[go: up one dir, main page]

WO2018158099A1 - Sels surbasés d'oligomères de phénol alkylés utilisés en tant qu'additifs de lubrifiants - Google Patents

Sels surbasés d'oligomères de phénol alkylés utilisés en tant qu'additifs de lubrifiants Download PDF

Info

Publication number
WO2018158099A1
WO2018158099A1 PCT/EP2018/054012 EP2018054012W WO2018158099A1 WO 2018158099 A1 WO2018158099 A1 WO 2018158099A1 EP 2018054012 W EP2018054012 W EP 2018054012W WO 2018158099 A1 WO2018158099 A1 WO 2018158099A1
Authority
WO
WIPO (PCT)
Prior art keywords
salt
lubricating composition
group
moiety
acyclic
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.)
Ceased
Application number
PCT/EP2018/054012
Other languages
English (en)
Inventor
Kevin Richard West
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.)
Castrol Ltd
Original Assignee
Castrol Ltd
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 Castrol Ltd filed Critical Castrol Ltd
Publication of WO2018158099A1 publication Critical patent/WO2018158099A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/235—Metal derivatives of a hydroxy group bound to a six-membered aromatic ring
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/52—Base number [TBN]
    • 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

  • This invention relates to salts of compounds which comprise an aromatic group linked to a hydrocarbon moiety, as well as compositions comprising said salts.
  • the salts may be used as detergents in a lubricating composition, in particular a lubricating composition for an internal combustion engine.
  • Internal combustion engines are typically used to provide power from fuel, e.g. in automotive applications, aviation applications and marine applications.
  • Deposits include for example high-temperature varnish and lacquer deposits.
  • detergents are used in order to counter the deposition of oxidation and thermal degradation products of a lubricant on engine surfaces. Moreover, detergents contribute to acid neutralisation which is thought to be beneficial in preventing the corrosion of engine surfaces.
  • salts of aromatic organic acids include for example, salts of mono- or poly-nuclear aromatic compounds which
  • salts of aromatic organic acids include phenates, sulphonates, salicylates, salixarates, carboxylates and saligenins.
  • TPP tetrapropenyl phenol
  • Tetrapropenyl phenol is a mono-cyclic aromatic compound comprising an aryl ring substituted with a hydroxyl group and a hydrocarbon moiety.
  • the hydrocarbon moiety is typically a C 12 moiety which contains a continuous chain length of eight carbon atoms with four methyl branches.
  • the hydrocarbon moiety may be in the ortho-, meta- or para- position on the aromatic ring relative to the hydroxy moiety.
  • the hydrocarbon moiety in tetrapropenyl phenol is typically derived from an olefin mixture comprising propylene oligomers. The use of propylene oligomers as the source of hydrocarbon moieties is believed to result in hydrocarbon moieties on the aryl rings that have carbon chain lengths that are multiples of three, including C 12 hydrocarbyl moieties.
  • US 7,943,796 relates to an overbased salt of an oligomerized alkylhydroxyaromatic compound.
  • the alkyl group of the alkylhydroxyaromatic compound is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 °C and a final boiling point of no more than about 325 °C, as measured by ASTM D86. It is stated therein that such compounds are substantially free of endocrine disruptive chemicals when the effects were quantified in an intact juvenile female rat.
  • the present invention provides a salt of a compound comprising an aromatic group linked to an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units.
  • the present invention provides a lubricating composition, preferably for an internal combustion engine, which comprises a salt of the first aspect.
  • the present invention provides use of a salt of the first aspect as a detergent, a deposit-reducing agent, an oxidation performance improver, and/or a corrosion inhibitor in a lubricating composition, and preferably a lubricating composition for an internal combustion engine.
  • the present invention provides a method for improving the detergency, deposit reduction, oxidation performance, and/or corrosion inhibition characteristics of a lubricating composition, wherein the method comprises adding a salt of the first aspect to the lubricating composition.
  • the present invention relates to salts of compounds which comprise an aromatic group linked to an acyclic isoprenoid moiety.
  • the aromatic group comprises at least one aryl ring.
  • the aromatic group may be a mono- or poly-nuclear aromatic group.
  • the aromatic group preferably comprises a hydrocarbon aryl ring, e.g. containing from 6 to 14 carbon atoms. Suitable aromatic groups comprise a benzene ring, toluene ring or naphthalene ring.
  • the aromatic group preferably comprises an aryl ring substituted with an acidic group.
  • Suitable acidic groups include a hydroxy group, a carboxy group or a sulfonic acid group.
  • Preferred aryl rings are substituted with a hydroxy group. Though less preferred, it will be appreciated that the aryl ring may be substituted with more than one acidic group, e.g. it may be substituted with a hydroxy and a carboxy group.
  • the aromatic group is linked to an acyclic isoprenoid moiety.
  • the aryl ring in the aromatic group is linked directly to the acyclic isoprenoid moiety (i.e. the isoprenoid moiety is a substituent of the aryl ring), though a linking group such as a Ci_io alkyl group may link the aromatic group and the acyclic isoprenoid moiety.
  • Alternative linking groups known to those skilled in the art for example linking groups such as ethers, esters, amides, thio-ethers, ketones, amines, which may in each case further comprise a hydrocarbon portion, such as a Ci_io alkyl group.
  • Isoprenoid moieties are oligomers of isoprene, but with a structure that may differ from the strict addition product of isoprene units by loss of a methyl group; by hydrogenation; and by substitution with one or more functional groups, e.g. functional groups selected from alkyl groups, halogens and hydroxy groups.
  • the acyclic isoprenoid moiety is an oligomer of isoprene, but with a structure that may differ from the addition product of isoprene units by hydrogenation; and substitution with one or more alkyl groups, e.g. no more than three C 1 -3 alkyl groups.
  • Preferred acyclic isoprenoid moieties are unsubstituted addition products of isoprene (i.e. terpenes), or the hydrogenation product thereof. It will be appreciated that, where the acyclic isoprenoid moiety is an unsubstituted addition product of isoprene, then one of the olefin bonds in the addition product will be converted to a single bond when the acyclic isoprenoid compound is linked to the aromatic group.
  • Hydrogenation products may be full or partial hydrogenation products, though full hydrogenation products are preferred (i.e. saturated compounds).
  • the acyclic isoprenyl moiety is unsaturated, e.g. with a single unsaturated bond present for each isoprene unit of the isoprenyl moiety.
  • the acyclic isoprenyl moiety is saturated. Since saturated isoprenoid moieties are less reactive in the lubricant environment, they are generally preferred.
  • the acyclic isoprenoid moiety is derived from 3 to 6 isoprenyl units.
  • the isoprenyl units may be connected for example head to tail or from head to head, in regular or random order.
  • Acyclic isoprenoid moieties may be derived from sesquiterpene groups (containing three isoprenyl units and fifteen carbon atoms), diterpene groups (containing four isoprenyl units and twenty carbon atoms), sesterterpene groups (containing five isoprenyl units and twenty-five carbon atoms), triterpene groups (containing six isoprenyl units and thirty carbon atoms).
  • the acyclic isoprenoid moiety is a sesquiterpene group, diterpene group, sesterterpene group, triterpene groups, or a hydrogenated derivative thereof.
  • the isoprenoid moiety is derived from 3 to 5 isoprenyl units, more preferably from 3 or 4 isoprenyl, and most preferably from 3 isoprenyl units.
  • At least 50 , preferably at least 70 , and more preferably at least 90 % of the acyclic isoprenoid moieties in the salt are derived from 3 isoprenyl units. These percentages may be determined on a molar or number basis.
  • the isoprenoid moiety is a farnesene group, or a hydrogenated derivative thereof.
  • Farnesene is an isoprenoid compound containing three isoprenyl units, a- farnesene and ⁇ -farnesene differ by the location of one double bond.
  • a-farnesene is 3,7,11-trimethyl- l, 3,6, 10-dodecatetraene:
  • ⁇ -farnesene is 7, l l-dimethyl-3-methylene- l,6, 10-dodecatriene:
  • the isoprenoid moiety may have a structure selected from:
  • isoprenoid moiety Although it is generally preferred for a single isoprenoid moiety to be linked to an aromatic group, it will be appreciated that more than one isoprenoid moiety may be linked to the aromatic group.
  • the isoprenoid moiety is preferably located in an ortho or para, and preferably para, position relative to the acidic group. Where there is more than one acidic group, the isoprenoid moiety is preferably located in the ortho or para, preferably para, position relative to the more acidic of the acidic groups (sulfonic acid groups being more acidic than carboxy groups which, in turn, are more acidic that hydroxyl groups).
  • a composition e.g. a lubricating composition
  • greater than 50%, preferably greater than 75%, and more preferably greater than 90% of the acyclic isoprenoid moieties are located in a para position relative to the acidic group.
  • the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety may have the formula:
  • Ar is an aryl group
  • A is an acidic group
  • a is 1 or 2;
  • X may be present or absent and is a non-acidic group
  • L may be present or absent and is a linking group
  • R 1 is an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units
  • B is a bridging group
  • Ar is preferably a benzene group or a naphthalene group. More preferably, Ar is a benzene group.
  • A is preferably selected from -OH, -C(0)OH and -S(0) 2 OH. More preferably, A is -
  • a is preferably 1. Where a is 2, at least one A is preferably -OH.
  • X is preferably absent or selected from -R 2 , -R 2 OH, -OR 2 , -C(0)R 2 and -C(0)OR 2 , where R is selected from Ci_ 5 alkyl. More preferably, X is absent or selected from -CH 3 and -CH 2 OH. Still more preferably, X is absent.
  • L is preferably absent or selected from -Ci-ioalkyl-, more preferably -Ci-salkyl-. More preferably, L is absent.
  • R 1 is preferably an acyclic isoprenoid moiety as discussed above. As detailed above, farnesene and farnesane moieties are particularly preferred. As also detailed above, the acyclic isoprenoid moiety is preferably located in an ortho or para, and preferably para, position relative to the acidic group A. Where there is more than one acidic group, R 1 is preferably located in the ortho or para, preferably para, position relative to the more acidic of the acidic groups.
  • B is preferably selected from -(S)d-, -(CH 2 )d- and -[CH 2 OCH 2 ]d-, where d is 1 to 10.
  • B is preferably selected from -(S)d- and -(CH 2 )d-.
  • d is 1 to 3, more preferably 1 to 2, and even more preferably 1.
  • b is preferably 0 to 5, more preferably 0 to 2, and even more preferably 1.
  • the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety has a formula selected from:
  • R , B and b are as defined previously.
  • Ri is selected from farnesene and farnesane moieties
  • B is selected from -(S)- and -(CH 2 )-;
  • b is 0 or 1.
  • the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety is:
  • the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units is used in the form of a salt.
  • the compound will generally form the anion in the salt (i.e. by loss of a proton from the acidic group).
  • the cation may be metallic or non-metallic, however it is generally preferred for the salt to be a metal salt with a metallic component as the cation.
  • metals which may be used in the metal salt include alkali metals (such as lithium, sodium, potassium, rubidium, caesium) and alkaline earth metals (such as beryllium, magnesium, calcium, strontium, barium).
  • alkali metals for use in the salt include sodium, potassium and lithium.
  • Preferred alkaline earth metals for use in the salt include magnesium, calcium and barium.
  • Non-metallic cations include amine-based cations such as a guanidinium cation.
  • the salt may be a neutral salt, i.e. the cation content is equal to that which would be present for stoichiometric neutralisation of an acidic organic compound.
  • the salt is overbased.
  • Overbased salts comprise a cation content that is in excess of that which would be present for
  • Overbased salts may be characterised by the Total Base Number (TBN) that they exhibit, which is the amount of strong acid needed to neutralise all of the basicity of the anion in the salt, expressed as mg potassium hydroxide per gram of compound.
  • TBN may be measured according to the method of ASTM D2896- 11, for example using procedure B of ASTM D2896- 11.
  • the TBN exhibited by the salt comprising the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units is from 100 to 450 mg KOH/g, preferably from 150 to 400 mg KOH/g, and more preferably from 150 to 300 mg KOH/g.
  • Salts of the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units may be prepared using a
  • the salts of the present invention may be obtained a method which comprises linking an aromatic compound with a precursor to an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units.
  • the aryl ring in the aromatic group is preferably linked directly to the acyclic isoprenoid moiety, in which case the salt may obtained by substituting the aryl ring in an aromatic compound with the precursor.
  • the precursor is obtained by a method in which an isoprene addition product of 3 to 6 isoprene units is partially hydrogenated.
  • the partial hydrogenation removes some but not all of the double bonds that are present in the isoprene addition product.
  • the partial hydrogenation may be performed in the presence of a catalyst, and/or under conditions selected to prevent thermal dimerization, cyclisation, isomerisation, or other competing or degradation process of the isoprenoid compound and/or its partially hydrogenated product. Selective hydrogenation reactions, and catalysts for use therein, are known in the art.
  • the precursor is obtained by a method which comprises: functionalising the alpha-olefin of an isoprene addition product of 3 to 6 isoprene units with a protecting group; hydrogenating the unprotected olefins; and removing the protecting group to give an acyclic isoprenyl moiety precursor which contains an alpha- olefin.
  • the method may further comprise preparing a salt of the present invention by substituting an aromatic compound with the acyclic isoprenyl moiety precursor.
  • the acyclic isoprenoid moiety may be derived from farnesene e.g. using a method which comprises: functionalising the alpha-olefin with a protecting group; hydrogenating the unprotected olefins; and removing the protecting group to give 3,7,11- trimethyl- l-dodecene, an acyclic isoprenyl moiety precursor.
  • An aromatic compound may then be substituted with the precursor to give a salt according to the present invention in which the acyclic isoprenyl moiety is farnesane.
  • a precursor may be obtained by a method which comprises: hydrogenating an isoprenyl alcohol (preferably in which the alcohol is a primary alcohol); to give an acyclic isoprenyl moiety precursor which contains an alcohol (preferably a primary alcohol).
  • the acyclic isoprenoid moiety may be derived from farnesol e.g. using a method which comprises: hydrogenating the olefins to give 3,7, 11-trimethyl-l- dodecanol, an acyclic isoprenyl moiety precursor. An aromatic compound may then be substituted with the precursor to give a salt according to the present invention in which the acyclic isoprenyl moiety is farnesane.
  • 3,7,11-trimethyl- l -dodecanol may be halogenated to give an acyclic isoprenyl moiety precursor, which may then be used to give a salt according to the present invention in which the acyclic isoprenyl moiety is farnesane.
  • the acyclic isoprenoid moiety may be hydrogenated once is linked to the aromatic group.
  • the precursor is added to the aromatic group in the form of an unsaturated acyclic isoprenoid moiety.
  • the precursor may be obtained by a method in which an isoprene addition product of 3 to 6 isoprene units is partially halogenated. Methods for the selective halogenation of olefins are known in the art (e.g. using phosphorus tribromide).
  • the method may further comprise preparing a compound which comprises an aromatic group linked to an unsaturated acyclic isoprenoid moiety by substituting an aromatic compound with the precursor.
  • the method may further hydrogenating the compound so that the aromatic group is linked to a saturated acyclic isoprenoid moiety.
  • farnesol may be partially halogenated to form 1 -halo, 3,7, 11- trimethyldodeca-2,6,10-triene, an acyclic isoprenyl moiety precursor.
  • the precursor may then be used to prepare a compound which comprises an aromatic group linked to an unsaturated acyclic isoprenoid moiety.
  • the method may further comprise hydrogenating the moiety.
  • sesquiterpene alcohols could also be used in the abovementioned methods e.g. nerolidol.
  • the acyclic isoprenoid moiety may be derived from isoprenoid compounds that have been prepared chemically or biologically. Suitable methods are known in the art and include the oligomerisation of isoprene units. In some embodiments, the acyclic isoprenoid moiety may be derived from a cyclic isoprenoid compound for example by methods including metathesis and hydrocracking.
  • Farnesene may be prepared chemically from nerolidol (see e.g. Anet: "Synthesis of ( ⁇ , ⁇ )- ⁇ -, ( ⁇ , ⁇ )- ⁇ -, and (Z)-P-farnesene", Aust. J. Chem. 23(10), 2101-2108; and US 4,546,110). Further chemical methods of preparing farnesene may include the conversion of farnesol and/or nerolidol into farnesene by dehydration with a dehydrating agent or an acid catalyst. Examples of dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulphuric acid.
  • the isoprenoid moiety may also be derived from isoprenoid compounds from natural sources. In nature, isoprenoid compounds may be synthesised by consecutive
  • IPP isopentenyl pyrophosphate
  • DMAPP isomer dimethylallyl pyrophosphate
  • Processes for producing of these precursors in nature include two pathways. Eukaryotes, with the exception of plants, generally use the mevalonate-dependent (MEV) pathway to covert acetyl co-enzyme A to IPP, which is subsequently isomerised. Prokaryotes, with some exceptions, typically employ only the mevalonate independent or deoxyxylulose-5-phosphate (DXP) pathway to produce IPP and DMAPP. Plants use both the MEV and DXP pathways.
  • MEV mevalonate-dependent pathway
  • DXP deoxyxylulose-5-phosphate
  • isoprenoid compounds used in the present invention may be extracted from natural sources, e.g. from plants, microbes, and animals.
  • farnesene may be derived from terpenes produced by plants, e.g. Copaifera langsdorfii, conifers, and spurges; by insects, e.g. swallowtail butterflies, leaf beetles, termites and pine sawflies; and by marine organisms, e.g. algae, sponges, corals, molluscs, and fish.
  • Natural sources of isoprenoid compounds also include essential oils.
  • Farnesol and farnesene may be found in essential oils. For instance, farnesol is present in many essential oils such as citronella, neroli, cyclamen, lemongrass, tuberose, rose, musk, balsam and tolu oils.
  • Isoprenoid compounds are also the main component of rubber, though it will usually be necessary to process the components found in rubber so as to reduce their chain length.
  • the isoprenoid moiety is preferably derived from isoprenoid compounds that are derived biosynthetically, e.g. via exploitation of the MEV and DXP pathways.
  • a key advantage of the biosynthetic preparation of isoprenoid compounds is that variation in the length of the alkyl chains produced by the methods may be minimised.
  • Suitable microbes for use in the biosynthetic preparation of isoprenoid compounds include those that have been engineered to overexpress a part of or the entire MEV pathway for production of an isoprenoid (see e.g. US 7, 172,886 and US 7, 192,751).
  • isoprenoids are produced by the use of IPP pathway enzymes that are under the control of at least one heterogeneous regulator or fermentation conditions, either alone or in combination.
  • Farnesene may be prepared using bioengineered microorganisms, e.g. as disclosed in US 7,399,323, US 2008/0,274,523, US 2009/0, 137,014, WO
  • the isoprenoid compound may be derived from a biobased feedstock.
  • the isoprenoid compound may be derived from organic or biomass sources. This may have a benefit of permitting the replacement of, at least in part, fossil fuel sources (for example propylene) which are typically used to prepare acyclic moieties in detergent additives.
  • fossil fuel sources for example propylene
  • Bio-derived feedstocks may be used as a source of farnesene and farnesol.
  • farnesene may be derived from organic compounds such as fermentable carbon sources, including sugars.
  • the salts disclosed herein may form part of a lubricating composition, e.g. a non- aqueous lubricating composition such as a lubricating composition for an internal combustion engine.
  • a lubricating composition comprises a major amount of oil of a base and a minor amount of a salt of the present invention.
  • Major amount means greater than 50% and minor amount means less than 50 % by weight.
  • the lubricating composition comprises base oil in an amount of from greater than 50 % to about 99.5 % by weight, for example from about 85% to about 95% by weight.
  • Base oils comprise one or more base stocks.
  • Base stocks may be defined as Group I, II, III, IV and V base stocks according to API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", March 2015 version, Appendix E.
  • Group I, Group II and Group III base stocks may be derived from mineral oils.
  • Group I base stocks are typically manufactured by known processes comprising solvent extraction and solvent dewaxing, or solvent extraction and catalytic dewaxing.
  • Group II and Group III base stocks are typically manufactured by known processes comprising catalytic hydrogenation and/or catalytic hydrocracking, and catalytic hydroisomerisation.
  • Examples of Group I base stocks include AP/E core 150, available from ExxonMobil.
  • Examples of Group II base stocks include EHC 50 and EHC 110, available from
  • Group III base stocks include Yubase 4 and Yubase 6 available for example from SK Lubricants.
  • Group V base stocks include ester base stocks, for example Priolube 3970, available from Croda International pic.
  • Group IV base stocks include hydrogenated oligomers of alpha olefins. Examples of processes for the preparation of the oligomers include free radical processes and catalysed processes.
  • polyalpha olefin base stocks are derived for example from Cg, Cm, Ci 2 , Ci 4 olefins and mixtures of one or more thereof.
  • the base oil comprises a base stock which is a natural oil, a mineral oil (sometimes called petroleum-derived oil or petroleum-derived mineral oil), a non-mineral oil or a mixture thereof.
  • Natural oils include for example animal oils, fish oils, and vegetable oils.
  • Mineral oils include for example paraffinic oils, naphthenic oils and paraffinic-naphthenic oils. Mineral oils may also include oils derived from coal or shale.
  • Suitable base stocks include those derived from processes including chemical combination of simpler or smaller molecules into larger or more complex molecules (for example polymerisation, oligomerisation, condensation, alkylation, acylation).
  • Suitable base oils include those derived from gas-to-liquids materials, coal-to-liquids materials, biomass-to-liquids materials and combinations thereof.
  • gas-to-liquids materials include those that are obtained by one or more process steps of synthesis, combination, transformation, rearrangement, degradation and combinations of two or more thereof applied to gaseous carbon-containing compounds.
  • GTL derived base stocks include those obtained from a Fischer-Tropsch synthesis process in which synthesis gas comprising a mixture of hydrogen and carbon monoxide is catalytically converted to hydrocarbons, usually waxy hydrocarbons that are generally converted to lower-boiling materials hydroisomerisation and/or dewaxing (see for example WO 2008/124191).
  • biomass-to-liquids materials include those that are manufactured from compounds of plant origin for example by hydrogenation of carboxylic acids or triglycerides to produce linear paraffins, followed by hydroisomerisation to produced branched paraffins (see for example WO
  • coal-to-liquids materials include those that are made by gasifying coal to make synthesis gas which is then converted to hydrocarbons.
  • the base oil preferably has a kinematic viscosity at 100 °C for example in the range of 2 to 100 cSt, suitably in the range of 3 to 50 cSt and more suitably in the range 3.5 to 25 cSt.
  • the lubricating composition of the present invention is for example a monograde lubricating oil composition according to API classification, for example SAE 4, 8, 12, 16, 20, 30, 40, 50 or 60 grade.
  • the lubricating composition of the present invention is for example, a multi-grade lubricating composition according to the API classification xW-y where x is 0, 5, 10, 15 or 20 and y is 4, 8, 12, 16, 20, 30, 40, 50 or 60 as defined by SAE J300 2015, for example 5W-20, 5W-30, 0W-20.
  • the lubricating composition has for example an HTHS viscosity at 150 °C of at least 2.6cP, e.g. as measured according to ASTM D4683.
  • the lubricating composition exhibits an HTHS viscosity at
  • the lubricating composition is prepared by mixing a base oil with a salt of the present invention and optionally at least one further lubricant additive.
  • the base oil may be mixed with the salt in the form of an additive concentrate or a part additive package concentrate, optionally comprising solvent or diluent.
  • the salts disclosed herein are preferably used in lubricating composition in an amount of from 0.001 to 5 %, preferably from 0.005 to 1 %, and more preferably from 0.01 to 0.5 %, by weight of the lubricating composition. These ranges are particularly suitable for automotive lubricant applications. In marine cylinder lubricant applications, the salts disclosed herein may be particularly suitably used in an amount of from 0.001 to 25% or from 1% to 25%, preferably from 5% to 20%, even more preferably from 10% to 15%.
  • the use of the salts of the present invention as detergents enables the content of other detergents that are typically found in a lubricating composition, some of which are known to have toxic effects, to be reduced.
  • the lubricating composition comprises tetrapropenylphenol in an amount of less than 10 , preferably less than 1%, more preferably less than 0.3%, and even more preferably less than 0.1 % by weight of the salt. Most preferably, the lubricating composition is substantially free from tetrapropenyl phenol.
  • the lubricating composition may additionally comprises at least one further lubricant additive, i.e. an additive other than the salts of the present invention.
  • at least one further lubricant additive i.e. an additive other than the salts of the present invention.
  • the further lubricant additive is multi-functional, that is, it may perform more than one function in the composition.
  • further additives include other detergents (metallic and non-metallic), friction modifiers, dispersants (metallic and non-metallic), dispersant viscosity modifiers, viscosity index improvers, viscosity modifiers, pour point depressants, rust inhibitors, corrosion inhibitors, antioxidants (sometimes also called oxidation inhibitors), anti-foams (sometimes also called anti- foaming agents), seal swell agents (sometimes also called seal compatibility agents), extreme pressure additives (metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulphur containing and non-sulphur containing), surfactants, demulsifiers, antiseizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents and metal deactivators.
  • the lubricating composition additionally comprises at least one detergent other than a salt of the present invention.
  • Detergents also called detergent additives
  • Detergents may also have acid-neutralising properties.
  • detergents include for example ashless detergents (that is, non-metal containing
  • Metal-containing detergent comprises at least one metal salt of at least one organic acid, which is called soap or surfactant.
  • the detergents are overbased in which the detergent comprises an excess of metal in relation to the stoichiometric amount required to neutralise the organic acid.
  • the excess metal is usually in the form of a colloidal dispersion of metal carbonate and/or hydroxide.
  • metals include Group I and Group 2 metals, for example calcium, magnesium and combinations thereof, especially calcium. More than one metal may be present.
  • organic acids include sulphonic acids, phenols (sulphurised or sulphurised and including for example phenols with more than one hydroxyl group, phenols with fused aromatic rings, modified phenols including alkylene bridged phenols, and Mannich base-condensed phenols and saligenin-type phenols, produced for example by reaction of phenol and an aldehyde under basic conditions) and sulphurised derivatives thereof, and carboxylic acids including for example aromatic carboxylic acids (for example hydrocarbyl- substituted salicylic acids and sulphurised derivatives thereof, for example hydrocarbyl substituted salicylic acid and derivatives thereof). More than one type of organic acid may be present.
  • phenols sulphurised or sulphurised and including for example phenols with more than one hydroxyl group, phenols with fused aromatic rings, modified phenols including alkylene bridged phenols, and Mannich base-condensed phenols and saligenin-type phenols, produced
  • detergents also include non-metallic detergents. Examples of non-metallic detergents are described for example in US7622431.
  • more than one further detergent is present in the lubricating composition.
  • the lubricating composition additionally comprises at least one friction modifier.
  • friction modifier additives include ash-producing additives and ashless additives.
  • friction modifiers include fatty acid derivatives including for example fatty acid esters, amides, amines, and ethoxylated amines.
  • ester friction modifiers include esters of glycerol for example mono-, di-, and tri-oleates, mono-palmitates and mono-myristates.
  • a suitable fatty acid ester friction modifier is glycerol monooleate.
  • friction modifiers also include molybdenum compounds for example organo molybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum dialkylthiophosphates, molybdenum disulphide, tri- molybdenum cluster dialkyldithiocarbamates, non-sulphur molybdenum compounds and the like.
  • molybdenum-containing compounds are described in EP 1533362 .
  • friction modifiers also include a combination of an alkoxylated hydrocarbyl amine and a polyol partial ester of a saturated or unsaturated fatty acid or a mixture of such esters, for example as described in WO 93/21288.
  • friction modifiers that are fatty acid derivative friction modifiers are present in the lubricating composition at a concentration, for example of 0.01 to 5 % by weight actives, or in the range of 0.01 to 1.5 % by weight actives.
  • molybdenum containing friction modifiers are present in the lubricating composition at a concentration, for example of 10 to 1000 ppm by weight molybdenum, or in the range of 400 to 600 ppm by weight.
  • the lubricating composition additionally comprises at least one anti-wear additive.
  • Anti-wear additives include ash -producing additives and ashless additives. Examples of anti-wear additives include non-phosphorus containing additives for example sulphurised olefins. Examples of anti-wear additives also include phosphorus- containing anti-wear additives. Examples of ashless phosphorus-containing anti-wear additives include trilauryl phosphite and triphenylphosphorothionate and those disclosed in paragraph [0036] of US2005/0198894. Examples of ash-forming, phosphorus-containing anti-wear additives include dihydrocarbyl dithiophosphate metal salts.
  • Examples of metals of the dihydrocarbyl dithiophosphate metal salts include alkali and alkaline earth metals, aluminium, lead, tin, molybdenum, manganese, nickel, copper and zinc.
  • Suitable dihydrocarbyl dithiophosphate metal salts are zinc dihydrocarbyl dithiophosphates (ZDDP).
  • ZDDP's include those which contain hydrocarbyl groups independently having 1 to 18 carbon atoms, or 2 to 13 carbon atoms or 3 to 18 carbon atoms, or suitably 2 to 12 carbon atoms or 3 to 13 carbon atoms, for example 3 to 8 carbon atoms.
  • hydrocarbyl groups include alkyl, cycloalkyl and alkaryl groups, including those which contain for example ether or ester linkages and also including those which contain for example substituent groups for example halogen or nitro groups.
  • Hydrocarbyl groups include for example alkyl groups which are linear or branched and which include those for example which contain from 3 to 8 carbon atoms.
  • Suitable ZDDP's contain hydrocarbyl groups which are a mixture of secondary alky groups and primary alkyl groups for example 90 mol. % secondary alkyl groups and 10 mol. % primary alkyl groups.
  • phosphorus-containing anti-wear additives are present in the lubricating composition at a concentration for example of 10 to 6000 ppm by weight of phosphorus, or 10 to 1000 ppm by weight of phosphorus, for example 200 to 1400 ppm by weight of phosphorus, or 200 to 800 ppm by weight of phosphorus or 200 to 600 ppm by weight of phosphorus.
  • Dispersants also called dispersant additives help hold solid and liquid contaminants for example resulting from oxidation of the lubricating composition during use, in suspension and thus reduce sludge flocculation, precipitation and/or deposition for example on lubricated surfaces. They generally comprise long-chain hydrocarbons, to promote oil-solubility, and a polar head capable of associating with material to be dispersed.
  • dispersants include oil soluble polymeric hydrocarbyl backbones each having one or more functional groups which are capable of associating with particles to be dispersed.
  • functional groups include amine, alcohol, amine-alcohol, amide and ester groups.
  • the functional groups are attached to the hydrocarbyl backbone through bridging groups.
  • more than one dispersant is present in the lubricating composition.
  • dispersants include oil soluble salts, esters, amino-esters, amides, imides and oxazolines of long chain hydrocarbon-substituted mono- and polycarboxylic acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto;
  • dispersants include derivatives of long chain hydrocarbyl- substituted carboxylic acids, for example in which the hydrocarbyl group has a number average molecular weight of up to 20000, for example 300 to 20000, 500 to 10000, 700 to 5000 or less than 15000.
  • dispersants include hydrocarbyl- substituted succinic acid compounds, for example succinimide, succinate esters or succinate ester amides and in particular, polyisobutenyl succinimide dispersants.
  • dispersants examples include borated and non-borated dispersants.
  • a suitable dispersant is ADX 222.
  • dispersancy is provided by polymeric compounds capable of providing viscosity index improving properties and dispersancy.
  • Such compounds are generally known as dispersant viscosity improver additives or multifunctional viscosity improvers.
  • Methods for preparing dispersant viscosity modifiers include for example chemically attaching functional moieties (for example amines, alcohols and amides) to polymers which tend to have number average molecular weights of at least 15000, for example in the range 20000 to 600000 (for example as determined by gel permeation chromatography or light scattering methods). Examples of dispersant viscosity modifiers and methods of making them are described in WO 99/21902, WO 2003/099890 and WO 2006/099250. In at least some examples, more than one dispersant viscosity modifier is present in the lubricating composition.
  • Viscosity index improvers (also called viscosity modifiers, viscosity improvers or VI improvers) impart high and low temperature operability to a lubricating composition and facilitate it remaining shear stable at elevated temperatures whilst also exhibiting acceptable viscosity and fluidity at low temperatures.
  • viscosity modifiers examples include high molecular weight hydrocarbon polymers (for example polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins); polyesters (for example polymethacrylates); hydrogenated poly(styrene-co- butadiene or isoprene) polymers and modifications (for example star polymers); and esterified poly(styrene-co-maleic anhydride) polymers.
  • Oil-soluble viscosity modifying polymers generally have number average molecular weights of at least 15000 to 1000000, preferably 20000 to 600000 as determined by gel permeation chromatography or light scattering methods.
  • viscosity modifiers include those which have additional functions as multifunction viscosity modifiers.
  • more than one viscosity index improver is present in the lubricating composition.
  • pour point depressants also called lube oil improvers or lube oil flow improvers
  • pour point depressants include C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, methacrylates, polyacrylates, polyarylamides, polymethacrylates, polyalkyl methacrylates, vinyl fumarates, styrene esters, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkyfumarates, vinyl esters of fatty acids and allyl vinyl ethers, wax naphthalene and the like.
  • more than one pour point depressant is present in the lubricating composition.
  • Rust inhibitors generally protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • rust inhibitors include non-ionic
  • polyoxyalkylene polyols and esters thereof polyoxyalkylene phenols, polyoxyalkylene polyols, anionic alky sulphonic acids, zinc dithiophosphates, metal phenolates, basic metal sulphonates, fatty acids and amines.
  • more than one rust inhibitor is present in the lubricating composition.
  • Corrosion inhibitors reduce the degradation of metallic parts contacted with the lubricating composition.
  • corrosion inhibitors include phosphosulphurised hydrocarbons and the products obtained by the reaction of phosphosulphurised hydrocarbon with an alkaline earth metal oxide or hydroxide, non-ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles, triazoles and anionic alkyl sulphonic acids. Examples of epoxidised ester corrosion inhibitors are described in US 2006/0090393.
  • more than one corrosion inhibitor is present in the lubricating composition.
  • Antioxidants (sometimes also called oxidation inhibitors) reduce the tendency of oils to deteriorate in use. Evidence of such deterioration might include for example the production of varnish-like deposits on metal surfaces, the formation of sludge and viscosity increase. ZDDP's exhibit some antioxidant properties.
  • antioxidants other than ZDDP' s include alkylated diphenylamines, N- alkylated phenylenediamines, phenyl-a-naphthylamine, alkylated phenyl-a- naphthylamines, dimethylquinolines, trimethyldihydroquinolines and oligomeric compositions derived therefrom, hindered phenolics (including ashless (metal-free) phenolic compounds and neutral and basic metal salts of certain phenolic compounds), aromatic amines (including alkylated and non-alkylated aromatic amines), sulphurised alkyl phenols and alkali and alkaline earth metal salts thereof, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, thiopropionates, metallic dithiocarbamates, 1,3,4-dimercaptothiadiazole and derivatives, oil soluble copper compounds (for example
  • alkylphenolthioesters suitably having C 5 to Cu alkyl side chains, calcium nonylphenol sulphide, barium i-octylphenyl sulphide, dioctylphenylamine, phosphosulphised or sulphurised hydrocarbons, oil soluble phenates, oil soluble sulphurised phenates, calcium dodecylphenol sulphide, phosphosulphurised hydrocarbons, sulphurised hydrocarbons, phosphorus esters, low sulphur peroxide decomposers and the like.
  • more than one antioxidant is present in the lubricating composition. In at least some examples, more than one type of antioxidant is present in the lubricating composition.
  • Anti-foams (sometimes also called anti-foaming agents) retard the formation of stable foams.
  • anti-foam agents include silicones, organic polymers, siloxanes (including poly siloxanes and (poly) dimethyl siloxanes, phenyl methyl siloxanes), acrylates and the like.
  • more than one anti-foam is present in the lubricating composition.
  • Seal swell agents (sometimes also called seal compatibility agents or elastomer compatibility aids) help to swell elastomeric seals for example by causing a reaction in the fluid or a physical change in the elastomer.
  • seal swell agents include long chain organic acids, organic phosphates, aromatic esters, aromatic hydrocarbons, esters (for example butylbenzyl phthalate) and polybutenyl succinic anhydride.
  • more than one seal swell agent is present in the lubricating composition.
  • additives which, in at least some examples, additionally are present in the lubricating composition include extreme pressure additives (including metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulphur containing and non-sulphur containing extreme pressure additives), surfactants, demulsifiers, anti-seizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents and metal deactivators.
  • extreme pressure additives including metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulphur containing and non-sulphur containing extreme pressure additives
  • surfactants including metallic, non-metallic, phosphorus containing, non-phosphorus containing, sulphur containing and non-sulphur containing extreme pressure additives
  • demulsifiers demulsifiers
  • anti-seizure agents wax modifiers
  • lubricity agents anti-staining agents
  • chromophoric agents and metal de
  • the lubricating composition may comprise a co-surfactant alongside the salt of the present invention.
  • co-surfactants are included in a composition in order to further improve the stability of the micelle structure that is typically formed by detergents present in the composition, such as the salt of the present invention.
  • co- surfactants include fatty acids, such as myristic acid, stearic acid, palmitic acid, oleic acid and linoleic acid, succinic acids or anhydrides such as dodecyl succinic acid/anhydride, and alkyl ethoxylates.
  • the co-surfactant may be present in the lubricating composition in an amount of up to 20% by weight of the salt of the present invention, for example from 0.01% to 10%, 0.1% to 5% or 0.5% to 2% by weight of the salt of the present invention.
  • the lubricating composition for a lubricating composition additionally comprises solvent.
  • Solvents are often used to solubilise the lubricant additives when they are in the form of additive concentrates, i.e. before they are mixed with a base oil.
  • solvents include highly aromatic, low viscosity base stocks, for example 100N, 60 N and 100SP base stocks.
  • the representative typical and more typical independent amounts of additives (if present) in the lubricating composition are given in Table 2.
  • concentrations expressed in Table 2 are by weight of active additive compounds (that is, independent of any solvent or diluent), and typically exclude the salts of the present invention.
  • each type of additive is present.
  • more than one class of that type of additive is present.
  • more than one additive of each class of additive is present.
  • additives are supplied by manufacturers and suppliers in solvent or diluents.
  • the salts of the present invention may be used as a detergent in a non-aqueous lubricating composition, e.g. a lubricating composition for an internal combustion engine. Accordingly, a method for improving the detergency of a lubricating composition, e.g. when used in an internal combustion engine, may comprise adding a salt of the present invention to the lubricating composition.
  • the detergency of lubricating compositions may be characterised by the Total Base Number (TBN) that they exhibit, which is the amount of strong acid needed to neutralise all of the basicity of any basic components (primarily detergents) present in a lubricating composition, expressed as mg potassium hydroxide per gram of lubricating composition.
  • TBN may be measured according to the method of ASTM D2896- 11, as described above for example using procedure B of ASTM D2896- 11.
  • Examples of internal combustion engines include engines used in automotive applications, aviation applications, marine applications and land-based power generation plants.
  • the non-aqueous lubricating composition is used to lubricate a surface at any typical temperature which is encountered in a lubricating environment, for example at a temperature such as is encountered in an internal combustion engine, for example a temperature in the range of ambient to 250 °C, for example 90 to 120 °C.
  • ambient temperature is 20 °C, but in at least some examples, ambient temperature is less than 20°C, for example 0°C.
  • Examples of internal combustion engines include spark-ignition, internal combustion engines and compression-ignition, internal combustion engines.
  • Examples of internal combustion engines include two-stroke and four-stroke compression-ignition engines.
  • the salts of the present invention may be used as a detergent in a system oil lubricating composition and/or in a cylinder oil lubricating composition used to lubricate the engine.
  • the two- stroke compression-ignition engine is used in marine applications.
  • the salts of the present invention are used as a detergent in a lubricating composition for the crankcase of an internal combustion engine.
  • the salts of the present invention may be added to the lubricating composition used to the lubricate the engine by slow release of the additive into the lubricating composition, such as by contacting the lubricating composition with a gel comprising the additive e.g. as described in US 6,843,916 and international PCT patent application publication WO 2008/008864 and/or by controlled release of the additive, such as when the back pressure of lubricating composition passing through a filter exceeds a define back pressure e.g. as described in international PCT patent application publication WO 2007/148047.
  • the salts of the present invention may be used, or be used in methods, for detergency, deposit reduction, friction reduction, oxidation performance improvement, storage stability and/or corrosion inhibition, in an internal combustion engine, such as a spark-ignition internal combustion engine or a compression-ignition internal combustion engine.
  • an internal combustion engine such as a spark-ignition internal combustion engine or a compression-ignition internal combustion engine.
  • the salt of the present invention as a detergent, a deposit- reducing agent, a friction-reducing agent, an oxidation performance improver, a storage stability enhancer, and/or a corrosion inhibitor in a lubricating composition, and preferably a lubricating composition for an internal combustion engine is contemplated, as are methods for improving the detergency, deposit reduction, friction reduction, oxidation performance, storage stability and/or corrosion inhibition characteristics of a lubricating composition, wherein the method comprises adding a salt of the present invention to the lubricating composition.
  • a salt as described in embodiment 1, wherein the aromatic group comprises a hydrocarbon aryl ring, preferably a benzene ring, a toluene ring or a naphthalene ring, and more preferably a benzene ring.
  • a salt as described in embodiment 1, wherein the aromatic group comprises a hydrocarbon aryl ring substituted with an acidic group, and preferably substituted with a hydroxyl group, a carboxy group or a sulfonic acid group, and more preferably substituted with a hydroxy group.
  • a salt as described in embodiment 1, wherein the acyclic isoprenoid moiety is an unsubstituted addition product of isoprene, or the hydrogenation product thereof.
  • a salt as described in embodiment 1, wherein the acyclic isoprenoid moiety is derived from 3 isoprenyl units, and is preferably a farnesene group or a hydrogenated derivative thereof.
  • a salt as described in embodiment 1, wherein the acyclic isoprenoid moiety has a structure selected from:
  • a salt as described in embodiment 1, wherein the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety has the formula:
  • Ar is an aryl group
  • A is an acidic group
  • a is 1 or 2;
  • X may be present or absent and is a non-acidic group
  • L may be present or absent and is a linking group
  • R 1 is an acyclic isoprenoid moiety derived from 3 to 6 isoprenyl units
  • B is a bridging group
  • b 0 to 10.
  • a salt as described in embodiment 10, wherein the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety has a formula selected from:
  • Ri is selected from farnesene and farnesane moieties
  • B is selected from -(S)- and -(CH 2 )-;
  • b is 0 or 1.
  • a salt as described in embodiment 11, wherein the compound which comprises an aromatic group linked to an acyclic isoprenoid moiety is:
  • a salt as described in embodiment 13, wherein the metallic salt comprises a metal selected from alkali metals, preferably from lithium, sodium and potassium, rubidium, , and from alkaline earth metals, preferably from magnesium, calcium, and barium.
  • a salt as described in embodiment 1, wherein the acyclic isoprenoid moiety is derived bio synthetically.
  • a salt as described in embodiment 1, wherein the isoprenoid compound is derived from a biobased feedstock, preferably from an organic or biomass source.
  • fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid and linoleic acid
  • succinic acids or anhydrides such as dodecyl succinic acid/anhydride
  • alkyl ethoxylates such as dodecyl succinic acid/anhydride
  • a salt as described in embodiment 1 as a detergent, a deposit-reducing agent, an oxidation performance improver, a storage stability enhancer, and/or a corrosion inhibitor in a lubricating composition, and preferably a lubricating composition for an internal combustion engine.
  • Phenol (340 g, 2 eq) was slurried in heptane (490 ml) and heated to 40°C. BF 3 .OEt 2 (68.05 ml, 0.3 eq) was added in one portion, followed by adding a solution of
  • Comparative Example B tabulated in Table 3 below, replacing all of the 250BN C12 conventional phenate with an equivalent amount (0.7% by weight) of the respective sample prepared above, in order to produce a lubricant composition with equivalent TBN to the starting lubricant composition. Comparative Example B: Table 3
  • TEOST Simulation Testing
  • the examples were also subjected to Indiana Stirring Oxidation Test (ISOT) in accordance with JIS Method K 2514-1982, operated by heating the lubricant composition sample to 165°C under vigorous stirring, until the kinematic viscosity has reached twice its starting value (as measured at 40°C), to determine the oxidative performance of the examples, a longer duration of test indicating improved oxidative performance.
  • ISOT Indiana Stirring Oxidation Test
  • HTCBT High Temperature Corrosion Bench Tests

Landscapes

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

Abstract

L'invention concerne un sel d'un composé comprenant un groupe aromatique lié à une fraction isoprénoïde acyclique dérivée de 3 à 6 unités isoprényles. Selon l'invention, le sel peut être utilisé comme détergent dans une composition lubrifiante, par exemple pour un moteur à combustion interne et dans des utilisations et des procédés associés.
PCT/EP2018/054012 2017-03-01 2018-02-19 Sels surbasés d'oligomères de phénol alkylés utilisés en tant qu'additifs de lubrifiants Ceased WO2018158099A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1703316.8A GB201703316D0 (en) 2017-03-01 2017-03-01 Salts, compositions, their preparation and uses
GB1703316.8 2017-03-01

Publications (1)

Publication Number Publication Date
WO2018158099A1 true WO2018158099A1 (fr) 2018-09-07

Family

ID=58544125

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/054012 Ceased WO2018158099A1 (fr) 2017-03-01 2018-02-19 Sels surbasés d'oligomères de phénol alkylés utilisés en tant qu'additifs de lubrifiants

Country Status (2)

Country Link
GB (1) GB201703316D0 (fr)
WO (1) WO2018158099A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112720A1 (fr) * 2017-12-04 2019-06-13 The Lubrizol Corporation Détergents à base d'alkylphénol
JP2022513048A (ja) * 2018-11-16 2022-02-07 ザ ルブリゾル コーポレイション アルキルベンゼンスルホネート洗浄剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011066115A2 (fr) * 2009-11-24 2011-06-03 Chevron U.S.A. Inc. Procédé de fabrication d'un sel sulfuré et surbasé d'un composé hydroxyaromatique alkylé
WO2011096920A1 (fr) * 2010-02-03 2011-08-11 Chevron Oronite Company Llc Additif pour huile lubrifiante et composition d'huile lubrifiante le contenant
WO2013070402A1 (fr) * 2011-11-10 2013-05-16 Chevron Oronite Company Llc Compositions d'huile lubrifiante

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011066115A2 (fr) * 2009-11-24 2011-06-03 Chevron U.S.A. Inc. Procédé de fabrication d'un sel sulfuré et surbasé d'un composé hydroxyaromatique alkylé
WO2011096920A1 (fr) * 2010-02-03 2011-08-11 Chevron Oronite Company Llc Additif pour huile lubrifiante et composition d'huile lubrifiante le contenant
WO2013070402A1 (fr) * 2011-11-10 2013-05-16 Chevron Oronite Company Llc Compositions d'huile lubrifiante

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112720A1 (fr) * 2017-12-04 2019-06-13 The Lubrizol Corporation Détergents à base d'alkylphénol
JP2022513048A (ja) * 2018-11-16 2022-02-07 ザ ルブリゾル コーポレイション アルキルベンゼンスルホネート洗浄剤

Also Published As

Publication number Publication date
GB201703316D0 (en) 2017-04-12

Similar Documents

Publication Publication Date Title
EP2449069B1 (fr) Détergents pour huiles lubrifiantes stable à température basse et leur procédé de fabrication
US6034039A (en) Lubricating oil compositions
AU2011268759B2 (en) Uses and compositions
CA2926013C (fr) Compositions d'estolide presentant des proprietes ameliorees dans une composition lubrifiante
EP3066180B1 (fr) Compositions d'huile lubrifiante pour cylindre diesel marin
EP3066181B1 (fr) Compositions d'huiles lubrifiantes pour cylindres diesels marins
EP1548089B1 (fr) Une méthode pour lubrifier avec une composition d'huile lubrifiante contenant un sel de metal alcalin d'acide salicylique
JP2011231339A (ja) 潤滑油用未硫化カルボキシレート含有添加剤
US20130167431A1 (en) Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy-carboxylic acids, and uses thereof
KR20170078706A (ko) 선박용 디젤 실린더 윤활유 조성물
EP3013925A1 (fr) Compositions de lubrification contenant des composants à base d'isoprène
KR102613191B1 (ko) 선박용 디젤 실린더 윤활유 조성물
WO2013189675A1 (fr) Modificateurs de friction et leur utilisation dans des lubrifiants et des carburants
WO2018158099A1 (fr) Sels surbasés d'oligomères de phénol alkylés utilisés en tant qu'additifs de lubrifiants
US10907111B2 (en) Use of a hydrocarbyl-substituted salicylic acid detergent as an inhibitor of lead corrosion
US9200229B2 (en) Friction modifier and their use in lubricants and fuels
EP3555249A1 (fr) Compositions lubrifiantes à base d'éther, procédés et utilisations
KR20190066630A (ko) 선박용 디젤 윤활유 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18706253

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18706253

Country of ref document: EP

Kind code of ref document: A1