EP3158034A1 - Lubricating composition - Google Patents

Lubricating composition

Info

Publication number
EP3158034A1
EP3158034A1 EP15729492.7A EP15729492A EP3158034A1 EP 3158034 A1 EP3158034 A1 EP 3158034A1 EP 15729492 A EP15729492 A EP 15729492A EP 3158034 A1 EP3158034 A1 EP 3158034A1
Authority
EP
European Patent Office
Prior art keywords
lubricating composition
composition according
molybdenum
hydrophobic
polymeric
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP15729492.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Mark Clift Southby
Hong Gao
Cheng Chen
Coleen Anne CHIN
Brian Lee Papke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP3158034A1 publication Critical patent/EP3158034A1/en
Withdrawn legal-status Critical Current

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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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M169/04—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
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
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    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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    • C10M2209/111—Complex polyesters having dicarboxylic acid centres
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    • C10M2209/112—Complex polyesters having dihydric acid centres
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    • C10N2030/54—Fuel economy
    • 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
    • C10N2030/68—Shear stability
    • 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
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to a lubricating oil composition, in particular to a lubricating oil
  • composition which is suitable for lubricating internal combustion engines and which has improved friction and wear reduction and improved fuel economy.
  • Optimising lubricants through the use of high performance base stocks and novel additives represents a flexible solution to a growing challenge.
  • Friction-reducing additives (which are also known as friction modifiers) are important lubricant components in reducing fuel consumption and various such additives are already known in the art .
  • Friction modifiers can be conveniently divided into two categories, that is to say, metal-containing friction modifiers and ashless (organic) friction modifiers.
  • Organo-molybdenum compounds are amongst the most common metal-containing friction modifiers. Typical organo-molybdenum compounds include molybdenum
  • MoDTC molybdenum dithiophosphates
  • MoDTP molybdenum dithiophosphates
  • molybdenum amines molybdenum alcoholates
  • molybdenum alcohol-amides molybdenum alcohol-amides .
  • WO-A-98/26030, WO-A-99/31113, WO-A-99/47629 and WO-A-99/66013 describe tri-nuclear molybdenum compounds for use in lubricating oil
  • Ashless (organic) friction modifiers which have been used in the past typically comprise esters of fatty acids and polyhydric alcohols, fatty acid amides, amines derived from fatty acids and organic dithiocarbamate or dithiophosphate compounds .
  • molybdenum friction modifiers typically outperform ashless friction modifiers in the boundary regime.
  • organo-molybdenum compounds are useful for providing high levels of friction modification, there are also known limitations with these compounds.
  • molybdenum-based friction modifiers can be used.
  • WO2011/107739 discloses an automotive engine oil and/or fuel comprising a base stock and an organic polymeric friction reducing additive.
  • a lubricating oil composition comprising a combination of organo-molybdenum compound and an organic polymeric friction reducing additive has improved friction and wear reduction and improved fuel economy, while requiring reduced levels of organo-molybdenum compounds .
  • the present invention provides a lubricating composition for use in the crankcase of an engine comprising (i) a base oil; (ii) one or more organo-molybdenum compounds at a level sufficient to provide from 100 to 1000 ppmw of molybdenum; and (iii) from 0.2 wt% to 5 wt%, by weight of the lubricating composition, of one or more organic polymeric friction reducing additives, wherein the one or more organic polymeric friction reducing additives has a molecular weight ranging from 1000 to 30000 Daltons and is the reaction product of :
  • hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins
  • hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides ;
  • Figure 1 shows a plot of friction coefficient measurements in the boundary and mixed regimes as a function of speed for the compositions set out in Table 2.
  • Figure 2 shows a plot of friction coefficient measurements in the boundary and mixed regimes as a function of speed for the compositions set out in Table 4.
  • compositions of the present invention is one or more organo-molybdenum compounds at a level sufficient to provide from 100 to 1000 ppmw of molybdenum, preferably at a level sufficient to provide from 100 to 300 ppmw of molybdenum .
  • the organo-molybdenum compound for use herein is preferably selected from molybdenum dithiocarbamates
  • MoDTC molybdenum dithiophosphates
  • MoDTP molybdenum dithiophosphates
  • molybdenum amines molybdenum alcoholates
  • molybdenum alcohol- amides molybdenum alcohol- amides
  • a preferred organo- molybdenum compound for use herein is molybdenum
  • the organo-molybdenum compound contains tri- nuclear molybdenum (referred to herein as "moly trimer”) .
  • Another essential component of the lubricating compositions of the present invention is one or more organic polymeric friction reducing additives wherein the one or more organic polymeric friction reducing additives has a molecular weight ranging from 1000 to 30000 Daltons and is the reaction product of:
  • hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins
  • hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides ;
  • the hydrophobic polymeric sub unit preferably comprises a hydrophobic polymer which is a polyolefin or a polyalphaolefin, more preferably a polyolefin.
  • the polyolefin is preferably derived from a polymer of a monolefin having from 2 to 6 carbon atoms such as ethylene, propylene, butene and isobutene, more
  • the said polymer preferably isobutene, the said polymer containing a chain of from 15 to 500, preferably 50 to 200 carbon atoms.
  • the hydrophilic polymeric sub unit comprises a hydrophilic polymer selected from a polyether, a
  • polyester examples include polyethylene terephthalate, polylactide and
  • polyether examples include
  • the hydrophilic polymeric sub unit comprises a hydrophilic polymer which is a polymer of a water soluble alkylene glycol.
  • a preferred hydrophilic polymeric sub unit comprises a hydrophilic polymer which is a polyethylene glycol (PEG) , preferably PEG having a molecular weight of 300 to 5000 Daltons, more preferably
  • a mixed poly (ethylene-propylene glycol) or mixed poly (ethylene-butylene glycol) may be used provided they achieve the desired water solubility criteria.
  • Exemplary hydrophilic polymer sub units for use in the present invention include PEG 400, PEG 600 and PEG 1000.
  • hydrophilic polymeric sub units may comprise hydrophilic polymers which are polyethers and polyamides derived from diols and diamines containing acidic groups, e.g. carboxylic acid groups, sulphonyl groups (e.g. sulphonyl styrenic groups), amine groups (e.g. tetraethylene pentamine (TEPA) or polyethylene imine (PEI)), or hydroxyl groups (e.g. sugar based mono- or co-polymers) .
  • hydrophilic polymers which are polyethers and polyamides derived from diols and diamines containing acidic groups, e.g. carboxylic acid groups, sulphonyl groups (e.g. sulphonyl styrenic groups), amine groups (e.g. tetraethylene pentamine (TEPA) or polyethylene imine (PEI)), or hydroxyl groups (e.g. sugar based mono- or co-polymers)
  • the hydrophilic polymeric sub unit may be either linear or branched.
  • hydrophobic and hydrophilic polymeric sub units may link together to form block copolymer units.
  • Either or both of the hydrophobic and hydrophilic polymeric sub units may comprise functional groups which enable them to link with the other sub unit.
  • the hydrophobic polymeric sub unit may be derivatised so that it has a diacid/anhydride grouping by reaction with an unsaturated diacid or anhydride, for examples maleic anhydride.
  • the diacid/anhydride can react by esterification with hydroxyl terminated hydrophilic polymeric sub units, for example a polyalkylene glycol.
  • the hydrophobic polymeric sub unit may be derivatised by an epoxidation reaction with a peracid, for example
  • the epoxide can then react with hydroxyl and/or acid terminated hydrophilic
  • a hydrophilic polymeric sub unit which has a hydroxyl group may be derivatised by esterification with unsaturated mono carboxylic acids, for example vinyl acids, specifically acrylic or methacrylic acid. This derivatised
  • hydrophilic polymeric sub unit can then react with a polyolefin hydrophobic polymeric sub unit by free radical copolymerisation .
  • a particularly preferred hydrophobic polymeric sub unit comprises polyisobutylene polymer which has been subjected to maleinisation to form polyisobutylene succinic anhydride (PIBSA) having a molecular weight in the range of 300 to 5000 Daltons, preferably 500 to 1500 Daltons, especially 800 to 1200 Daltons.
  • PIBSA polyisobutylene succinic anhydride
  • Polyisobutylene succinic anhydrides are commercially available compounds made by an addition reaction between poly (isobutene ) having a terminal unsaturated group and maleic anhydride .
  • Such block copolymer units may be directly linked to each other and/or they may be linked together by the at least one backbone moiety. Preferably they are linked together by the at least one backbone moiety.
  • the choice of backbone moiety capable of linking together the block copolymer units is governed by whether the linking of units is between two hydrophobic polymeric sub units, between two hydrophilic polymeric sub units or between a hydrophobic polymeric sub unit and a
  • hydrophilic polymeric sub unit Generally polyols and polycarboxylic acids form suitable backbone moieties.
  • the polyol may be a diol, triol, tetrol, and/or related dimers or trimers or chain extended polymers of such compounds.
  • suitable polyols include
  • the polyol is a glycerol.
  • the at least one backbone moiety is derived from a polycarboxylic acid, for example a di- or tricarboxylic acid. Dicarboxylic acids are preferred polycarboxylic acids, though branched chain dicarboxylic acids may also be suitable.
  • straight chained dicarboxylic acids having a chain length of between 2 and 10 carbon atoms, for example oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic acid.
  • Unsaturated dicarboxylic acids such as maleic acid may also be suitable.
  • polycarboxylic acid backbone moiety to link units is adipic acid.
  • Alternative linking backbone moieties are low molecular weight alkenyl succinic anhydrides (ASA) such as Ci eASA .
  • any of the organic polymeric friction reducing additives different or same backbone moieties can be used to link together such block copolymer units.
  • the number of block copolymer units in the organic polymeric friction reducing additive typically ranges from 1 to 20 units, preferably from 1 to 15, more preferably from 1 to 10 and especially 1 to 7 units.
  • Suitable fatty acids include C12 -C22 linear saturated, branched saturated, linear unsaturated and branched unsaturated acids, including, but not limited to lauric acid, erucic acid, isostearic acid, palmitic acid, oleic acid, and linoleic acid, preferably palmitic acid, oleic acid and linoleic acid.
  • TOFA a derivative of tall oil, which is primarily oleic acid.
  • the organic polymeric friction reducing additive used herein has a molecular weight of from 1000 to 30000 Daltons, preferably from 1500 to 25000, more preferably from 2000 to 20000 Daltons.
  • a composition comprising the organic polymeric friction reducing additive will comprise a range of polymer chains of different lengths such that there will be a range of molecular masses in a particular composition. In such a case it is desirable that a substantial portion of the organic polymeric friction reducing additive molecules are within the above mentioned size ranges.
  • the organic polymeric friction reducing additive herein has a desired acid value of less than 20,
  • hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins
  • hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides;
  • the preferred molecular weight range is 1000 to 3000 Daltons and the desired acid value is less than 15.
  • hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins
  • hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides;
  • the preferred molecular weight range is 3000 to 25000, more preferably 5000 to 20000 Daltons .
  • the desired acid value is preferably less than 10, more preferably less than 7.
  • the organic polymeric friction reducing additive is the reaction product of: a) a hydrophobic polymeric sub unit which comprises a hydrophobic polymer selected from polyolefins,
  • hydrophilic polymeric sub unit which comprises a hydrophilic polymer selected from polyethers, polyesters, polyamides ;
  • the preferred molecular weight range is 2000 to 10000, more preferably 2000 to 5000 Daltons.
  • the desired acid value is preferably less than 15, more preferably less than 10.
  • the ingredients of the reactions a) , b) and c) when present and d) when present may be mixed in a single step process or they may be mixed together in a multi step- process .
  • the organic polymeric friction reducing additive described hereinabove is commercially available from Croda under the trade names Perfad 3050 and Perfad 3006.
  • the organic polymeric friction reducing additive is present at a level of from 0.2 wt% to 5.0 wt%, preferably at a level of from 0.3 wt% to 3.0 wt%, more preferably 0.2 wt% to 1.5 wt%, by weight of the lubricating
  • the total amount of base oil incorporated in the lubricating oil composition of the present invention is preferably present in an amount in the range of from 60 to 92 wt . %, more preferably in an amount in the range of from 75 to 90 wt . % and most preferably in an amount in the range of from 75 to 88 wt . %, with respect to the total weight of the lubricating oil composition.
  • base oil used in the present invention there are no particular limitations regarding the base oil used in the present invention, and various conventional known mineral oils and synthetic oils may be conveniently used.
  • the base oil 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 oils of the paraffinic, naphthenic, or mixed
  • paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
  • Naphthenic base oils have low viscosity index (VI) (generally 40-80) and a low pour point.
  • Such base oils are produced from feed stocks rich in naphthenes and low in wax content and are used mainly for lubricants in which colour and colour stability are important, and VI and oxidation stability are of secondary importance.
  • Paraffinic base oils have higher VI (generally >95) and a high pour point. Said base oils are produced from feed stocks rich in paraffins, and are used for
  • Fischer-Tropsch derived base oils may be
  • the base oil in the lubricating oil composition of the present invention for example, the
  • Fischer-Tropsch derived base oils disclosed in EP-A- 776959, EP-A-668342, WO-A-97/21788, WO-00/15736, WO- 00/14188, WO-00/14187, WO-00/14183, WO-00/14179, WO- 00/08115, WO-99/41332, EP-1029029, WO-01/18156 and WO- 01/57166.
  • Synthetic processes enable molecules to be built from simpler substances or to have their structures modified to give the precise properties required.
  • dibasic acids esters dibasic acids esters
  • polyol esters polyol esters
  • dewaxed waxy raffinate dewaxed waxy raffinate
  • hydrocarbon base oils sold by the Royal Dutch/Shell Group of Companies under the designation "XHVI” (trade mark) may be conveniently used.
  • the base oil comprises mineral oils and/or synthetic oils which contain more than 80% wt of saturates, preferably more than 90 % wt . , as measured according to ASTM D2007.
  • the base oil contains less than 1.0 wt . %, preferably less than 0.1 wt . % of sulphur, calculated as elemental sulphur and measured according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.
  • the viscosity index of the base oil is more than 80, more preferably more than 120, as measured according to ASTM D2270.
  • the lubricating oil composition has a kinematic viscosity in the range of from 2 to 80 mm 2 /s at
  • the total amount of phosphorus in the lubricating oil composition of the present invention is preferably in the range of from 0.04 to 0.12 wt . %, more preferably in the range of from 0.04 to 0.09 wt . % and most preferably in the range of from 0.045 to 0.08 wt . %, based on total weight of the lubricating oil composition.
  • the lubricating oil composition of the present invention preferably has a sulphated ash content of not greater than 2.0 wt . %, more preferably not greater than 1.0 wt . % and most preferably not greater than 0.8 wt . %, based on the total weight of the lubricating oil
  • the lubricating oil composition of the present invention preferably has a sulphur content of not greater than 1.2 wt . %, more preferably not greater than 0.8 wt . % and most preferably not greater than 0.2 wt . %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition of the present invention may further comprise additional additives such as anti-oxidants , anti-wear additives, detergents, dispersants, additional friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal
  • additional additives such as anti-oxidants , anti-wear additives, detergents, dispersants, additional friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal
  • a particularly preferred additional additive for use herein in combination with the organo-molybdenum compound and the organic polymeric friction reducing additive described hereinabove is a hydroxy alkyl amine friction modifier, such as that commercially available from Adeka under the trade name Adeka FM926.
  • the hydroxy alkyl amine friction modifier is present at a level of from 0.2 wt% to 3.0 wt%, more preferably at a level of from 0.3 wt% to 1.0 wt%, by weight of the lubricating composition.
  • Antioxidants that may be conveniently used include those selected from the group of aminic antioxidants and/or phenolic antioxidants.
  • said antioxidants are present in an amount in the range of from 0.1 to 5.0 wt . %, more preferably in an amount in the range of from 0.3 to 3.0 wt . %, and most preferably in an amount 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--naphthylamines and alkylated a-naphthylamines .
  • Preferred aminic antioxidants include
  • dialkyldiphenylamines such as p, p ' -dioctyl-diphenylamine, p, p ' -di-OC-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-1- naphthylamine and n-t-dodecylphenyl-l-naphthylamine, 1- naphthylamine, arylnap
  • phenylenediamines such as N, ' -diisopropyl-p- phenylenediamine and N, ' -diphenyl-p-phenylenediamine, and phenothiazines such as phenothiazine and 3,7- dioctylphenothiazine .
  • Preferred aminic antioxidants include those available under the following trade designations: “Sonoflex OD-3” (ex. Seiko Kagaku Co.), “Irganox L-57” (ex. Ciba).
  • phenolic antioxidants which may be conveniently used include C 7 -C 9 branched alkyl esters of 3, 5-bis (1, 1-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) propionate, 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-OC-dimethylamino-p-cresol, 2,2' -methylene- bis (4-alkyl-6-t-butyl
  • 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.),
  • 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 oil composition may comprise a single zinc dithiophosphate or a combination of two or more zinc dithiophosphates as anti-wear additives, the or each zinc dithiophosphate being selected from zinc dialkyl-, diaryl- or alkylaryl- dithiophosphates .
  • Zinc dithiophosphate is a well known additive in the art and may be conveniently represented by general formula II;
  • R z to R may be the same or different and are each a primary alkyl group containing from 1 to 20 carbon atoms preferably from 3 to 12 carbon atoms, a secondary alkyl group containing from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, an aryl group or an aryl group substituted with an alkyl group, said alkyl substituent containing from 1 to 20 carbon atoms
  • Zinc dithiophosphate compounds in which to are all different from each other can be used alone or in admixture with zinc dithiophosphate compounds in which R 2 to R 5 are all the same.
  • the or each zinc dithiophosphate used in the present invention is a zinc dialkyl dithiophosphate.
  • Examples of suitable zinc dithiophosphates which are commercially available include those available ex.
  • dithiophosphates such as those available ex. Lubrizol Corporation under the trade designations “Lz 1370” and “Lz 1373” and that available ex. Chevron Oronite under the trade designation "OLOA 260”.
  • the lubricating oil composition according to the present invention may generally comprise in the range of from 0.4 to 1.2 wt . % of zinc dithiophosphate, based on total weight of the lubricating oil composition.
  • composition of the present invention may be conveniently used in the composition of the present invention .
  • lubricating oil of the present invention include one or more salicylate and/or phenate and/or sulphonate
  • metal organic and inorganic base salts which are used as detergents can contribute to the sulphated ash content of a lubricating oil composition, in a preferred embodiment of the present invention, the amounts of such additives are minimised.
  • salicylate detergents can be used.
  • the lubricating oil composition of the present invention may comprise one or more salicylate detergents.
  • said detergents are preferably used in amounts in the range of 0.05 to 20.0 wt . %, more
  • lubricating oil composition preferably from 1.0 to 10.0 wt . % and most preferably in the range of from 2.0 to 5.0 wt . %, based on the total weight of the lubricating oil composition.
  • said detergents independently, have a TBN (total base number) value in the range of from 10 to 500 mg.KOH/g, more preferably in the range of from 30 to 350 mg.KOH/g and most preferably in the range of from 50 to 300 mg.KOH/g, as measured by ISO 3771.
  • TBN total base number
  • the lubricating oil compositions of the present invention may additionally contain an ash-free dispersant which is preferably admixed in an amount in the range of from 5 to 15 wt . %, based on the total weight of the lubricating oil composition.
  • ash-free dispersants examples include the polyalkenyl succinimides and polyalkenyl succininic acid esters disclosed in Japanese Patent Nos .
  • Preferred dispersants include borated succinimides.
  • viscosity index improvers which may be conveniently used in the lubricating oil composition of the present invention include the styrene-butadiene copolymers, styrene-isoprene stellate copolymers and the polymethacrylate copolymer and ethylene-propylene copolymers .
  • Such viscosity index improvers may be conveniently employed in an amount in the range of from 1 to 20 wt . %, based on the total weight of the lubricating oil composition.
  • Polymethacrylates may be conveniently employed in the lubricating oil compositions of the present invention as effective pour point depressants.
  • polycyclohexane and polyacrylates may be conveniently used in the lubricating oil composition of the present
  • seal fix or seal compatibility agents include, for example, commercially available aromatic esters.
  • inventions may be conveniently prepared using conventional formulation techniques by admixing base oil with the organo-molybdenum compound and polymeric friction reducing additive together with and one or more other optional additives at a temperature of 60°C.
  • a method of lubricating an internal combustion engine comprising applying a lubricating oil composition as hereinbefore described thereto.
  • the present invention further provides the use of a lubricating composition as described herein for reducing friction .
  • the present invention further provides the use of a lubricating composition as described herein for reducing wear.
  • the present invention further provides the use of a lubricating composition as described herein for improving fuel economy.
  • a lubricating composition was formulated using conventional lubricant blending procedures ("Baseline Oil
  • a Fischer-Tropsch derived base oil having a
  • kinematic viscosity at 100°C (ASTM D445) of approximately 4 cSt which may be conveniently prepared by the process described in WO 02/070631.
  • polyisobutylene succinimide dispersant zinc alkyl dithiophosphate, overbased calcium alkyl salicylate detergent, borated dispersant and diphenylamine
  • Baseline Oil A had a kVlOO (as measured according to ASTM D445) of 8.02 mm 2 /s, a kV40 (as measured according to ASTM D445) of 35.18 mm 2 /s, a CCS at -35°C (as measured according to ASTM D5293) of 4330 mPa.s, and an HTHS (as measured according to ASTM D4741) of 2.74 mPa.s.
  • Baseline Oil A were an organo-molybdenum compound
  • MoDTC molybdenum dithiocarbamate
  • Moly Trimer trinuclear molybdenum, referred to in Table 2 and Figure 1 as "Moly Trimer”
  • Perfad 3006 commercially available from Croda
  • glycerol monooleate a well known and generally available friction modifier .
  • Friction measurements were carried out on the compositions set out in Table 2 using a Mini-Traction Machine (MTM) manufactured by PCS Instruments.
  • MTM Mini-Traction Machine
  • the MTM Test was described by R.I. Taylor, E.
  • the ball specimen was a polished steel ball bearing, 19.05 mm in diameter.
  • the disc specimen was secured concentrically on a motor driven shaft.
  • the disc specimen was secured concentrically on another motor driven shaft.
  • the ball was loaded against the disc to create a point contact area with minimum spin and skew components. At the point of contact, a slide to roll ratio of 100% was maintained by adjusting the surface speed of the ball and disc.
  • Friction coefficients of the relevant Test Oils were measured and the results are detailed in Table 2 below.
  • the boundary friction coefficient is the averaged value at the low speeds from 0.05 m/s to 0.05 m/s
  • the mixed friction coefficient is the averaged value at the higher speeds from 1.0 m/s to 2.6 m/s.
  • Figure 1 shows a plot of friction coefficient measurements in the boundary and mixed regimes as a function of speed for the compositions set out in Table 2.
  • a further lubricating composition was formulated using conventional lubricant blending procedures
  • Baseline Oil B having the composition set out in Table 3 below.
  • a Fischer-Tropsch derived base oil having a
  • kinematic viscosity at 100°C (ASTM D445) of approximately 4 cSt which may be conveniently prepared by the process described in WO 02/070631.
  • succinimide dispersant zinc alkyl dithiophosphate, overbased calcium alkyl phenate and sulphonate
  • Baseline Oil B had a kVlOO (as measured according to ASTM D445) of 8.93 mm 2 /s, a kV40 (as measured according to ASTM D445) of 45.20 mm 2 /s, a VI of 183, an HTHS at 150°C (as measured according to ASTM D4741) of 2.52 CPs, an HTHS at 100°C (as measured according to ASTM D4741) of 5.55 CPs .
  • Friction coefficients of the relevant Test Oils were measured using the MTM test method described above and the results are detailed in Table 4 below.
  • Table 4 the boundary friction
  • the mixed friction coefficient is the averaged value at the low speeds from 0.05 m/s to 0.05 m/s, and the mixed friction coefficient is the averaged value at the higher speeds from 1.0 m/s to 2.6 m/s .
  • Moly Trimer Figure 2 shows a plot of friction coefficient measurements in the boundary and mixed regimes as a function of speed for the compositions set out in
  • Lubrication regimes fall into four main categories: (1) Hydrodynamic, where the surfaces are completely separated by a fluid film, (2) Elastohydrodynamic, where the surfaces are separated by a very thin fluid film (3) Mixed, where the surfaces are partially separated with some asperity contact and (4) Boundary, where the surfaces are mostly in contact, even though a fluid film is present.
  • Hydrodynamic where the surfaces are completely separated by a fluid film
  • Elastohydrodynamic where the surfaces are separated by a very thin fluid film
  • Mixed where the surfaces are partially separated with some asperity contact
  • Boundary where the surfaces are mostly in contact, even though a fluid film is present.
  • the mixed and boundary regimes rely on chemical antiwear additives and/or friction modifiers, and the like, to reduce wear and friction.
  • Molybdenum containing friction modifiers are generally expected to perform well in reducing boundary friction and organic friction modifiers are thought to be more effective under mixed conditions.
  • hydroxy alkyl amine friction modifier (Adeka FM926) is more effective in the mixed regime, but a little less effective at reducing boundary friction.

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EP15729492.7A 2014-06-19 2015-06-17 Lubricating composition Withdrawn EP3158034A1 (en)

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JP2017518426A (ja) 2017-07-06
US20170275555A1 (en) 2017-09-28
RU2017101549A (ru) 2018-07-19
RU2017101549A3 (ja) 2019-01-16
RU2692794C2 (ru) 2019-06-27
CN106414686A (zh) 2017-02-15

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