.
- the Fischer-Tropsch derived base oil has a viscosity index of at least 125, preferably 130. Also it is preferred that the viscosity index is below 180, preferably below 150.
- Fischer-Tropsch derived base oil contains a blend of two or more Fischer-Tropsch derived base oils
- the above values apply to the blend of the two or more Fischer-Tropsch derived base oils.
- PAOs Poly-alpha olefin base oils
- lubricating compositions of the present invention may be derived from linear C 2 to C32, preferably C 6 to Ci 6 , alpha olefins.
- Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, l ⁇ dodecene and 1-tetradecene .
- the base oil as used in the lubricating composition according to the present invention comprises at least a base oil selected from the group consisting of a poly-alpha olefin base oil and a Fischer-Tropsch derived base oil or a combination thereof.
- the base oil contains more than 50 wt.%, preferably more than 60 wt.%, more preferably more than 70 wt.%, even more preferably more than 80 wt.%. most preferably more than 90 wt.% Fischer-Tropsch derived base oil.
- not more than 5 wt.%, preferably not more than 2 wt.%, of the base oil is not a Fischer-Tropsch derived base oil. It is even more preferred that 100 wt% of the base oil is based on one or more Fischer-Tropsch derived base oils.
- the base oil or base oil blend comprising the Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C of between 2 and 35 cSt, preferably between 2 and 10.5 cSt (according to ASTM D 445) .
- the lubricating composition may comprise one or more other types of mineral derived or synthetic base oils, including Group I, II, IV and V base oils according to the definitions of American Petroleum Institute (API) . These API categories are defined in API
- the total amount of base oil incorporated in the lubricating composition of the present invention is preferably an amount in the range of from 60 to 99 wt.%, more preferably an amount in the range of from 65 to 90 wt.% and most preferably an amount in the range of from 70 to 85 wt.%, with respect to the total weight of the lubricating composition.
- solvency booster means a component which enhances the solvency of the Group III/PAO base oil, for example as measured by improvement of deposit reduction properties, as measured by the TEOST test method (thermo-oxidation engine oil simulation test) according to ASTM D7097-09) and the KHTT test method ( Komatsu Hot Tube Test according to JPI-5S- 55-99) .
- the use of a solvency booster in the lubricating composition of the present invention is particularly useful when the base oil is selected from a Fischer-
- the solvency booster is present at a level of 30 wt% or less, preferably 20 wt% of less, more preferably 15 wt% or less, by weight of the lubricating oil
- the solvency booster is preferably present at a level of 1 wt% or more, more preferably 3 wt% or more, even more preferably 5 wt% or more, by weight of the lubricating oil composition.
- Suitable solvency boosters for use herein are preferably selected from alkylated aromatic compounds, naphthenic base oils and ester base oils, and mixtures thereof .
- Preferred alkylated aromatic compounds for use as a solvency booster herein include alkylated benzenes, alkylated anthracenes, alkylated phenanthrenes, alkylated biphenyls, and alkylated naphthalenes and mixtures thereof .
- Alkylated naphthalenes may be produced by any suitable means known in the art, from naphthalene itself or from substituted naphthalenes which may contain one or more short chain alkyl groups having up to about eight carbon atoms, such as methyl, ethyl, or propyl, etc.
- Suitable alkyl-substituted naphthalenes include
- Naphthalene itself is especially suitable since the resulting mono-alkylated products have better thermal and oxidative stability than the more highly alkylated materials. Suitable alkylated
- naphthalene lubricant compositions are described in
- alkylated aromatic compound for use herein is preferably selected from alkylbenzene compounds
- alkylnaphthalene compounds and mixtures thereof.
- the alkylaromatic component preferably has a
- kinematic viscosity at 100°C in the range of from 3 to 12 mmVs, more preferably in the range of from 3.8 to 7 mmVs.
- alkylaromatic component is above 40, more preferably at or above 70.
- alkylnaphthalene compound An especially preferred alkylated aromatic compound for use herein is an alkylnaphthalene compound.
- alkylnaphthalene compounds are those available from King Industries under the tradename NA-Lube such as NA-Lube KR 008 , NA-Lube KR019, and the like, and those available from ExxonMobil under the tradename Mobil MCP.
- alkyl benzenes examples include that available from Formasan under the tradename Fusyn-22, those available from Janex under the tradename Janex HAL, and those available from Shreive Chemical
- Suitable naphthenic base oils for use as a solvency booster herein includes naphthenic base oils having low viscosity index (VI) (generally 40-80 ⁇ and a low pour point. Such base oils are produced from feedstocks rich in naphthenes and low in wax content.
- VI viscosity index
- Such base oils are produced from feedstocks rich in naphthenes and low in wax content.
- mineral-derived naphthenic base oil which can be used in the base oil composition herein. Any mineral-derived naphthenic base oil which is suitable for use in a lubricating oil composition can be used herein.
- Naphthenic base oils are defined as Group V base oils according to API.
- Such mineral-derived base oils are obtained by refinery processes starting from naphthenic crude feeds.
- Mineral-derived naphthenic base oils for use herein preferably have a pour point of below -20 °C and a
- Mineral-derived naphthenic base oils are well known and described in more detail in “Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel
- naphthenic base oils for use as a solvency booster herein include those available from Calumet Specialty Products under the tradenames Hydrocal, Hydrosol and HR Tufflo, and those commercially available from Nynas Oil Company under the tradename Nynas.
- Suitable esters for use as a solvency booster herein include natural and synthetic esters such as diesters and polyol esters.
- An example of a suitable ester for use as a solvency booster herein is the saturated polyol ester commercially available from Croda International PLC under the tradename Priolube 3970.
- Other suitable esters for use as a solvency booster herein include those available from Oleon under the tradename Radialube, those available from Emery under the tradename Emery and those available from ExxonMobil Chemical under the tradename Esterex.
- the lubricating oil compositions of the present invention comprise detergent, wherein the detergent comprises (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM D2896) in the range of from 50 to 150; (ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400.
- TBN total base number equivalent, as determined by ASTM D2896
- Suitable alkaline earth metal salicylates include calcium, magnesium and barium salicylates, and mixtures thereof, preferably calcium salicylates.
- the lubricating oil compositions of the present invention preferably comprises from 0,01 wt% to 9 wt%, more preferably from 1 wt% to 6 wt%, even more preferably from 3.5 wt% to 5.5 wt%, of detergent, by weight of the lubricating oil composition.
- the level of an alkaline earth metal salicylate having a TBNE (total base number equivalent, as
- the level of an alkaline earth metal salicylate having a TBN in the range of from 150 to 250 is
- the level of alkaline earth metal salicylate having a TBN in the range of from 250 to 400 is preferably in the range of 0.01 wt% to 3 wt%, more preferably from 1 wt% to 2 wt%, by weight of the lubricating oil
- the lubricating oil compositions of the present invention comprises one or more anti-oxidants.
- Suitable anti-oxidants for use herein include phenolic
- antioxidants and/or aminic antioxidants.
- said antioxidants are present in an amount in the range of from 0.1 to 5.0 t. %, more preferably in an amount in the range of from 0.3 to 3.0 wt. %, and most preferably in an amount of in the range of from 0.5 to 1.5 wt. %, based on the total weight of the lubricating oil composition.
- alkylated diphenylamines phenyl-a-naphthylamines, phenyl-p-naphthylamines and alkylated -naphthylamines .
- Preferred aminic antioxidants include
- dialkyldiphenylamines such as p, p ' -dioctyl-diphenylamine, p, ' -di-a-methylbenzyl-diphenylamine and N-p-butylphenyl- N-p ' -octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis (dialkylphenyl) amines such as di- ⁇ 2,4- diethylphenyl) amine and di (2-ethyl ⁇ 4 ⁇ nonylphenyl ⁇ amine, alkylphenyl ⁇ l-naphthylamines such as octylphenyl-l- naphthylamine and n-t-dodecylphenyl-l-naphthylamine, 1- naphthylamine, arylnap
- phenylenediamines such as N, N 1 -diisopropyl-p- phenylenediamine and N, ' -diphenyl-p-phenylenediamine, an phenothiazines such as phenothiazine and 3,7- dioctylphenothiazine .
- Preferred aminic antioxidants include those availabl under the following trade designations: "Sonoflex OD-3" (ex. Seiko agaku Co.), “Irganox L-57” (ex. Ciba Specialty Chemicals Co.) and phenothiazine (ex. Hodogaya agaku Co. ) .
- phenolic antioxidants which may be conveniently used include C7-C9 branched alkyl esters of 3, 5-bis (1, l-dimethyl-ethyl) -4-hydroxy-benzenepropanoic acid, 2-t-butylphenol, 2 ⁇ t-butyl-4- ⁇ methylphenol, 2-t- butyl-5-methylphenol, 2, 4-di ⁇ t-butylphenol, 2, 4-dimethyl- 6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl ⁇ 4- methoxyphenol, 2, 5-di-t-butylhydroquinone, 2, 6-di-t-butyl 4TMalkylphenols such as 2, 6-di-t ⁇ butylphenol, 2,6-di-t- butyl-4-methylphenol and 2, 6-di-t-butyl-4-ethylphenol, 2, 6 ⁇ di-tTMbutyl-4- ⁇ alkoxyphenols such as 2, 6-di-t ⁇ butyl
- phenolic antioxidants include those available under the following trade designations:
- the lubricating oil composition of the present invention may comprise mixtures of one or more phenolic antioxidants with one or more aminic antioxidants.
- the lubricating composition preferably comprises 30 wt% or less of a viscosity modifier, based on the total weight of the lubricating composition.
- the lubricating composition preferably comprises 30 wt% or less of a viscosity modifier, based on the total weight of the lubricating composition.
- lubricating composition comprises from 20 wt% to 30 wt% of viscosity modifier. In another embodiment, the lubricating composition comprises 20 wt% or less of viscosity modifier. In a preferred embodiment of the present invention, the lubricating composition is
- the lubricating composition comprises 0 wt% of a viscosity modifier.
- viscosity index improvers examples include
- copolymers of alpha-olefins and dicarboxylic acid esters such as those described in US 4 931 197.
- Commercially available copolymers of alpha-olefins and dicarboxylic acid diesters include the Ketjenlube polymer esters available from Italmatch ⁇ and previously Akzo Nobel
- viscosity index improvers are polyisobutylenes; commercially available polyisobutylenes include the Oloa (RTM) products available from Chevron Oronite.
- viscosity index improvers which may conveniently be used in the lubricating compositions of the present invention include the styrene-butadiene stellate copolymers, styrene-isoprene stellate copolymers and the polymethacrylate copolymers and ethylene- propylene copolymers (also known as olefin copolymers) of the crystalline and non-crystalline type.
- Suitable olefin copolymers include those
- Suitable polyisoprene polymers include those commercially available from Infineum International Limited, e.g. under the trade designation "SV200”.
- Suitable diene-styrene copolymers include those commercially available from Infineum International
- compositions herein may include one or more anti-wear additives.
- Suitable anti-wear additives for use herein include zinc dithiophosphate compounds
- ashless anti-wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
- ashless thiophosphates examples are known in the art. These compounds are metal-free organic compounds. Suitable ashless thiophosphates for use in the
- lubricating oil composition of the present invention may include esters and/or salts of thiophosphoric acids, and substituted thiophosphoric acids.
- the ashless thiophosphates are substituted by one or more hydrocarbyl groups which hydrocarbyl groups can
- the hydrocarbyl moiety preferably is an alkyl group containing up to 12 carbon atoms.
- the hydrocarbyl- substituted thiophosphate preferably contains 2 or 3 hydrocarbyl groups, or is a mixture of thiophosphates containing 2 and 3 hydrocarbyl groups.
- the ashless thiophosphates can contain any number of sulphur atoms directly linked to the phosphorus atom.
- the thiophosphates are monothiophosphates and/or dithiophosphates .
- ashless thiophosphates which may be conveniently used in the lubricating oil composition of the present invention are described in ⁇ - ⁇ -0375324 , US- A-5922657, US-A-4333841 and US-A-5093016 and may be conveniently made according to the methods described therein.
- composition comprises one or more anti-wear additives selected from one or more zinc dithiophosphates .
- the or each zinc dithiophosphate may be selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates .
- the lubricating composition according to the present invention comprises a phosphorus containing compound, preferably selected from the group consisting of phosphonates, phosphates, phosphites,
- dithiophosphates and phosphates are "IRGALUBE 63" and IRGALUBE 349", respectively, both available from Ciba Specialty Chemicals.
- the lubricating oil composition of the present invention has a kinematic viscosity at 40 °C in the range of from 2 mm2/s to 220 mm2/s, preferably in the range of from 32 mm2/s to 220 mm2/s.
- inventions may further comprise one or more additional additives such as anti-oxidants , dispersants, detergents, extreme-pressure additives, friction modifiers, viscosity index improvers, pour point depressants, metal
- passivators corrosion inhibitors, demulsifiers , anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
- the above-mentioned additives are typically present in an amount in the range of from 0.01 to 35.0 wt.%, based on the total weight of the lubricating composition, preferably in an amount in the range of from 0.05 to 25.0 wt.%, more preferably from 0.1 to 20.0 wt.%, based on the total weight of the lubricating composition.
- inventions may be conveniently prepared by admixing the one or more additives with the base oil(s).
- the lubricating composition according to the present invention may be used in various applications, such as in internal combustion engines (as an engine oil), as a transmission oil, a grease, a hydraulic oil, an
- the present invention provides a method for improving one or more of oxidation stability and deposit reduction properties, which method comprises lubricating with a lubricating composition according to the invention.
- the present invention provides the use of a lubricating composition as
- oxidation stability properties in particular as determined by ASTM D6186-98
- deposit reduction properties in particular as determined according to ASTM D7097-09 or JPI-5S-55-99.
- Table 1 shows the properties of the base oils.
- Table 2 indicates the amounts of additives, base oils and solvency boosters incorporated into the respective formulations; the amounts are given in wt.%, based on the total weight of the lubricating composition.
- Base oil 1 (or W B01" or “GTL 4”) was a Fischer- Tropsch derived base oil having a kinematic viscosity at 100°C (ASTM D445) of approximately 3.89 cSt (mm 2 s -1 ) ⁇ Base oil 1 may be conveniently manufactured by the process described in e.g. WO-A-02/070631, the teaching of which is hereby incorporated by reference.
- Base oil 2 (or “B02") was a commercially available Group III base oil having a kinematic viscosity at 100 °C (ASTM D445) of approximately 4.3 cSt.
- Base oil 2 is commercially available from e.g. S Energy (Ulsan, South Korea) under the trade designation "Yubase 4".
- Base oil 3 (or “B03") was a polyalphaolefin base oil (“PAO 4") having a kinematic viscosity at 100°C (ASTM D445) of approximately 4 cSt .
- Base Oil 3 is commercially available from INEOS under the trade designation "Durasyn D164".
- HPDSC-OIT High Pressure Differential Scanning Calorimetry
- OIT oxidation induction time
- n.d. means "not determined”.
- Liquid high molecular weight phenolic antioxidant commercially available from CIBA Speciality Chemicals, Basel, Switzerland
- Naphthenic base oil commercially available from China National Petroleum Corporation under the tradename KN 4006.
- the lubricating compositions according to the present invention show improved oxidation stability and deposit control properties, in comparison to the lubricating compositions falling outside the scope of the present invention.
- compositions in Tables 3-7 below are examples of Group Ill-based lubricating oil compositions. Such compositions could be reformulated to contain a solvency booster, antioxidant and detergent as per examples 5, 6, 11, 12, 17, 18, 24, 25, 31, 32, 38, 39, 46, 47, 53, 54, 61 and 62 above, and would be expected to show similar performance benefits in terms of oxidation stability and deposit control.
- Table 3 gives details of a typical HDDEO lubricant formulation .
- Table 5 gives details of a typical grease formulation.
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Abstract
A lubricating oil composition comprising: (a) base oil selected from Group III base oils, Group IV polyalphaolefins, or a combination thereof; (b) 30 wt% or less solvency booster; (c) antioxidant selected from aminic antioxidants, phenolic antioxidants, and mixtures thereof; (d) detergent comprising (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM D2896) in the range of from 50 to 150; (ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400. The lubricating oil composition of the present invention provides improved oxidation and improved piston cleanliness properties.
Description
LUBRICATING COMPOSITION
The present invention relates to a lubricating composition, in particular a lubricating composition having improved oxidation stability and deposit
reduction.
As is disclosed in for example D.J. Wedlock et al.,
"Gas-to~Llquids Base Oils to assist in meeting OEM requirements 2010 and beyond", presented at the 2nd Asia- Pacific base oil Conference, Beijing, China, 23-25
October 2007, the use of Fischer-Tropsch derived base oils in lubricating compositions such as engine oils, transmission fluids, and industrial lubricants results in various performance benefits. Examples of performance benefits by the use of Fischer-Tropsch derived base oils mentioned in the above article are: improved oxidation properties, improved engine cleanliness, improved wear protection, improved emissions and improved after- treatment device compatibility. Also the Fischer-Tropsch base oils allow to formulate low-viscosity energy
conserving formulations.
Fischer-Tropsch derived base oils are highly
paraffinic API group III base oils (API Base Oil
Interchangeability Guidelines) exhibiting very good cold flow properties, high oxidative stability and high viscosity indices. However, due to the high paraffin content the solvency of the base oils is generally low, resulting in incompatibility with other lubricant
components and additives.
Fischer-Tropsch base oils have relatively low solvency. As used herein the term "solvency" in relation to a base oil means the ability of that base oil to
dissolve performance additives. It would be desirable to develop lubricating compositions having acceptable solvency at the same time as exhibiting the other
performance benefits mentioned above, in particular improved oxidation stability and reduced piston deposits.
One or more of the above or other objects can be obtained by a lubricating oil composition comprising:
(a) base oil selected from Group III base oils, Group IV polyalphaolefins, or a combination thereof;
(b) 30 wt% or less solvency booster;
(c) antioxidant selected from aminic antioxidants, phenolic antioxidants, and mixtures thereof;
(d) detergent comprising (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM D2896) in the range of from 50 to 150;
(ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400.
It has surprisingly been found that the lubricating compositions according to the present invention exhibit improved oxidation stability and improved piston
cleanliness properties.
The base oil used in the lubricating composition according to the present invention is selected from a Group III base oil, a polyalphaolefin and mixtures thereof. The base oil used in the present invention may conveniently comprise mixtures of one or more Group III base oils and/or polyalphaolefins, thus, according to the present invention, the term "base oil" may refer to a mixture containing more than one base oil.
Suitable base oils for use in the lubricating oil composition of the present invention are Group III
mineral base oils, Group IV poly-alpha olefins (PAOs) , Group III Fischer-Tropsch derived base oils and mixtures thereof .
By "Group III" and "Group IV" base oils in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum
Institute (API) for category III and IV. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
Fischer-Tropsch derived base oils are known in the art. By the term "Fischer-Tropsch derived" is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process. A Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To- Liquids} base oil. Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating 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.
Typically, the aromatics content of a Fischer- Tropsch derived base oil, suitably determined by ASTM D 4629, will typically be below 1 wt . % , preferably below 0.5 wt . % and more preferably below 0.1 wt.%. Suitably, the base oil has a total paraffin content of at least 80 wt.%, preferably at least 85, more preferably at least 90, yet more preferably at least 95 and most preferably at least 99 wt.%. It suitably has a saturates content (as measured by IP-368) of greater than 98 wt.%.
Preferably the saturates content of the base oil is greater than 99 wt.%, more preferably greater than 99.5 wt.%. It further preferably has a maximum n-paraffin
content of 0.5 wt.%. The base oil preferably also has a content of naphthenic compounds of from 0 to less than 20 wt.%, more preferably of from 0.5 to 10 wt.%.
Typically, the Fischer-Tropsch derived base oil or base oil blend has a kinematic viscosity at 100°C {as measured by AST D 7042) in the range of from 1 to 35 irattVs (cSt), preferably from 1 to 25 mm2/s (cSt) , more preferably from 2 mm2/s to 12 mmVs. Preferably, the Fischer-Tropsch derived base oil has a kinematic
viscosity at 100°C {as measured by ASTM D 7042) of at least 2.5 mm2/s more preferably at least 3.0 mm2/s. In one embodiment of the present invention, the Fischer- Tropsch derived base oil has a kinematic viscosity at 100 °C of at most 5.0 mm2/s, preferably at most 4.5 mm2/s, more preferably at most 4.2 mm2/s (e.g. "GTL 4"). In another embodiment of the present invention, the Fischer- Tropsch derived base oil has a kinematic viscosity at 100 °C of at most 8.5 mm2/s, preferably at most 8 mm2/s (e.g. "GTL 8") .
Further, the Fischer-Tropsch derived base oil typically has a kinematic viscosity at 40 °C (as measured by ASTM D 7042) of from 10 to 100 mm2/s (cSt), preferably from 15 to 50 ram2/s.
Also, the Fischer-Tropsch derived base oil
preferably has a pour point (as measured according to ASTM D 5950) of below -30°C, more preferably below ~40°C, and most preferably below -45 °C.
The flash point {as measured by ASTM D92) of the Fischer-Tropsch derived base oil is preferably greater than 120°C, more preferably even greater than 140°C.
The Fischer-Tropsch derived base oil preferably has a viscosity index (according to ASTM D 2270) in the range of from 100 to 200. Preferably, the Fischer-Tropsch
derived base oil has a viscosity index of at least 125, preferably 130. Also it is preferred that the viscosity index is below 180, preferably below 150.
In the event the Fischer-Tropsch derived base oil contains a blend of two or more Fischer-Tropsch derived base oils, the above values apply to the blend of the two or more Fischer-Tropsch derived base oils.
Poly-alpha olefin base oils (PAOs) and their
manufacture are well known in the art. Preferred poly- alpha olefin base oils that may be used in the
lubricating compositions of the present invention may be derived from linear C2 to C32, preferably C6 to Ci6, alpha olefins. Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, l~dodecene and 1-tetradecene .
According to the present invention, the base oil as used in the lubricating composition according to the present invention comprises at least a base oil selected from the group consisting of a poly-alpha olefin base oil and a Fischer-Tropsch derived base oil or a combination thereof.
There is a strong preference for using a Fischer- Tropsch derived base oil over a PAO base oil, in view of the high cost of manufacture of the PAOs. Thus,
preferably, the base oil contains more than 50 wt.%, preferably more than 60 wt.%, more preferably more than 70 wt.%, even more preferably more than 80 wt.%. most preferably more than 90 wt.% Fischer-Tropsch derived base oil. In an especially preferred embodiment not more than 5 wt.%, preferably not more than 2 wt.%, of the base oil is not a Fischer-Tropsch derived base oil. It is even more preferred that 100 wt% of the base oil is based on one or more Fischer-Tropsch derived base oils.
Preferably the base oil or base oil blend comprising the Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C of between 2 and 35 cSt, preferably between 2 and 10.5 cSt (according to ASTM D 445) .
In addition to the Group III base oil and/or
polyalphaolefin base oil, the lubricating composition may comprise one or more other types of mineral derived or synthetic base oils, including Group I, II, IV and V base oils according to the definitions of American Petroleum Institute (API) . These API categories are defined in API
Publication 1509, 15th Edition, Appendix E, July 2009.
The total amount of base oil incorporated in the lubricating composition of the present invention is preferably an amount in the range of from 60 to 99 wt.%, more preferably an amount in the range of from 65 to 90 wt.% and most preferably an amount in the range of from 70 to 85 wt.%, with respect to the total weight of the lubricating composition.
Another essential component of the lubricating oil compositions of the present invention is a solvency booster. As used herein, the term "solvency booster" means a component which enhances the solvency of the Group III/PAO base oil, for example as measured by improvement of deposit reduction properties, as measured by the TEOST test method (thermo-oxidation engine oil simulation test) according to ASTM D7097-09) and the KHTT test method (Komatsu Hot Tube Test according to JPI-5S- 55-99) . The use of a solvency booster in the lubricating composition of the present invention is particularly useful when the base oil is selected from a Fischer-
Tropsch derived base oil.
The solvency booster is present at a level of 30 wt% or less, preferably 20 wt% of less, more preferably 15
wt% or less, by weight of the lubricating oil
composition. The solvency booster is preferably present at a level of 1 wt% or more, more preferably 3 wt% or more, even more preferably 5 wt% or more, by weight of the lubricating oil composition.
Suitable solvency boosters for use herein are preferably selected from alkylated aromatic compounds, naphthenic base oils and ester base oils, and mixtures thereof .
Preferred alkylated aromatic compounds for use as a solvency booster herein include alkylated benzenes, alkylated anthracenes, alkylated phenanthrenes, alkylated biphenyls, and alkylated naphthalenes and mixtures thereof .
Alkylated naphthalenes may be produced by any suitable means known in the art, from naphthalene itself or from substituted naphthalenes which may contain one or more short chain alkyl groups having up to about eight carbon atoms, such as methyl, ethyl, or propyl, etc.
Suitable alkyl-substituted naphthalenes include
alphamethylnaphthalene, dimethylnaphthalene, and
ethylnaphthalene . Naphthalene itself is especially suitable since the resulting mono-alkylated products have better thermal and oxidative stability than the more highly alkylated materials. Suitable alkylated
naphthalene lubricant compositions are described in
US-B-3812036, and US-A-5602086. The preparation of alkylnaphthalenes is further disclosed in US-A-4714794.
The alkylated aromatic compound for use herein is preferably selected from alkylbenzene compounds,
alkylnaphthalene compounds, and mixtures thereof.
The alkylaromatic component preferably has a
kinematic viscosity at 100°C in the range of from 3 to 12
mmVs, more preferably in the range of from 3.8 to 7 mmVs. Preferably the viscosity index of the
alkylaromatic component is above 40, more preferably at or above 70.
An especially preferred alkylated aromatic compound for use herein is an alkylnaphthalene compound. Examples of commercially available alkylnaphthalene compounds are those available from King Industries under the tradename NA-Lube such as NA-Lube KR 008 , NA-Lube KR019, and the like, and those available from ExxonMobil under the tradename Mobil MCP.
Examples of commercially available alkyl benzenes include that available from Formasan under the tradename Fusyn-22, those available from Janex under the tradename Janex HAL, and those available from Shreive Chemical
Products, Inc. (SCP) under the tradename ZEROL.
Suitable naphthenic base oils for use as a solvency booster herein includes naphthenic base oils having low viscosity index (VI) (generally 40-80} and a low pour point. Such base oils are produced from feedstocks rich in naphthenes and low in wax content. There is no particular limitation on the type of mineral-derived naphthenic base oil which can be used in the base oil composition herein. Any mineral-derived naphthenic base oil which is suitable for use in a lubricating oil composition can be used herein.
Naphthenic base oils are defined as Group V base oils according to API.
Such mineral-derived base oils are obtained by refinery processes starting from naphthenic crude feeds.
Mineral-derived naphthenic base oils for use herein preferably have a pour point of below -20 °C and a
viscosity index of below 70. Such base oils are produced
from feedstocks rich in naphthenes and low in wax
content. Mineral-derived naphthenic base oils are well known and described in more detail in "Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel
Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 28-35.
Methods of manufacture of naphthenic base oils can be found in "Lubricants and Lubrication (Second,
Completely Revised and Extended Edition)", published by iley-VCH Verlag GmbH & Co. KgaA, Chapter 4, pages 46-48.
An example of a suitable naphthenic base oil for use as a solvency booster herein is that commercially
available from China National Petroleum Corporation under the tradename KN4006. Other examples of suitable
naphthenic base oils for use as a solvency booster herein include those available from Calumet Specialty Products under the tradenames Hydrocal, Hydrosol and HR Tufflo, and those commercially available from Nynas Oil Company under the tradename Nynas.
Suitable esters for use as a solvency booster herein include natural and synthetic esters such as diesters and polyol esters. An example of a suitable ester for use as a solvency booster herein is the saturated polyol ester commercially available from Croda International PLC under the tradename Priolube 3970. Other suitable esters for use as a solvency booster herein include those available from Oleon under the tradename Radialube, those available from Emery under the tradename Emery and those available from ExxonMobil Chemical under the tradename Esterex.
The lubricating oil compositions of the present invention comprise detergent, wherein the detergent comprises (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM
D2896) in the range of from 50 to 150; (ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400.
It has been found that this particular combination of alkaline earth metal salicylates, together with the specified base oil, solvency booster and antioxidant has been found to be especially helpful in providing improved oxidation stability and reduced deposits.
Suitable alkaline earth metal salicylates include calcium, magnesium and barium salicylates, and mixtures thereof, preferably calcium salicylates.
The lubricating oil compositions of the present invention preferably comprises from 0,01 wt% to 9 wt%, more preferably from 1 wt% to 6 wt%, even more preferably from 3.5 wt% to 5.5 wt%, of detergent, by weight of the lubricating oil composition.
The level of an alkaline earth metal salicylate having a TBNE (total base number equivalent, as
determined by ASTM D2896) in the range of from 50 to 150 is preferably in the range of 0.01 wt% to 5 wt%, more preferably from 1 wt% to 4 wt%, by weight of the
lubricating oil composition.
The level of an alkaline earth metal salicylate having a TBN in the range of from 150 to 250 is
preferably in the range of 0.01 wt% to 5 wt%, more preferably from 1 wt% to 3 wt%, by weight of the
lubricating oil composition.
The level of alkaline earth metal salicylate having a TBN in the range of from 250 to 400 is preferably in the range of 0.01 wt% to 3 wt%, more preferably from 1 wt% to 2 wt%, by weight of the lubricating oil
composition .
The lubricating oil compositions of the present invention comprises one or more anti-oxidants. Suitable anti-oxidants for use herein include phenolic
antioxidants and/or aminic antioxidants.
In a preferred embodiment, said antioxidants are present in an amount in the range of from 0.1 to 5.0 t. %, more preferably in an amount in the range of from 0.3 to 3.0 wt. %, and most preferably in an amount of in the range of from 0.5 to 1.5 wt. %, based on the total weight of the lubricating oil composition.
Examples of aminic antioxidants which may be
conveniently used include alkylated diphenylamines, phenyl-a-naphthylamines, phenyl-p-naphthylamines and alkylated -naphthylamines .
Preferred aminic antioxidants include
dialkyldiphenylamines such as p, p ' -dioctyl-diphenylamine, p, ' -di-a-methylbenzyl-diphenylamine and N-p-butylphenyl- N-p ' -octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis (dialkylphenyl) amines such as di-{2,4- diethylphenyl) amine and di (2-ethyl~4~nonylphenyl} amine, alkylphenyl~l-naphthylamines such as octylphenyl-l- naphthylamine and n-t-dodecylphenyl-l-naphthylamine, 1- naphthylamine, arylnaphthylamines such as phenyl-1- naphthylamine, phenyl-2-naphthylamine, N-hexylphenyl-2- naphthylamine and N-octylphenyl-2~naphthylamine,
phenylenediamines such as N, N 1 -diisopropyl-p- phenylenediamine and N, ' -diphenyl-p-phenylenediamine, an phenothiazines such as phenothiazine and 3,7- dioctylphenothiazine .
Preferred aminic antioxidants include those availabl under the following trade designations: "Sonoflex OD-3" (ex. Seiko agaku Co.), "Irganox L-57" (ex. Ciba
Specialty Chemicals Co.) and phenothiazine (ex. Hodogaya agaku Co. ) .
Examples of phenolic antioxidants which may be conveniently used include C7-C9 branched alkyl esters of 3, 5-bis (1, l-dimethyl-ethyl) -4-hydroxy-benzenepropanoic acid, 2-t-butylphenol, 2~t-butyl-4-~methylphenol, 2-t- butyl-5-methylphenol, 2, 4-di~~t-butylphenol, 2, 4-dimethyl- 6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl~4- methoxyphenol, 2, 5-di-t-butylhydroquinone, 2, 6-di-t-butyl 4™alkylphenols such as 2, 6-di-t~butylphenol, 2,6-di-t- butyl-4-methylphenol and 2, 6-di-t-butyl-4-ethylphenol, 2, 6~di-t™butyl-4-~alkoxyphenols such as 2, 6-di-t~butyl-4- methoxyphenol and 2, 6™di-t-butyl-4-ethoxyphenol, 3,5-di-t butyl-4-hydroxybenzylmercaptooctylacetate, alkyl-3- {3, 5- di-t-butyl-4-hydroxyphenyl) propionates such as n- octadecyl-3- (3, 5-di-t~butyl-4-hydroxyphenyl) ropionate, n butyl-3™ (3, 5-di-t~butyl-4~hydroxyphenyl) propionate and 2' ethylhexyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2 , 6™d-t-butyl~ -dimethylamino-p~cresol r 2,2' -methylene- bis (4-alkyl-6~t-butylphenol) such as 2 , 2 ' -methylenebis (4- raethyl-6~t-butylphenol, and 2, 2-methylenebis (4-ethyl-6-t- butylphenol} , bisphenols such as 4, 4 ' -butylidenebis {3- methyl~6-t-butylphenol, 4,4' -methylenebis (2 , 6-di-t- butylphenol) , 4 , 4 ' -bis (2, 6-di-t-butylphenol) , 2,2~(di-p- hydroxyphenyl) propane, 2, 2-bis (3, 5-di-t-butyl-4- hydroxyphenyl } ropane, 4, 4 ' -cyclohexylidenebis (2, 6-t- butylphenol) , hexamethyleneglycol-bis [3- (3, 5-di-t-butyl-4 hydroxyphenyl) propionate] , triethyleneglycolbis [3- (3-t- butyl-4-hydroxy-5~methylphenyl) propionate] , 2,2'~thio- [diethyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] , 3, 9-bis {1, l-dimethyl-2- [3- ( 3-t-butyl~-4-hydroxy-5-methyl- phenyl) ropionyloxy] ethyl } 2, , 8, 10- tetraoxaspiro [5, 5] undecane, 4,4' -thiobis ( 3-methyl-6-t-
12 076850
- 13 - butylphenol) and 2, 2 ' -thiobis (4, 6-di-t-butylresorcinol) , polyphenols such as tetrakis [methylene-3- { 3, 5™di-t-butyl- 4-hydroxyphenyl) propionate] methane, 1,1, 3-tris (2-methyl-4- hydroxy-5-t-butylphenyl) butane, 1, 3, 5-trimethyl-2, 4, 6- tris (3, 5-di-~t-butyl-4~hydroxybenzyl) benzene, bis- [3, 3 ' - bis {4 ' -hydroxy-3 ' -t-butylphenyl) butyric acid] glycol ester 2- (3 ' , 5 ' -di~t-butyl~4-hydroxyphenyl)methyl-4-~ (2", 4"-di-t- butyl""3"-hydroxyphenyl)methyl-6-t-butylphenol and 2,6- bis (2 ' -hydroxy-3 ' ~t-b tyl~5 T -methylbenzyl) ~4-methylphenol and p-t-butylphenol - formaldehyde condensates and p-t™ butylphenol - acetaldehyde condensates .
Preferred. phenolic antioxidants include those available under the following trade designations:
"Irganox L-135" (ex. Ciba Specialty Chemicals Co.),
"Yoshinox SS" {ex. Yoshitomi Seiyaku Co.), "Antage W-400" (ex. Kawaguchi Kagaku Co.), "Antage W-500" {ex. Kawaguchi Kagaku Co.), "Antage -300" (ex. Kawaguchi Kagaku Co.), "Irganox L-109" {ex. Ciba Speciality Chemicals Co.), "Tominox 917" {ex. Yoshitomi Seiyaku Co.), "Irganox L-115 (ex. Ciba Speciality Chemicals Co.), "Sumilizer GA80" {ex Sumitomo Kagaku), "Antage RC" (ex. Kawaguchi Kagaku Co.), "Irganox L-101" (ex. Ciba Speciality Chemicals Co.), "Yoshinox 930" (ex. Yoshitomi Seiyaku Co.).
The lubricating oil composition of the present invention may comprise mixtures of one or more phenolic antioxidants with one or more aminic antioxidants.
According to the present invention, the lubricating composition preferably comprises 30 wt% or less of a viscosity modifier, based on the total weight of the lubricating composition. In one embodiment, the
lubricating composition comprises from 20 wt% to 30 wt% of viscosity modifier. In another embodiment, the lubricating composition comprises 20 wt% or less of
viscosity modifier. In a preferred embodiment of the present invention, the lubricating composition is
essentially free of viscosity modifier. In a
particularly preferred embodiment of the present
invention, the lubricating composition comprises 0 wt% of a viscosity modifier.
Examples of viscosity index improvers include
copolymers of alpha-olefins and dicarboxylic acid esters such as those described in US 4 931 197. Commercially available copolymers of alpha-olefins and dicarboxylic acid diesters include the Ketjenlube polymer esters available from Italmatch {and previously Akzo Nobel
Chemicals) . Other suitable examples of viscosity index improvers are polyisobutylenes; commercially available polyisobutylenes include the Oloa (RTM) products available from Chevron Oronite.
Further examples of viscosity index improvers which may conveniently be used in the lubricating compositions of the present invention include the styrene-butadiene stellate copolymers, styrene-isoprene stellate copolymers and the polymethacrylate copolymers and ethylene- propylene copolymers (also known as olefin copolymers) of the crystalline and non-crystalline type.
Suitable olefin copolymers include those
commercially available from Chevron Oronite Company LLC under the trade designation "PARATONE (RTM) " (such as "PARATONE (RTM) 8921" and "PARATONE (RTM) 8941"); those commercially available from Afton Chemical Corporation under the trade designation "HiTEC (RTM)" (such as "HiTEC (RTM) 5850B"} ; and those commercially available from The Lubrizol Corporation under the trade designation
"Lubrizol (RTM) 7067C". Suitable polyisoprene polymers include those commercially available from Infineum
International Limited, e.g. under the trade designation "SV200". Suitable diene-styrene copolymers include those commercially available from Infineum International
Limited, e.g. under the trade designation "SV 260".
The compositions herein may include one or more anti-wear additives. Suitable anti-wear additives for use herein include zinc dithiophosphate compounds
selected from zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates, molybdenum-containing compounds, and ashless anti-wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
Examples of ashless thiophosphates are known in the art. These compounds are metal-free organic compounds. Suitable ashless thiophosphates for use in the
lubricating oil composition of the present invention may include esters and/or salts of thiophosphoric acids, and substituted thiophosphoric acids. Preferably, the ashless thiophosphates are substituted by one or more hydrocarbyl groups which hydrocarbyl groups can
optionally contain an acid, a hydroxy and/or an ester group. The hydrocarbyl moiety preferably is an alkyl group containing up to 12 carbon atoms. The hydrocarbyl- substituted thiophosphate preferably contains 2 or 3 hydrocarbyl groups, or is a mixture of thiophosphates containing 2 and 3 hydrocarbyl groups.
The ashless thiophosphates can contain any number of sulphur atoms directly linked to the phosphorus atom. Preferably, the thiophosphates are monothiophosphates and/or dithiophosphates .
Examples of ashless thiophosphates which may be conveniently used in the lubricating oil composition of the present invention are described in ΕΡ-Ά-0375324 , US- A-5922657, US-A-4333841 and US-A-5093016 and may be
conveniently made according to the methods described therein.
Examples of commercially available ashless
thiophosphates that may be conveniently used in the lubricating oil composition of the present invention include those available from Ciba Specialty Chemicals under the trade designations "IRGALUBE L~63" and
"IRGALUBE 353" and that available from Lubrizol under the trade designation "LZ 5125".
In a preferred embodiment, the lubricating
composition comprises one or more anti-wear additives selected from one or more zinc dithiophosphates . The or each zinc dithiophosphate may be selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates .
Examples of zinc dithiophosphates which are
commercially available include those available from
Lubrizol Corporation under the trade designations "L z
677A", "Lz 1095", "Lz 1097", "Lz 1370", "Lz 1371", ttLz 1373" and "Lz 1395", those available from Chevron Oronite under the trade designations "OLOA 260", "OLOA 262", "OLOA 267" and "OLOA 269R", and those available from Afton Chemical under the trade designation "HITEC 7169" and "HITEC 7197".
Preferably, the lubricating composition according to the present invention comprises a phosphorus containing compound, preferably selected from the group consisting of phosphonates, phosphates, phosphites,
phosphorothionates and dithiophosphates, and combinations thereof. Examples of commercially available
dithiophosphates and phosphates are "IRGALUBE 63" and IRGALUBE 349", respectively, both available from Ciba Specialty Chemicals.
The lubricating oil composition of the present
invention has a kinematic viscosity at 40 °C in the range of from 2 mm2/s to 220 mm2/s, preferably in the range of from 32 mm2/s to 220 mm2/s.
In addition to the components mentioned above, the lubricating composition according to the present
invention may further comprise one or more additional additives such as anti-oxidants , dispersants, detergents, extreme-pressure additives, friction modifiers, viscosity index improvers, pour point depressants, metal
passivators, corrosion inhibitors, demulsifiers , anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
As the person skilled in the art is familiar with the above and other additives, these are not further discussed here in detail.
Specific examples of such additives are described in for example irk-Othmer Encyclopedia of Chemical
Technology, third edition, volume 14, pages 477-526.
The above-mentioned additives are typically present in an amount in the range of from 0.01 to 35.0 wt.%, based on the total weight of the lubricating composition, preferably in an amount in the range of from 0.05 to 25.0 wt.%, more preferably from 0.1 to 20.0 wt.%, based on the total weight of the lubricating composition.
The lubricating compositions of the present
invention may be conveniently prepared by admixing the one or more additives with the base oil(s).
The lubricating composition according to the present invention may be used in various applications, such as in internal combustion engines (as an engine oil), as a transmission oil, a grease, a hydraulic oil, an
industrial gear oil, a turbine oil, a compressor oil, and the like.
In another aspect the present invention provides a method for improving one or more of oxidation stability and deposit reduction properties, which method comprises lubricating with a lubricating composition according to the invention. In another aspect, the present invention provides the use of a lubricating composition as
described herein, for improving one or more of oxidation stability properties (in particular as determined by ASTM D6186-98) and deposit reduction properties, in particular as determined according to ASTM D7097-09 or JPI-5S-55-99.
The present invention is described below with
reference to the following Examples, which are not
intended to limit the scope of the present invention in any way.
Examples
Lubricating Oil Compositions
Various combinations of additives, base oils and solvency boosters were formulated. Table 1 shows the properties of the base oils. Table 2 indicates the amounts of additives, base oils and solvency boosters incorporated into the respective formulations; the amounts are given in wt.%, based on the total weight of the lubricating composition.
"Base oil 1" (or WB01" or "GTL 4") was a Fischer- Tropsch derived base oil having a kinematic viscosity at 100°C (ASTM D445) of approximately 3.89 cSt (mm2s-1) · Base oil 1 may be conveniently manufactured by the process described in e.g. WO-A-02/070631, the teaching of which is hereby incorporated by reference.
"Base oil 2" (or "B02") was a commercially available Group III base oil having a kinematic viscosity at 100 °C (ASTM D445) of approximately 4.3 cSt. Base oil 2 is commercially available from e.g. S Energy (Ulsan, South
Korea) under the trade designation "Yubase 4".
"Base oil 3" (or "B03") was a polyalphaolefin base oil ("PAO 4") having a kinematic viscosity at 100°C (ASTM D445) of approximately 4 cSt . Base Oil 3 is commercially available from INEOS under the trade designation "Durasyn D164".
Table 1
ccording to ASTM D 445
According to ASTM D 2270
According to ASTM D 5950
^According to CEC L-40-A-93 / ASTM D 5800
According to IP 368 (modified)
According to 13C NMR
According to FIMS
According to ASTM D 5293
n.d. = not determined
HPDSC-OIT Test
In order to measure the oxidation stability
properties of the various lubricating compositions set out in Table 2 , the lubricating compositions were
subjected to the HPDSC-OIT (High Pressure Differential Scanning Calorimetry) test according to ASTM D6186-08, at a temperature of 200°C, and oxygen at 200 psig) .
Improved anti-oxidation properties are evidenced by greater oxidation induction time (OIT) .
TEOST Test
In order to measure the oxidation stability
properties of the various lubricating compositions set out in Table 2, the lubricating compositions were subjected to the TEOST test (thermo-oxidation engine oil simulation test) according to ASTM D7097-09. Improved deposit control properties are evidence by reduced deposit weights.
KHTT Test
In order to measure deposit reduction properties of the various lubricating compositions set out in Table 2 , the lubricating compositions were subjected to the KHTT test (Koraatsu Hot Tube Test) at 280 QC according to JPI- 5S-55-99. Improved deposit reduction properties are evidenced by both a higher merit rating average, and a lower weighted deposit average.
Table 2
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
Table 2 continued
In Table 2 above Examples 1-4, 7-10, 13-16, 19-23, 26-30, 33-37, 40-45, 48-52, 55-60 and 63-67 are
Comparative Examples.
In Table 2 above, n.d. means "not determined".
In Table 2, the components marked with superscripts 1-10 are as follows:
1. Alkylated naphthalene commercially available from King Industries
2. Dialkyl benzene commercially available from Formosan Chemicals
3. Octylated/butylated (DPA) , available from CIBA
Speciality Chemicals, Basel, Switzerland
4. Liquid high molecular weight phenolic antioxidant commercially available from CIBA Speciality Chemicals, Basel, Switzerland
5. Dinuclear molybdenum-sulphur compound, available from Infineum International Ltd (Abingdon, UK)
6. Low BI (Basicity Index) salicylate detergent (Ca~ based) commercially available from Infineum International Ltd (Abingdon, UK)
7. Medium BI salicylate detergent (Ca-based)
commercially available from Infineum International Ltd, Abingdon, UK
8. High BI salicylate detergent (Ca-based) commercially available from Infineum International Ltd, Abingdon, UK
9. Polyol ester commercially available from Croda
International PLC under the tradename Priolube 3970.
10. Naphthenic base oil commercially available from China National Petroleum Corporation under the tradename KN 4006.
Discussion
As can be seen from the results in Table 2, as a general trend, the lubricating compositions according to
the present invention show improved oxidation stability and deposit control properties, in comparison to the lubricating compositions falling outside the scope of the present invention.
The formulation examples in Tables 3-7 below are examples of Group Ill-based lubricating oil compositions. Such compositions could be reformulated to contain a solvency booster, antioxidant and detergent as per examples 5, 6, 11, 12, 17, 18, 24, 25, 31, 32, 38, 39, 46, 47, 53, 54, 61 and 62 above, and would be expected to show similar performance benefits in terms of oxidation stability and deposit control.
Table 3
Table 3 gives details of a typical HDDEO lubricant formulation .
Wt%
Medium TBN salicylate 0.1 - 4
High TBN salicylate 0.1 - 3
Low TBN salicylate 0.1 - 6
High mw, high N
0.1 - 12
dispersant
ZDTP 0.05 - 2
Phenolic antioxidant 0.1 - 3
Aminic antioxidant 0.01 ~2
Corrosion inhibitor 0.1 - 2
Dispersant PMA 0.01 - 4
Viscosity Modifier 0.1 - 10
GTL 4 and/or GTL 8 Balance
PAO 4 0.0 - 10
Table 4
Table 4 gives details of a typical PCMO formu
Wt%
Medium TBN salicylate 0.1 - 4
High TBN salicylate 0.1 - 3
Low TBN salicylate 0.1 - 6
High mw, high N
0.1 - 12
dispersant
ZDTP 0.05 - 2
Phenolic antioxidant 0.1 - 3
Aminic antioxidant 0.01 -2
Corrosion inhibitor 0.1 - 2
Dispersant PMA 0.01 - 4
Viscosity Modifier 0.1 - 10
Organic friction
0-2
modifier
Molybdenum containing
0-2
Friction Modifier
Borated succinimide
0-4
dispersant
Low TBN phenate 0-3
High BN sulphonate 0-3
Non-dispersant PMA pour
0.1-2.0
point depressant
GTL 4 and/or GTL 8 Balance
PAO 4 0.0 - 10
Table 5
Table 5 gives details of a typical grease formulation.
Component Wt%
GTL 4 and/or GTL 8 Balance
Lithium hydroxide thickener 1.0-4.0
component
Hydrogenated castor oil fatty 7.1-28.0
acid thickener component
Castor Oil Lubricity Enhancer 0.5-3.0
Glycerol Lubricity Enhancer 0.5-3.0
Phenolic antioxidant 0.1-2.0
Aminic antioxidant 0.1-2.0
Zinc naphthenate corrosion 0.5-5.0
inhibitor
Overbased calcium salicylate 0.2-7.0
Sulphurised ester 1.0-13
Zinc oxide 0.2-1.0
Total 100
Table 6
Component Wt%
GTL 4 and/or GTL 8 Balance
Lithium hydroxide thickener 1.0-4.0
component
Hydrogenated castor oil fatty 3.0-18.0
acid thickener component
Boric Acid thickener 0.4-3.0
component
Castor Oil Lubricity Enhancer 0.5-3.0
Glycerol Lubricity Enhancer 0.5-3.0
Phenolic antioxidant 0.1-2.0
Aminic antioxidant 0.1-2.0
Zinc naphthenate corrosion 0.5-5.0
inhibitor
Overbased calcium salicylate 0.2-7.0
Sulphurised ester 1.0-13
Zinc oxide 0.4
Total 100
Table 7
Component Wt%
GTL 4 and/or GTL 8 Balance
MDI (methylene 2.0-8.0
diisocyanate) (4,4'~
diphenylmethane diisocyanate)
thickener component
Octylamine thickener 2.3-9.0
component
Dodecylamine thickener 0.8-3.5
component
Aminic antioxidant 0.1-2.0
Zinc naphthenate corrosion 0.5-5.0
inhibitor
Methylenebis 0.2-3.0
(dibutyldithiocarbamate)
ZDTP 0.05-5.0
N-alkylated tolutriazole 0-0.2
Total 100
It will be appreciated by those skilled in the art that the thickener components in the grease formulations in Tables 5, 6 and 7 need to be used in the correct stoichimetric ratios.
Claims
1. A lubricating oil composition comprising:
(a) base oil selected from Group III base oils, Group IV polyalphaolefins, or a combination thereof;
(b) 30 wt% or less solvency booster;
(c) antioxidant selected from aminic antioxidants, phenolic antioxidants, and mixtures thereof;
(d) detergent comprising (i) an alkaline earth metal salicylate having a TBN (total base number equivalent, as determined by ASTM D2896) in the range of from 50 to 150; (ii) an alkaline earth metal salicylate having a TBN in the range of from 150 to 250; and (iii) an alkaline earth metal salicylate having a TBN in the range of from 250 to 400,
2. A lubricating oil composition according to Claim 1 wherein the Group III base oil is a Fischer-Tropsch derived base oil.
3. A lubricating oil composition according to Claim 1 or 2 wherein the solvency booster is selected from alkylated naphthalenes, alkyl benzenes, naphthenics, esters, and mixtures thereof.
4. A lubricating oil composition according to any of Claims 1 to 3 wherein the solvency booster is present at a level of from 1 wt% to 20 wt%, by weight of the
lubricant composition.
5. A lubricating oil composition according to any of
Claims 1 to 4, wherein the antioxidant is an aminic antioxidant, preferably a diphenylamine .
6. A lubricating oil composition according to Claim 1 to 5 wherein the alkaline earth metal salicylates are calcium salicylates.
7. A lubricating oil composition according to any of Claims 1 to 6 wherein the lubricating oil composition has a kinematic viscosity at 100°C of from 1 mm2/s to 35 mm2/s .
8. A lubricating oil composition according to any of Claims 1 to 8 wherein the Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C of from 1 mm2/s to 35 mm2/s .
9. A lubricating oil composition according to any of Claims 1 to 9 wherein the base oil contains more than 50 wt.%, preferably more than 60 wt.%, more preferably more than 70 wt.%, even more preferably more than 80 wt.%, most preferably more than 90 wt.% Fischer-Tropsch derived base oil.
10. Use of a lubricating oil composition according to any of Claims 1 to 10 for providing improved anti- oxidation properties, in particular as determined by ASTM D6186-08.
11. Use of a lubricating oil composition according to any of Claims 1 to 10 for providing improved deposit reduction properties, in particular as determined according to ASTM D7097-09 or JPI-5S-55-99.
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CN116083144A (en) * | 2022-12-26 | 2023-05-09 | 上海森帝润滑技术有限公司 | Screw type air compressor lubricating oil composition |
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