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
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
  • C10M171/007—Coloured or dyes-containing lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/003—Marking, e.g. coloration by addition of pigments
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
  • C10L1/1895—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom polycarboxylic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
• • 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
  • C10M2207/28—Esters
  • C10M2207/285—Esters of aromatic polycarboxylic acids
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
• • 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
  • C10M2215/08—Amides
• • 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
  • C10N2030/20—Colour, e.g. dyes
• • 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
  • C10N2030/70—Soluble oils
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
• • 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
  • C10N2040/252—Diesel engines
• • 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
  • C10N2040/255—Gasoline engines
• • 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
  • C10N2040/255—Gasoline engines
  • C10N2040/26—Two-strokes or two-cycle engines
• • 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
  • C10N2040/42—Flashing oils or marking oils
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• This invention relates to dyes and their use in lubricating oil compositions and for detecting leakage of a lubricating oil composition in lubricated apparatus.
• This invention also relates to lubricating oil compositions, fuel compositions and additive concentrates comprising oil-soluble dyes and to the use of dyes to determine ingress of components from the combustion chamber of an internal combustion engine into the crankcase of the engine.
• US 2004/0203159A1 relates to the use of fluorescent dyes based on pyrromethane difluoroborate complexes in fluorescent marking of lubricants and for the determination of leakages.
• US 2004/02031591A1 also relates to fluorescent dye concentrates based upon octanoic acid as a solvent.
• a problem which may be encountered when using a dye to detect leakage of lubricating oil composition in a lubricated apparatus is that the dye may not be suitably stable under the operating conditions of the lubricated apparatus. This may be a problem for example, when the lubricated apparatus is an internal combustion engine or part thereof, for example the crankcase of an internal combustion engine.
• the dye may undergo degradation, for example when used in the operating conditions of an internal combustion engine, for example in the crankcase of an internal combustion engine. This may limit the usefulness of the dye.
• the degradation may be thermal degradation.
• the degradation may be chemical degradation.
• the degradation may be a combination of thermal and chemical degradation. Examples of chemical degradation include nitration, oxidative degradation and combinations thereof.
• compositions comprising at least one oil-soluble dye which overcome or at least mitigate these problems.
• a nonaqueous lubricating oil composition comprising a major amount of a base oil of lubricating viscosity, at least one internal combustion engine crankcase lubricating oil additive and a minor amount of at least one oil-soluble dye which dye comprises at least one
• chromophore which is incarcerated, at least partially, within at least one macrocycle.
• the present invention solves the technical problem identified above by the use of at least one oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle.
• the macrocycle may shield the chromophore against degradation and hence provide a dye which has enhanced resistance to degradation, for example thermal and/or chemical degradation.
• An advantage of the oil-soluble dye having enhanced resistance to degradation is that it may extend the lifetime of the dye, for example when used in a lubricating oil composition which is used to lubricate an internal combustion engine or part thereof (for example the crankcase of an internal combustion engine).
• the lubricating oil composition comprising oil-soluble dye may be a crankcase lubricant for an internal combustion engine, for example, a first-fill crankcase lubricant.
• the crankcase lubricant may be used for the first fill of lubricating oil composition in the crankcase of an internal combustion engine.
• Any leakage of lubricating oil composition comprising oil-soluble dye during the operation of the lubricated apparatus may be detected by detecting the presence of dye, for example on the external surface of the apparatus.
• the presence of leaked dye may be detected by visual inspection. Visual inspection may be facilitated by using ultra-violet light, if the dye is a fluorescent dye.
• the dye may suitably be a luminescent dye.
• the luminescent dye may be a fluorescent dye or a phosphorescent dye. Fluorescent dyes absorb light at certain wavelength(s) and in turn emit their fluorescence energy at a different wavelength, which may be of a higher wavelength than the wavelength(s) of the absorbed light.
• a fluorescent dye may absorb light in the ultra-violet region of the spectrum and emit light in the visible region of the spectrum. Fluorescence is usually a short term effect.
• Phosphorescence is usually a long term effect.
• the presence of leaked dye may be detected by visual inspection.
• the dye is a fluorescent dye
• detection of leaked dye may be facilitated by using ultra-violet light, for example by illuminating the lubricated apparatus with ultra-violet light which may cause the leaked dye to fluoresce.
• the fluorescing dye may be more readily detected by visual inspection than dye which is not fluorescing.
• the dye may comprise 1 to 5 chromophores incarcerated, at least partially, within at least one macrocycle.
• the chromophores are substantially incarcerated within at least one macrocycle.
• the macrocycle is generally a rigid, bulky, chemically-stable compound.
• the macrocycle may have a generally hydrophobic interior and a generally hydrophilic exterior.
• the macrocycle may suitably comprise at least 7 carbon atoms.
• the at least one chromophore may be part of a chromophoric compound.
• the chromophoric compound may comprise one or more chromophores.
• the chromophoric compound may be partially incarcerated within at least one macrocycle.
• chromophoric compound may be substantially incarcerated within at least one macrocycle.
• a suitable oil soluble dye in which the at least one chromophore is part of a chromophoric compound which is partly incarcerated within at least one macrocycle is a rotaxane.
• the oil-soluble dye is a rotaxane.
• a rotaxane comprises a mechanically-interlocked molecular architecture comprising a generally "dumbbell" shaped molecule which is threaded through a macrocycle.
• the ends of the dumbbell (often called stoppers) are generally larger than the internal diameter of the macrocycle ring.
• the part of the dumbbell which is generally smaller than the internal diameter of the macrocycle is often referred to as the thread.
• the thread comprises the chromophore of the dye which is incarcerated, at least partially, within a macrocycle.
• the dumbbell shaped molecule of the rotaxane being a chromophoric compound is only partially incarcerated within the macrocycle.
• the chromophore of the dumbbell shaped chromophoric molecule may be partially incarcerated within the macrocycle.
• the chromophore of the dumbbell shaped chromophoric molecule may be substantially incarcerated within the macrocycle.
• the stoppers (which are potentially exposed) need not comprise any chromophore but should generally have sufficient steric bulk to prevent 'de-threading' or disassociation of the dumbbell and the macrocycle and should be generally resistive to degradation, for example generally chemically inert.
• the macrocycle may be a
• cyclodextrin for example an a-cyclodextrin or a ⁇ -cyclodextrin.
• a suitable macrocycle is a-cyclodextrin.
• Rotaxane dyes may be made according to the Suzuki synthesis coupling method.
• the Suzuki synthesis coupling method is described by Anderson et al in Chem. Commun., 2001, 493-494, the contents of which are incorporated by reference and which describes stilbenes and tolan rotaxanes of a-cyclodextrins and ⁇ -cyclodextrins prepared from diboronic acids 3a to 3c with stoppers 2a and 2b.
• Suitable tolan rotaxane Id a- cyclodextrin rotaxane derivative of 4,4'-(ethyne-l,2-diylbis(4,l- phenylene))bis(naphthalene-2,7-disulfonic acid), may be made using the diboronic acid of tolan 3b, with stopper 2a and ⁇ -cyclodextrin, and tolan rotaxane le, beta-cyclodextrin rotaxane derivative of 4,4'-(ethyne-l,2-diylbis(4,l-phenylene))bis(naphthalene-2,7- disulfonic acid), may be made using the diboronic acid of tolan 3b, with stopper 2a and ⁇ - cyclodextrin.
• alpha-cyclodextrin rotaxane derivative of (E)- 4',4'"-(ethene-l,2-diyl)bis(([l, -biphenyl]-3,5-dicarboxylic acid)) may be made using the diboronic acid of tolan 3b, with stopper 2b and a-cyclodextrin.
• Suitable tolan rotaxane lg, alpha-cyclodextrin rotaxane derivative of 4',4'"-(ethyne-l,2-diyl)bis(([l,r-biphenyl]-3,5- dicarboxylic acid)), may be made using the diboronic acid of tolan 3c, with stopper 2b and a-cyclodextrin.
• suitable stilbene rotaxane lb, alpha-cyclodextrin rotaxane derivative of (E)-4,4'-(ethene-l,2-diylbis(4,l-phenylene))bis(naphthalene-2,7-disulfonic acid) may be made using the diboronic acid of stilbene 3c, with stopper 2a and a-cyclodextrin.
• Suitable stilbene rotaxane lc, beta-cyclodextrin rotaxane derivative of (E)-4,4'-(ethene-l,2- diylbis(4,l-phenylene))bis(naphthalene-2,7-disulfonic acid), may be made using the diboronic acid of stilbene 3c, with stopper 2a and ⁇ -cyclodextrin.
• the diboronic ester may be prepared by reacting the corresponding diboronic acid, with ethylene glycol and toluene, for example at an elevated temperature of for example 130 °C, for a period for example of 12 hours.
• the diboronic ester may then be coupled with a cyclodextrin for example by the Suzuki coupling reaction. This may involve reacting the diboronic acid with a-cyclodextrin in the presence of sodium salt of 5-iodo isophthalic acid, sodium carbonate, palladium acetate and deionised water. This may be performed at elevated temperature for example at 45 °C, for a period for example of 12 hours.
• the diboric acid may be made by reacting the corresponding bromo-compound with tri-isopropyl borate in the presence of n-butyl lithium to produce the corresponding boric acid compound which may then be reacted with ethylene glycol to make the borate ester, which may be used in the Suzuki reaction.
• Rotaxanes with stilbene having the sulphonic acid stoppers of the stilbene referred to by Anderson et al may be used if the polarity of the sulphonic acids is mitigated to facilitate oil solubility for example through the formation of sulphonamide bonds with pendant alkyl groups of suitable length.
• the at least one chromophore may be part of a chromophoric compound which is substantially incarcerated within at least one macrocycle.
• the macrocycle may be a carcerand or part thereof.
• a carcerand is a molecule that irreversibly incarcerates one or more guest molecules within its confines for example by virtue of having small pores relative to the size of the guest(s).
• Such a combination of carcerand and one or more guest molecules is usually called a carceplex
• Carceplexes may comprise two or more covalently bonded bowl shaped molecules
• Carceplexes may comprise two cavitands or more than two cavitands, for example three, four, five, six or seven cavitands
• the carceplex may be a bis or tris carceplex.
• Bis carceplexes comprise two cavities each comprised of two or more cavitands.
• Tris carceplexes comprise three cavities each comprised of two or more cavitands.
• the chromophore of the dye is part of a chromophoric compound.
• Suitable chromophoric compounds include tolans.
• Other suitable chromophoric compounds include stilbenes.
• Other suitable chromophoric compounds include azo compounds.
• chromophoric compounds include fluorescent fused polycyclic aromatic compounds, for example pyrene, perylene, coronene and derivatives thereof including fused polycyclic aromatic compounds comprising one or more of pyrene moiety, perylene moiety, coronene moiety and combinations thereof.
• Perylene has the general structural formula (II):
• Phthalocyanine has the general structural formula (IV):
• Suitable chromophoric compounds include cyanines, for example cyanine 3 and cyanine 5.
• Cyanine 3 and cyanine 5 have the general structural formulae (V) and (VI):
• R groups are independently hydrocarbyl or substituted hydrocarbyl groups.
• Suitable R groups include independently, alkyl groups, for example methyl groups.
• Other suitable cyanines include those shown with structural formula (V) and (VI) but with counter ions other than iodide anion.
• Suitable other counter ions include any halide, PF 6 ⁇ BF 4 " , sulphate, alkyl or aryl sulfonate and alky or aryl perchlorate.
• Non-halide counter ions would be preferred for lubricant compositions where halide is undesirable, for example alkyl or aryl sulphonate.
• Carboxylate may be suitable counter ions, if sufficiently stable.
• Another suitable chromophoric compound may be a BODIPY (boron- dipyrromethene).
• BODIPY boron- dipyrromethene
• Such compounds are fluorescent chromophoric compounds. These compounds are characterised by comprising a dipyrromethene complexed with a disubstituted boron atom; commonly the boron atom is bonded to two fluorine atoms and may have the general structural formula VII.
• heteroatoms and functional groups thereof are directly attached to the dipyrromethane moiety.
• Heteroatoms (and functional groups thereof) or hydrocarbyl groups may be directly attached to the boron atom as in the general structural formula VIII in which Xi and X 2 groups may be independently F, CI, Br, I, O-hydrocarboyl (aromatic or aliphatic), hydrocarboyl (aromatic or aliphatic),
• the chromophoric compound When a chromophoric compound is incarcerated within a carcerand of a carceplex, the chromophoric compound will be smaller than the cavity of the carceplex.
• the tolans, stilbenes, azo or cyanine compounds are dumbbell shaped molecules in which the chromophore is part of a thread which is generally smaller than the internal diameter of the macrocycle and the ends of the dumbbells or stoppers are generally larger than the internal diameter of the macrocycle.
• the X- and Y- hydrocarbyl groups may independently be substituted.
• the X- and Y- hydrocarbyl groups may be independently phenyl groups which may be independently substituted.
• the substituents may independently comprise heteroatoms.
• the heteroatoms may be one or more of nitrogen, sulphur and oxygen.
• Suitable azo compounds include:
• Suitable azo compounds include derivatives of such compounds.
• Suitable azo compounds are also described in EP- 1831313 -B 1.
• Tolans have a general chemical structure comprising two substituted or unsubstituted phenyl groups bridged through an alkynyl group, usually an ethynyl group.
• Suitable tolans include:
• tolan also sometimes called 2-phenylethynyl benzene or diphenylacetylene
• l,4-bis(phenylethynyl) benzene also sometimes called 2-phenylethynyl benzene or diphenylacetylene
• Suitable tolans include derivatives of such compounds.
• Stilbenes have a general chemical structure comprising two substituted or unsubstituted phenyl groups bridged through an alkenyl group, usually an ethylene group. Suitable stilbenes include:
• E-Stilbene also sometimes called trans-stilbene, E-l,2-diphenylethylene, trans- 1,2-diphenylethylene or 1,2-diphenylethylene;
• Z-Stilbene (sometimes called cis-stilbene, Z-l,2-diphenlyethylene or cis- 1,2- diphenylethylene);
• Suitable stilbenes include derivatives of such compounds.
• the chromophoric compound may comprise more than one chromophore, for example it may comprise two or more conjugated chromophores.
• Such multiple chromophoric compounds may be incarcerated by more than one macrocycle and/or by a macrocycle comprising more than one cavity, for example by a bis or tris carceplex.
• the chromophoric compound is a dumbbell shaped molecule
• one or both of the stoppers of the chromophoric compound may be linked to the stopper of another macrocycle.
• the dye is a rotaxane
• the chromophore is part of a chromophoric compound which is a tolan, stilbene or azo compound and the macrocycle is a-cyclodextrin or a substituted derivative thereof.
• the dye is a rotaxane
• the chromophore is part of a chromophoric compound which is a tolan or a stilbene and the macrocycle is a- cyclodextrin or a substituted derivative thereof.
• the dye is a rotaxane
• the chromophore is part of a chromophoric compound which is a tolan, stilbene or azo compound and the macrocycle is ⁇ -cyclodextrin or a substituted derivative thereof.
• the dye is a rotaxane
• the chromophore is part of a chromophoric compound which is a tolan or a stilbene and the macrocycle is ⁇ -cyclodextrin or a substituted derivative thereof.
• the chromophoric compound(s), may comprise independently, one or more substituents, independently of any substituents on the macrocycle(s).
• the chromophore of the dye is part of a chromophoric compound which is a dumbbell shaped molecule having ends or stoppers.
• the ends or stoppers may comprise independently, one or more substituents.
• the chromophoric compound is a fluorescent stilbene dye comprising independently, one or more substituents which may be independently, for example alkyl or aryl ester, ether or amide substituent groups.
• the macrocycle(s), may comprise one or more substituents, independently of any substituents on the chromophoric compound(s).
• substituents may be introduced onto or formed on the macrocycle
• the one or more substituents may aid solubility of the dye, for example in an oil of lubricating viscosity in a lubricating oil composition.
• the one or more substituents may aid solubility of the dye, for example in a liquid fuel composition.
• Suitable substituents comprise hydrocarbyl moieties.
• the hydrocarbyl moieties are alkyl groups or aryl groups.
• the substituents may comprise functional moieties.
• the functional moieties may link hydrocarbyl moieties to the chromophoric compound and/or macrocycle.
• Suitable substituents include alkyl or aryl: ethers, esters, amides, sulfonates, sulfonamides, imides, thioethers, ketals, acetals, heterocyclic groups (for example triazoles, which may be substituted through an azide alkyne Huisgen cycloaddition), borate esters, amines, hydrazines, hydroxyl groups, thioesters and siloxanes.
• Suitable substituents also include:
• antioxidants for example phenolic, stearic, diphenylamine or hindered phenol substituents
• Suitable amines substituent groups include C ⁇ to C 30 amines, for example C 6 to C 8 amines.
• Suitable ester substituents may be esters of carboxylic acids.
• carboxylic acids include Q to C 30 carboxylic acids, for example C 18 , C 20 , C 22 and C 24 carboxylic acids.
• the carboxylic acids may be saturated.
• the carboxylic acids may be unsaturated.
• the chromophoric compound and/or macrocycle comprises carboxylic acid groups, these may be esterified with an alkanol to form ester substituents (for example by reaction of an unsubstituted compound with thionyl chloride and an alkanol).
• Suitable alkanols include Ci to C 30 alkanols, for example alkanols which comprises alkyl groups which are independently methyl, ethyl, propyl, t-butyl, hexyl, octyl or decyl alkyl groups.
• Suitable amide substituents include amides of carboxylic acids.
• carboxylic acids include d to C 30 carboxylic acids, for example C 18 , C 20 , C 22 and C 24 carboxylic acids.
• the carboxylic acids may be saturated.
• the carboxylic acids may be unsaturated. Also, if the
• chromophoric compound and/or macrocycle comprises carboxylic acid groups, these may be reacted with an amine to form amide substituents.
• Suitable amines include Ci to C 30 amines, for example amines comprising alkyl groups which are independently methyl, ethyl, propyl, t-butyl, hexyl, octyl or decyl alkyl groups.
• Amide substituted compounds may be made by reaction of the corresponding ester with an amine.
• Suitable ether substituents include alkyl ether substituents. Suitable alkyl groups of the ether substituents include independently d to C 30 alkyl groups. More suitable alkyl groups are independently methyl, ethyl, propyl, t-butyl, hexyl, octyl or decyl alkyl groups. Ether substituted compound may be made by reduction of the corresponding ester or reduction of the corresponding alkanol followed by etherification.
• Thioether substituents may be made by alkylation of thiol substituents, for example by reaction with a hydrocarbyl halide in the presence of a base.
• the macrocycle (for example a cyclodextrin) may be formed from a compound having hydroxyl groups. Substituents may be introduced onto the macrocycle by reaction of the hydroxyl groups with suitable reagents for example, when the macrocycle is a- cyclodextrin shown in simplified form with general structural formula (IX) below:
• ether substituents may be introduced using Williamson etherification by reaction of ⁇ -cyclodextrin with alkyl halide R-X, according to the reaction scheme (X) below in which R is an alkyl group:
• Silane ether substituents may be introduced to the macrocycle (for example a-cyclodextrin) by reaction of the hydroxyl groups with a silyl halide (for example silyl chloride) according to the reaction scheme (XI) below in which TBS corresponds to tert-butyl silane:
• hydroxyl groups of a macrocycle for example a-cyclodextrin
• substituents with or without inversion of stereochemistry
• Thiol substituents might be introduced this way. These being more nucleophilic than the hydroxyl groups might facilitate introduction of other substituents.
• the substituents may also include low molecular weight polymers.
• the low molecular weight polymers may have a molecular weight in the range of 500 to 50000.
• the low molecular weight polymers might comprise functional groups for example amines.
• Low molecular weight substituted dyes may be made by grafting the low molecular weight polymer onto the macrocycle and/or onto the stopper of a rotaxane dye.
• the dye is oil-soluble.
• oil-soluble is meant that the dye is soluble in an oil of lubricating viscosity and/or a liquid fuel in an effective amount.
• the dye may be soluble in an oil of lubricating viscosity in an amount of at least 5 ppm by weight.
• the dye may be soluble in a liquid fuel in an amount of at least 5 ppb by weight.
• the dye may be soluble in an oil of lubricating viscosity and/or a liquid fuel in an amount of up to 1000 ppm weight.
• the solubility may be determined at ambient temperature, for example at 20 °C.
• the solubility may be determined at atmospheric pressure.
• the dye is present in the lubricating oil composition in an amount of at least
• the dye is present in the lubricating oil composition in an amount of up to 2000 ppm by weight, for example in an amount of up to 1000 ppm by weight.
• the dye is present in the lubricating oil composition in an amount of 5 to 2000 ppm by weight, for example 5 to 1000 ppm by weight. More suitably, the dye is present in the lubricating oil composition in an amount of 10 to 500 ppm by weight, for example 10 to 200 ppm by weight.
• the lubricating oil composition comprises a major amount of a base oil of lubricating viscosity and a minor amount of at least one oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle.
• Major amount means greater than 50% and minor amount means less than 50 % by weight.
• the lubricating oil composition and the oil of lubricating viscosity may comprise base oil.
• Base oil comprises at least one base stock.
• the oil of lubricating viscosity may comprise one or more additives other than the dye.
• the lubricating oil composition and/or the oil of lubricating viscosity 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.
• the base stocks may be Group I, II, III, IV and V base stocks as defined according to
• 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.
• a suitable Group I base stock is AP/E core 150, available from ExxonMobil.
• Suitable Group II basestocks are EHC 50 and EHC 110, available from ExxonMobil.
• Suitable group III base stocks include Yubase 4 and Yubase 6. Yubase 4 and Yubase 6 basestocks are available from SK Lubricants.
• Suitable Group V base stocks are ester base stocks, for example Priolube 3970, available from Croda International pic.
• Suitable Group IV base stocks include hydrogenated oligomers of alpha olefins.
• the oligomers may be made by free radical processes, Zeigler catalysis or by cationic Friedel-Crafts catalysis.
• Polyalpha olefin base stocks may be derived from Cg, C 10 , C 12 , C 14 olefins and mixtures of one or more thereof.
• Suitable Group V basestocks include poly alkoxy glycols (PAG's) and alkylated naphthalenes. Table 1
• the lubricating oil composition and the oil of lubricating viscosity may comprise one or more base oil and/or base stock which is/are natural oil, mineral oil (sometimes called petroleum-derived oil or petroleum-derived mineral oil), non-mineral oil and mixtures thereof.
• Natural oils include animal oils, fish oils, and vegetable oils.
• Mineral oils include paraffinic oils, naphthenic oils and paraffinic-naphthenic oils. Mineral oils may also include oils derived from coal or shale.
• Suitable base oils and base stocks may be derived from processes such as chemical combination of simpler or smaller molecules into larger or more complex molecules (for example polymerisation, oligomerisation, condensation, alkylation, acylation).
• Suitable base oils and base stocks may be derived from gas-to-liquids materials, coal- to-liquids materials, biomass-to-liquids materials and combinations thereof.
• Gas-to-liquids may be 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 and base oils may be obtained from the 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. Such processes are described in WO 2008/124191.
• Biomass-to-liquids (sometimes also referred to as BTL materials) may be
• Coal-to-liquids materials may be made by gasifying coal to make synthesis gas which is then converted to hydrocarbons.
• the base oil and/or oil of lubricating viscosity may have a kinematic viscosity at 100 °C 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 oil composition may be a multi-grade lubricating oil composition according to the API classification xW-y where x is 0, 5, 10, 15 or 20 and y is 20, 30, 40, 50 or 60 as defined by SAE J300 2004, for example 5W-20, 5W-30 or OW-20.
• the lubricating oil composition may have an HTHS viscosity at 150 °C of at least 2.6cP.
• HTHS viscosity may be measured according to ASTM D4683, CEC L-36-A-90 or ASTM D5481.
• the lubricating oil composition may have an HTHS viscosity at 150 °C according to
• ASTM D4683 of from 1 to ⁇ 2.6cP, for example about 1.8cP.
• the lubricating composition may be a monograde lubricating oil composition according to the API classification, for example an SAE 20, 30, 40, 50 or 60 grade.
• the lubricating oil composition may be prepared by admixing an oil of lubricating viscosity with an effective amount of the oil-soluble dye together with optionally at least one other lubricating oil additive.
• the oil of lubricating viscosity may be admixed with the oil-soluble dye in one or more steps by methods known in the art.
• the at least one oil-soluble dye may be admixed as one or more additive concentrates or part additive package concentrates, optionally comprising solvent or diluent.
• the oil of lubricating viscosity may be prepared by admixing in one or more steps by methods known in the art, one or more base oils and/or base stocks optionally with one or more additives and/or part additive package
• an additive concentrate for use in the preparation of a lubricating oil composition which concentrate comprises (i) at least one oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and (ii) at least one internal combustion engine lubricating oil composition additive.
• the concentration of the oil-soluble dye in the additive concentrate may be an amount suitable to provide the required concentration when used in a lubricating oil composition.
• the additive concentrate may be used in a lubricating oil composition in an amount of 0.5 to 20 % by weight. Therefore, the amount of the oil-soluble dye and any other additives in the lubricant additive concentrate may be more concentrated than that in the lubricating oil composition, for example by a factor of from 1 :0.005 to 1 :0.20.
• Lubricating oil composition additives for example internal combustion engine crankcase lubricating oil additives, which may be present in the lubricating oil composition and/or additive concentrate include anti-wear additives and friction modifiers.
• the lubricating oil composition and the additive concentrate for a lubricating oil composition may also comprise other lubricating oil composition additives, for example other internal combustion engine lubricating oil additives.
• additives include dispersants (metallic and non-metallic), dispersant viscosity modifiers, detergents (metallic and non-metallic), 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, anti-seizure agents, wax modifiers, lubricity agents, anti-staining agents, chromophoric agents and metal deactivators.
• the lubricating oil composition and the additive concentrate for a lubricating oil composition may further comprise at least one anti-wear additive.
• Suitable anti-wear additives may be ash-producing additives or ashless additives.
• Suitable anti-wear additives include non-phosphorus containing additives for example, sulphurised olefins.
• Suitable anti-wear additives also include phosphorus-containing antiwear additives.
• Suitable ashless phosphorus-containing anti-wear additives include trilauryl phosphite and triphenylphosphorothionate and those disclosed in paragraph [0036] of US2005/0198894.
• Suitable ash-forming, phosphorus-containing anti-wear additives include dihydrocarbyl dithiophosphate metal salts.
• Suitable metals of the dihydrocarbyl dithiophosphate metal salts include alkali and alkaline earth metals, aluminium, lead, tin, molybdenum, manganese, nickel, copper and zinc.
• Particularly suitable dihydrocarbyl dithiophosphate metal salts are zinc dihydrocarbyl dithiophosphates (ZDDP).
• ZDDP's may have hydrocarbyl groups independently having 1 to 18 carbon atoms, suitably 2 to 13 carbon atoms or 3 to 18 carbon atoms, more suitably 2 to 12 carbon atoms or 3 to 13 carbon atoms, for example 3 to 8 carbon atoms.
• Suitable hydrocarbyl groups include alkyl, cycloalkyl and alkaryl groups which may contain ether or ester linkages and also which may contain substituent groups for example, halogen or nitro groups.
• the hydrocarbyl groups may be alkyl groups which are linear and/or branched and suitably may have from 3 to 8 carbon atoms.
• Particularly suitable ZDDP's have 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 may be present in the lubricating oil composition at a concentration of 10 to 6000 ppm by weight of phosphorus, suitably 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.
• the lubricating oil composition and the additive concentrate for a lubricating oil composition may further comprise at least one friction modifier.
• Such friction modifiers may be ash-producing additives or ashless additives.
• Examples of such friction modifiers include fatty acid derivatives including for example, fatty acid esters, amides, amines, and ethoxylated amines.
• Suitable ester friction modifiers include esters of glycerol for example, mono-, di-, and tri-oleates, mono-palmitates and mono-myristates.
• a particularly suitable fatty acid ester friction modifier is glycerol monooleate.
• friction modifiers may 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 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-A1 - see paragraphs [0101] to [0117].
• Friction modifiers may 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. Suitable friction modifiers are described in WO 93/21288.
• Friction modifiers may be present in the lubricating oil composition at a
• concentration of 0.01 to 5 % by weight actives more suitably in the range of 0.01 to 1.5 % by weight actives.
• Molybdenum containing friction modifiers may be present in the lubricating oil composition at a concentration of 10 to 1000 ppm by weight molybdenum, more suitably in the range of 400 to 600 ppm by weight.
• Dispersants also called dispersant additives help hold solid and liquid contaminants for example resulting from oxidation of the lubricating oil 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. Suitable dispersants include oil soluble polymeric hydrocarbyl backbones each having one or more functional groups which are capable of associating with particles to be dispersed. The functional groups may be amine, alcohol, amine-alcohol, amide or ester groups. The functional groups may be attached to the hydrocarbyl backbone through bridging groups. More than one dispersant may be present in the additive concentrate and/or lubricating oil composition.
• Suitable ashless 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;
• Suitable 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.
• Suitable dispersants include hydrocarbyl-substituted succinic acid compounds, for example succinimide, succinate esters or succinate ester amides and in particular, polyisobutenyl succinimide dispersants.
• the dispersants may be borated or non-borated.
• a suitable dispersant is ADX 222. Dispersant Viscosity Modifiers.
• dispersancy may be provided by polymeric compounds capable of providing viscosity index improving properties and dispersancy.
• Such compounds are generally known as dispersant viscosity improver additives or
• Suitable dispersant viscosity modifiers may be prepared by 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 (molecular weights may be determined by gel permeation chromatography or light scattering methods). Suitable dispersant viscosity modifiers and methods of making them are described in WO 99/21902,
• More than one dispersant viscosity modifier may be present in the additive concentrate and/or lubricating oil composition.
• Detergents may help reduce high temperature deposit formation for example on pistons in internal combustion engines, including for example high-temperature varnish and lacquer deposits, by helping to keep finely divided solids in suspension in the lubricating oil composition.
• Detergents may also have acid- neutralising properties. Ashless (that is non-metal containing detergents) may be present.
• Metal-containing detergent comprises at least one metal salt of at least one organic acid, which is called soap or surfactant.
• Detergents may be 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. Suitable metals include Group I and Group 2 metals, more suitably calcium, magnesium and combinations thereof, especially calcium. More than one metal may be present.
• Suitable organic acids include sulphonic acids, phenols (sulphurised or preferably sulphurised and including for example, phenols with more than one hydroxyl group, phenols with fused aromatic rings, phenols which have been modified for example 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.
• non-metallic detergents may be present. Suitable non- metallic detergents are described in US7622431.
• More than one detergent may be present in the lubricating oil composition and/or additive concentrate.
• the detergents may be present in the lubricating oil composition in a total amount of 0.01 to 20 %, for example 0.01 to 6 % (for example for applications such as automotive engine lubricants) or for example 5 to 20 % by weight (for example for applications such as marine engine lubricants).
• Viscosity index improvers (also called viscosity modifiers, viscosity improvers or VI improvers) impart high and low temperature operability to a lubricating oil composition and facilitate it remaining shear stable at elevated temperatures whilst also exhibiting acceptable viscosity and fluidity at low temperatures.
• Suitable viscosity modifiers include high molecular weight hydrocarbon 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 may have additional functions as multifunction viscosity modifiers. More than one viscosity index improver may be present.
• pour point depressants also called lube oil improvers or lube oil flow improvers
• Suitable 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 may be present.
• Rust inhibitors generally protect lubricated metal surfaces against chemical attack by water or other contaminants.
• Suitable 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 may be present.
• Corrosion inhibitors reduce the degradation of metallic parts contacted with the lubricating oil composition.
• Suitable 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.
• Suitable epoxidised ester corrosion inhibitors are described in US2006/0090393.
• More than one corrosion inhibitor may be present.
• 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.
• Suitable 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
• More than one antioxidant may be present. More than one type of antioxidant may be present. More than one type of antioxidant may be present. More than one type of antioxidant may be present.
• Anti-foams (sometimes also called anti-foaming agents) retard the formation of stable foams.
• Suitable 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 may be present.
• 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.
• Suitable 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 may be present.
• lubricating oil composition additives that is internal combustion engine crankcase lubricating oil additives, which may be present in the lubricating oil composition and/or additive concentrate 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
• Some additives may exhibit more than one function.
• the additive concentrate for a lubricating oil composition may comprise solvent.
• the solvent is a non-aqueous solvent.
• Suitable solvents include highly aromatic, low viscosity base stocks, for example 100N, 60 N and 100SP base stocks.
• the additive concentrate for a lubricating oil composition comprises oil-soluble dye which comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and a non-aqueous solvent, optionally with at least one lubricating oil additive.
• lubricating oil composition additives that is internal combustion engine crankcase lubricating oil additives, in the lubricating oil 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.
• each type of additive may be present. Within each type of additive, more than one class of that type of additive may be present. More than one additive of each class of additive may be present. Additives may suitably be supplied by
• the oil-soluble dye may be used for detecting leakage in a lubricated apparatus.
• a method of detecting leakage of a lubricating oil composition in a lubricated apparatus which is an internal combustion engine comprises lubricating the apparatus with a non- aqueous lubricating oil composition, supplying to the lubricating oil composition at least one oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and detecting the presence of leaked lubricating oil composition by detecting the presence of the dye.
• the lubricating oil composition may be a lubricating oil composition according to the present invention.
• Oil-soluble dye comprising a chromophore
• Friction modifiers 0.01 to 5 % 0.01 to 1.5 %
• Dispersants 0.1 to 20 % 0.1 to 8 %
• Detergents example 0.01 to 6% 0.01 to 4 %
• Corrosion and/or rust inhibitors 0.01 to 5 % 0.01 to 1.5%
• Anti-oxidants 0.1 to 10 % 0.5 to 5 %
• an oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle for marking a non-aqueous internal combustion engine crankcase lubricating oil composition.
• the dye comprising at least one chromophore which is incarcerated, at least partially, within at least one macrocycle, for example a stilbene rotaxane dye exhibits enhanced resistance to thermal and/or chemical degradation, for example when used in the operating conditions of the crankcase of an internal combustion engine - for example when the dye is used in a non-aqueous lubricating oil composition which is used to lubricate the crankcase of an internal combustion engine.
• the lubricated apparatus may comprise the crankcase of an internal combustion engine.
• the dye may be supplied to the lubricating oil as a component in liquid fuel composition used to operate the internal combustion engine, at least a portion of said liquid fuel composition comprising dye passing into the lubricating oil composition in the crankcase of the engine during operation of the engine.
• the lubricating oil composition used to lubricate the crankcase of the internal combustion engine may be a lubricating oil composition of the present invention.
• the oil-soluble dye may be used for marking a non-aqueous lubricating oil composition and/or a liquid fuel composition.
• a liquid fuel composition which fuel composition comprises an oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle.
• the fuel composition may be used in a method of detecting leakage of a lubricating oil composition in a lubricated apparatus which comprises the crankcase of an internal combustion engine, which method comprises lubricating the apparatus with a nonaqueous lubricating oil composition and supplying to the lubricating oil composition at least one oil-soluble dye as a component in the liquid fuel composition used to operate the engine, at least a portion of said fuel and dye passing into the lubricating oil composition in the crankcase of the engine during operation of the engine.
• the lubricating oil comprises an oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle.
• composition used to lubricate the crankcase of the internal combustion engine may be a lubricating oil composition comprising a major amount of a base oil of lubricating viscosity, at least one internal combustion engine crankcase lubricating oil additive and a minor amount of at least one oil-soluble dye, which dye comprises at least one
• the lubricating oil composition used to lubricate the crankcase of the internal combustion engine may be a lubricating oil composition of the present invention.
• the oil-soluble dye may be used to determine leakage of lubricating oil composition from one lubricated part of an apparatus to another lubricated part of the apparatus.
• the lubricated apparatus is an internal combustion engine (for example a 2 stroke engine, which might be used for example in marine applications), having a split lubrication system (for example using a cylinder oil composition to lubricate the combustion chamber and a system lubricating oil composition to lubricate the crankcase), supplying the oil-soluble dye to one or other of the lubricating oil compositions may be used to determine leakage of that lubricating oil composition into the other part of the lubricated apparatus.
• a split lubrication system for example using a cylinder oil composition to lubricate the combustion chamber and a system lubricating oil composition to lubricate the crankcase
• the oil-soluble dye may be used in a method of detecting leakage of system lubricating oil composition into a cylinder lubricating system in a lubricated apparatus comprising an internal combustion engine having a cylinder(s) lubricated with a cylinder lubricating oil composition and a crankcase lubricated with a system lubricating oil composition which method comprising supplying to the system lubricating oil composition an oil-soluble dye comprising at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and detecting the presence of leaked system lubricating oil composition in the cylinder lubricating oil composition by detecting the presence of the dye in the cylinder lubricating oil composition.
• the oil-soluble dye may be supplied to the system lubricating oil composition by being present in the lubricating oil composition when it is provided to the engine.
• the system lubricating oil composition may be a lubricating oil composition according to an aspect of the present invention.
• the oil-soluble dye may be used in a method of detecting leakage of cylinder lubricating oil composition into a system (e.g. crankcase) lubricating system in a lubricated apparatus comprising an internal combustion engine having a cylinder(s) lubricated with a cylinder lubricating oil composition and a crankcase lubricated with a system lubricating oil composition which method comprising supplying to the cylinder lubricating oil composition an oil-soluble dye comprising at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and detecting the presence of leaked cylinder lubricating oil composition in the system lubricating oil composition by detecting the presence of the dye in the system lubricating oil composition.
• the oil-soluble dye may be supplied to the system lubricating oil composition by being present in the lubricating oil composition when it is provided to the engine.
• the oil-soluble dye may be used to detect the ingress of components from the combustion chamber of an internal combustion engine into the crankcase of the internal combustion engine.
• the oil-soluble dye may be supplied to the combustion chamber of an internal combustion engine and the ingress of components into the crankcase of the of the engine, which is lubricated with a crankcase lubricating oil composition, may be detected by detecting and/or monitoring the presence of the dye in the crankcase lubricating oil composition.
• the dye may be supplied to the combustion chamber in a liquid fuel composition used to operate the engine. Additionally or alternatively, the dye may be supplied to the combustion chamber by being present in a lubricating oil composition.
• the internal combustion engine is a 2 stroke compression ignition engine
• the oil-soluble dye may be supplied as a component of cylinder oil supplied to the combustion chamber. Such 2 stroke engines may be used for marine applications.
• the presence of dye in the crankcase lubricating oil composition may be detected and/or monitored qualitatively or quantitatively.
• the presence of dye in the crankcase lubricating oil composition may be detected and/or monitored by visual inspection which may be facilitated using ultra-violet light, if the dye is a fluorescent dye.
• the presence of dye into the crankcase lubricating oil composition may be detected and/or monitored by spectroscopic or other analytical techniques.
• a method of detecting the ingress of components from the combustion chamber of an internal combustion engine into the crankcase of the internal combustion engine comprises:
• an oil soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle
• the method may be qualitative.
• the method may be quantitative.
• the method may be used to determine the rate of ingress of components from the combustion chamber of an internal combustion engine into the crankcase of the internal combustion engine, which method comprises:
• an oil- soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle
• a cylinder lubricating oil composition comprising at least one oil-soluble dye, which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle.
• oil soluble dye as hereindefined to a combustion chamber of an internal combustion engine (for example in liquid fuel used to operate the engine and/or in lubricating oil, for example a cylinder oil), ingress of components from the combustion chamber into the crankcase of the engine may be determined and/or leakage of lubricating oil composition from the crankcase of the engine may be detected.
• Enhanced resistance to degradation of dyes as hereindefined renders them suitable for such methods/uses.
• the internal combustion engine may be a spark-ignition, internal combustion engine, or a compression-ignition, internal combustion engine.
• the internal combustion engine may be a spark-ignition internal combustion engine used in automotive or aviation applications.
• the internal combustion engine may be a compression-ignition internal combustion engine used in automotive or marine applications.
• the internal combustion engine may be a two-stroke compression-ignition engine.
• the apparatus is an internal combustion engine and may be for example, a compression ignition engine, including a homogeneous charge compression ignition engine.
• the apparatus may be a power transmission. Suitable power transmissions include automatic transmissions, clutches (for example a dual clutch), turbines and gears.
• the apparatus may be used in automotive, aviation or marine applications and the like.
• the rate of ingress of fuel into crankcase lubricant is higher for spark- ignition internal combustion engines than for compression-ignition engines.
• the rate at which fuel ingresses into the crankcase lubricant for compression-ignition engines may depend and may increase depending upon the use of post-injection strategies for operation of the engine.
• the dye is present in the liquid fuel composition in an amount of at least 5 ppb by weight.
• the oil soluble dye is present in the liquid fuel composition in an amount of up to 1000 ppm by weight.
• the dye is present in the liquid fuel composition in an amount of 5 ppb to 250 ppm by weight.
• Suitable liquid fuels, particularly for internal combustion engines include
• Hydrocarbon fuels may be derived from mineral sources and/or from renewable sources such as biomass (e.g.
• biomass-to-liquid sources and/or from gas-to-liquid sources and/or from coal-to-liquid sources.
• Suitable sources of biomass include sugar (e.g. sugar to diesel fuel) and algae.
• Suitable oxygenate fuels include alcohols for example, straight and/or branched chain alkyl alcohols having from 1 to 6 carbon atoms, esters for example, fatty acid alkyl esters and ethers, for example methyl tert butyl ether.
• Suitable fuels may also include LPG-diesel fuels (LPG being liquefied petroleum gas).
• the fuel composition may be an emulsion. However, suitably, the fuel composition is not an emulsion. 2012/060368
• Suitable fatty acid alkyl esters include methyl, ethyl, propyl, butyl and hexyl esters.
• the fatty acid alkyl ester is a fatty acid methyl ester.
• the fatty acid alkyl ester may have 8 to 25 carbon atoms, suitably, 12 to 25 carbon atoms, for example 16 to 18 carbon atoms.
• the fatty acid may be saturated or unsaturated.
• the fatty acid alkyl ester is acyclic.
• Fatty acid alkyl esters may be prepared by esterification of one or more fatty acids and/or by transesterification of one or more triglycerides of fatty acids.
• the triglycerides may be obtained from vegetable oils, for example, castor oil, soyabean oil, cottonseed oil, sunflower oil, rapeseed oil (which is sometimes called canola oil), Jatropha oil or palm oil, or obtained from tallow (for example sheep and/or beef tallow), fish oil or used cooking oil.
• Suitable fatty acid alkyl esters include rapeseed oil methyl ester (RME), soya methyl ester or combinations thereof.
• the liquid fuel composition may be prepared by admixing in one or more steps (i) a hydrocarbon fuel, an oxygenate fuel or a combination thereof or one or more components therefor with (ii) an effective amount of at least one oil-soluble dye which dye comprises at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and (iii) optionally one or more additive for liquid fuel compositions.
• the fuel, fuels and/or components therefor may be admixed with at least one oil- soluble dye and optional one or more additives for liquid fuel compositions in one or more steps by methods known in the art.
• the oil-soluble dye and additives may independently be admixed as one or more additive concentrates or part additive package concentrates, optionally comprising solvent or diluent.
• the hydrocarbon fuel, oxygenate fuel or combination thereof may be prepared by admixing in one or more steps by methods known in the art, one or more base fuels and components therefor, optionally with one or more additives and/or part additive package concentrates.
• the additives, additive concentrates and/or part additive package concentrates may be admixed with the fuel or components therefor in one or more steps by methods known in the art.
• an additive concentrate for use in the preparation of a liquid fuel composition for use in an internal combustion engine which concentrate comprises an oil-soluble dye which comprises (i) at least one chromophore which is incarcerated, at least partially, within at least one macrocycle and (ii) at least one additive for liquid fuel compositions.
• the liquid fuel composition may be suitable for use in an internal combustion engine which is a compression-ignition internal combustion engine, suitably a direct injection diesel engine, for example of the rotary pump, in-line pump, unit pump, electronic unit injector or common rail type, or in an indirect injection diesel engine.
• the liquid fuel composition may be suitable for use in heavy and/or light duty diesel engines.
• the liquid fuel composition for compression-ignition internal combustion engines may have a sulphur content of up to 500 ppm by weight, for example, up to 15 ppm by weight or up to 10 ppm by weight.
• the fuel composition for compression-ignition internal combustion engines may meet the requirements of the EN590 standard, for example as set out in BS EN 590:2009.
• Suitable oxygenate components in the liquid fuel composition for compression- ignition internal combustion engines include fatty acid alkyl esters, for example fatty acid methyl esters.
• the fuel may comprise one or more fatty acid methyl esters complying with EN 14214 at a concentration of up to 7 % by volume.
• Oxidation stability enhancers may be present in the fuel composition comprising one or more fatty acid alkyl or methyl esters, for example at a concentration providing an action similar to that obtained with 1000 mg/kg of 3,5-di-tert-butyl-4-hydroxy-toluol (also called butylated hydroxyl -toluene or BHT).
• the liquid fuel composition may comprise one or more other dyes and/or markers.
• the liquid fuel composition for compression-ignition internal combustion engines may have one or more of the following, for example, as defined according to BS EN 590:2009 :- a minimum cetane number of 51.0, a minimum cetane index of 46.0, a density at 15 °C of 820.0 to 845.0 kg/m 3 , a maximum polycyclic aromatic content of 8.0% by weight, a flash point above 55°C, a maximum carbon residue (on 10% distillation) of 0.30 % by weight, a maximum water content of 200 mg/kg, a maximum contamination of 24 mg/kg, a class 1 copper strip corrosion (3 h at 50 °C), a minimum oxidation stability limit of 20 h according to EN 15751 and a maximum oxidation stability limit of 25 g/m according to EN ISO 12205, a maximum limit for lubricity corrected wear scar diameter at 60 °C of 460 ⁇ , a minimum viscosity at 40°C of 2.00 mm 2 /s and a maximum viscosity at 40
• the liquid fuel composition and the additive concentrate for a fuel composition suitable for use in a compression-ignition internal combustion engine may further comprise at least one friction modifier.
• friction modifiers include compounds described herein as friction modifiers for lubricating oil compositions and additive concentrates for lubricating oil compositions.
• the liquid fuel composition and the additive concentrate for a fuel composition suitable for use with a compression-ignition internal combustion engine may further comprise at least one lubricity additive.
• Suitable lubricity additives include tall oil fatty acids, mono- and di-basic acids and esters.
• the liquid fuel composition and the additive concentrate for a fuel composition suitable for use in a compression-ignition internal combustion engine may further comprise independently one or more cetane improver, one or more detergent, one or more anti- oxidant, one or more anti-foam, one or more demulsifier, one or more cold flow improver, one or more pour point depressant, one or more biocide, one or more odorant, one or more colorant (sometimes called dyes), one or more marker, one or more spark aiders and/or combinations of one or more thereof.
• suitable additives which may be present include thermal stabilizers, metal deactivators, corrosion inhibitors, antistatic additives, drag reducing agents, emulsifiers, dehazers, anti-icing additives, antiknock additives, anti- valve-seat recession additives, surfactants and combustion improvers.
• thermal stabilizers metal deactivators, corrosion inhibitors, antistatic additives, drag reducing agents, emulsifiers, dehazers, anti-icing additives, antiknock additives, anti- valve-seat recession additives, surfactants and combustion improvers.
• the additive concentrate for a fuel composition for a compression-ignition internal combustion engine may comprise solvent.
• the solvent in a non-aqueous solvent.
• suitable solvents include carrier oils (for example mineral oils), polyethers (which may be capped or uncapped), non-polar solvents (for example toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL”), and polar solvents (for example esters and alcohols e.g. hexanol, 2-ethylhexanol, decanol, isotridecanol and alcohol mixtures, for example those sold by Shell companies under the trade mark
• carrier oils for example mineral oils
• polyethers which may be capped or uncapped
• non-polar solvents for example toluene, xylene, white spirits and those sold by Shell companies under the trade mark "SHELLSOL”
• polar solvents for example esters and alcohols e.g. hexanol, 2-ethyl
• the additive concentrate for a liquid fuel composition comprises at least one dye comprising at least one chromophore which is incarcerated within at least on macrocycle, a non aqueous solvent and at least one additive for a liquid fuel composition.
• Suitable cetane improvers include 2-ethyl hexyl nitrate, cyclohexyl nitrate and di- tert-butyl peroxide.
• Suitable antifoams include siloxanes.
• Suitable detergents include polyolefin substituted succinimides and succinamides of polyamines, for example polyisobutylene succinimides, polyisobutylene amine succinimides, aliphatic amines, Mannich bases and amines and polyolefin (e.g. polyisobutylene) maleic anhydride.
• Suitable antioxidants include phenolic antioxidants (for example 2,6-di-tert-butylphenol) and aminic antioxidants (for example N,N'-di-sec-butyl-p-phenylenediamine).
• Suitable anti-foaming agents include polyether-modified polysiloxanes.
• the representative suitable and more suitable independent amounts of additives (if present) in the fuel composition suitable for a compression-ignition engine are given in Table 3.
• concentrations expressed in Table 3 are by weight of active additive compounds that is, independent of any solvent or diluent.
• the additive concentrate for a liquid fuel composition suitable for use in a compression-ignition internal combustion engine is suitably present in the fuel composition in a total amount in the range of 100 to 1500 ppm by weight. Therefore, the concentration ranges for each additive in an additive concentrate will be correspondingly higher than in the fuel composition, for example by a factor of 1 : 0.0002 to 0.0015.
• the additives may be used as part-packs, for example part of the additives (sometimes called refinery additives) being added at the refinery during manufacture of a fungible fuel and part of the additives (sometimes called terminal or marketing additives) being added at a terminal or distribution point.
• the at least one oil-soluble dye comprising at least one chromophore which is incarcerated within at least one macrocycle may suitably be added or used as a refinery or marketing additive, preferably as a marketing additive for example at a terminal or distribution point.
• the liquid fuel composition of the present invention may be suitable for use in an internal combustion engine which is a spark-ignition internal combustion engine.
• the liquid fuel composition for spark-ignition internal combustion engines may have a sulphur content of up to 50.0 ppm by weight, for example up to 10.0 ppm by weight.
• the liquid fuel composition for spark-ignition internal combustion engines may be leaded or unleaded.
• the liquid fuel composition for spark-ignition internal combustion engines may meet the requirements of EN 228, for example as set out in BS EN 228:2008.
• the fuel composition for spark-ignition internal combustion engines may meet the requirements of ASTM D 4814-09b.
• the liquid fuel composition for spark-ignition internal combustion engines may have one or more of the following, for example, as defined according to BS EN 228:2008 :- a minimum research octane number of 95.0, a minimum motor octane number of 85.0 a maximum lead content of 5.0 mg/1, a density of 720.0 to 775.0 kg/m 3 , an oxidation stability of at least 360 minutes, a maximum existent gum content (solvent washed) of 5 mg/100 ml, a class 1 copper strip corrosion (3 h at 50 °C), clear and bright appearance, a maximum olefin content of 18.0 % by weight, a maximum aromatics content of 35.0 % by weight, and a maximum benzene content of 1.00 % by volume.
• Suitable oxygenate components in the fuel composition for spark-ignition internal combustion engines include straight and/or branched chain alkyl alcohols having from 1 to 6 carbon atoms, for example methanol, ethanol, n-propanol, n-butanol, isobutanol, tert- butanol.
• Suitable oxygenate components in the fuel composition for spark-ignition internal combustion engines include ethers, for example having 5 or more carbon atoms.
• the fuel composition may have a maximum oxygen content of 2.7% by mass.
• composition may have maximum amounts of oxygenates as specified in EN 228, for example methanol: 3.0% by volume, ethanol: 5.0% by volume, iso-propanol: 10.0 % by volume, iso-butyl alcohol: 10.0 % by volume, tert-butanol: 7.0% by volume, ethers (C 5 or higher): 10% by volume and other oxygenates (subject to suitable final boiling point): 10.0% by volume.
• the fuel composition may comprise ethanol complying with EN 15376 at a concentration of up to 5.0% by volume.
• composition suitable for use in a spark-ignition internal combustion engine may comprise at least one friction modifier.
• friction modifiers include compounds described herein as friction modifiers for lubricating oil compositions and additive concentrates for lubricating oil compositions.
• composition suitable for use in a spark-ignition internal combustion engine may further comprise independently one or more detergent, one or more octane improver, one or more friction modifier, one or more anti-oxidant, one or more valve seat recession additive, one or more corrosion inhibitor, one or more anti-static agent, one or more odorant, one or more colorant, one or more marker and/or combinations of one or more thereof.
• the additive concentrate for a liquid fuel composition for a spark-ignition internal combustion engine may comprise solvent.
• Suitable solvents include polyethers and aromatic and/or aliphatic hydrocarbons, for example heavy naphtha e.g. Solvesso (Trade mark), xylenes and kerosine.
• Suitable detergents include poly isobutylene amines (PIB amines) and polyether amines.
• Suitable octane improvers include N-methyl aniline, methyl cyclopentadienyl manganese tricarbonyl (MMT) (for example present at a concentration of up to 120 ppm by weight), ferrocene (for example present at a concentration of up to 16 ppm by weight) and tetra ethyl lead (for example present at a concentration of up to 0.7 g/1, e.g. up to 0.15 g/i).
• MMT methyl cyclopentadienyl manganese tricarbonyl
• ferrocene for example present at a concentration of up to 16 ppm by weight
• tetra ethyl lead for example present at a concentration of up to 0.7 g/1, e.g. up to 0.15 g/i).
• Suitable anti-oxidants include phenolic anti-oxidants (for example 2,4-di-tert- butylphenol and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) and aminic antioxidants (for example para-phenylenediamine, dicyclohexylamine and derivatives thereof).
• phenolic anti-oxidants for example 2,4-di-tert- butylphenol and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid
• aminic antioxidants for example para-phenylenediamine, dicyclohexylamine and derivatives thereof.
• Suitable corrosion inhibitors include ammonium salts of organic carboxylic acids, amines and heterocyclic aromatics, for example alkylamines, imidazolines and
• Valve seat recession additives may be present at a concentration of up to 15000 ppm by weight, for example up to 7500 ppm by weight.
• the representative suitable and more suitable independent amounts of additives (if present) in the liquid fuel composition suitable for a spark-ignition engine are given in Table 4.
• concentrations expressed in Table 4 are by weight of active additive compounds that is, independent of any solvent or diluent.
• the additive concentrate for a liquid fuel composition suitable for use in a spark- ignition internal combustion engine is suitably present in a total amount in the range of 20 to 25000 ppm by weight. Therefore, the concentration ranges for each additive in an additive concentrate will be correspondingly higher than in the fuel composition, for example by a factor of 1 : 0.00002 to 0.025.
• the additives may be used as part-packs, for example part of the additives (sometimes called refinery additives) being added at the refinery during manufacture of a fungible fuel and part of the additives (sometimes called terminal or marketing additives) being added at a terminal of distribution point.
• the at least one dye comprising at least one chromophore which is incarcerated, at least partially, within at least one macrocycle may suitably be added or used as a refinery or marketing additive, preferably as a marketing additive for example at a terminal or distribution point.
• Figure 1 represents in schematic form the general molecular structure of an oil-soluble dye which is a rotaxane
• Figure 2 represents in schematic form, the general molecular structure of a cavitand
• Figures 3 and 5 represent in schematic form, the general molecular structure of carcerands
• Figures 4 and 6 represent in schematic form, the general molecular structure of carceplexes.
• Figure 2 represents in schematic form, the general molecular structure of a cavitand 8.
• Figure 3 represents in schematic form, the general molecular structure of a carcerand 9 which is a macrocycle comprised of two cavitands 8. Suitable cavitands are shown schematically in Figure 2.
• the cavitands 8 are covalently bonded together to define a cavity 12.
• Figure 4 represents in schematic form, the general molecular structure of a carceplex 10.
• the carceplex comprises a chromophoric compound 1 1 which comprising at least one chromophore 3.
• the chromophoric compound 1 1 is a guest molecule within the carceplex 10 being kinetically trapped within the confines of a carcerand 9.
• a suitable carcerand is shown schematically in Figure 3.
• the carcerand is a macrocycle comprised of two cavitands 8. Suitable cavitands are shown schematically in Figure 2.
• the cavitands 8 are covalently bonded together to define a cavity 12.
• the chromophoric compound and its chromophore are kinetically trapped in the cavity 12 and hence incarcerated within the carcerand 9 which is a macrocycle.
• the carceplex may comprise one or more than one guest chromophoric compounds, each of which may comprise one or more chromophore incarcerated within the macrocycle which is the carcerand.
• FIG 5 represents in schematic form a carcerand 9 which is a macrocycle comprised of four cavitands 8. Suitable cavitands are shown schematically in Figure 2. The cavitands are covalently bonded together to define a cavity 12.
• Figure 6 represents in schematic form, the general molecular structure of a carceplex
• the carceplex comprises a chromophoric compound 1 1 which comprising at least one chromophore 3.
• the chromophoric compound 1 1 is a guest molecule within the carceplex 10 being kinetically trapped within the confines of a carcerand 9.
• a suitable carcerand is shown schematically in Figure 5.
• the carcerand is a macrocycle comprised of four cavitands 8. Suitable cavitands are shown schematically in Figure 2.
• the cavitands 8 are covalently bonded together to define a cavity 12.
• the chromophoric compound and its chromophore are kinetically trapped in the cavity 12 and hence incarcerated within the carcerand 9 which is a macrocycle.
• the carceplex may comprise one or more than one guest chromophoric compounds, each of which may comprise one or more chromophore incarcerated within the macrocycle which is the carcerand.
• Diboronic ester was prepared according to the following equation (XII) in a 6 g lab scale according to the procedure described by Anderson et al in Chem. Commun., 2001, 493-494:
• Reagents Diboronic ester, sodium salt of 5-iodo isophthalic acid, ⁇ -cyclodextrin, sodium carbonate, palladium acetate and deionised water.
• the product was characterised by NMR.
• Aromatic protons were observed at 8.6 -7.3 ppm.
• the rotaxane compounds prepared according to Equations (XVIII) and (XIX) were found to be particularly hydrophobic and dissolved in heptane, cyclohexane and pentane at room temperature. Each of these two compounds was also dissolved under standard blending conditions (65° C) into a fully formulated engine oil comprising Group III base oil, a pour point depressant, a viscosity modifier and a market-general additive package comprising detergent(s), dispersants(s), antioxidant(s), anti-wear additive(s), friction modifier(s), antifoam additive(s) and diluent base oil for a storage stability test; each additive remained dissolved under storage stability conditions for over three months at concentrations of up to 1000 ppm. This indicates that they would be useful as stable dye components in lubricating oil compositions.
• Example - Testing of Dye Example - Testing of Dye.
• oil-soluble dye prepared in Experiment 3 (ethyl ester of a-cyclodextrin rotaxane of (E)-4',4'"-(ethane-l,2-diyl)bis(([l,l'-biphenyl]-3,5-dicarboxylic acid)) was tested in lubricating oil compositions in internal combustion engine tests.
• the lubricating oil composition comprised a base oil which consisted of a mixture of
• the lubricating oil also comprised lubricating oil composition additives: a pour point depressant, a viscosity modifier and a market-general additive pack comprising detergent(s), dispersant(s), anti-oxidant(s), ant-wear additive(s), friction modifier(s), antifoam additive(s) and diluent base oil.
• lubricating oil composition additives a pour point depressant, a viscosity modifier and a market-general additive pack comprising detergent(s), dispersant(s), anti-oxidant(s), ant-wear additive(s), friction modifier(s), antifoam additive(s) and diluent base oil.
• the lubricating oil compositions also comprised 0.005 % by weight rotaxane dye prepared in accordance with Experiment 3.
• the lubricating oil composition was tested as a crankcase lubricating oil in a spark ignition internal combustion engine in a TU5 (10 hour running in and flush followed by 72 hour main test run in 1.6 litre 4 cylinder, 8 valve engine) engine test protocol and as a crankcase lubricating oil in a compression ignition internal combustion engine in a DV4 engine test protocol (10 hour running-in and flush followed by 120 hour main test run in 1.4 litre, 4 cylinder, 8 valve CR DI engine).
• the presence of the dye did not appear to adversely affect the performance of the lubricating oil composition when used to lubricate the crankcase of the internal combustion engines.
• crankcase lubricating oil composition Samples of crankcase lubricating oil composition were taken during the tests and firstly cleaned using dialysis to remove high molecular weight additives and solid debris, from the low molecular weight additives (including dye) and base oil. The uv response of 15 ⁇ samples of the unused lubricating oil and dialysed fractions were compared photographically.
• soot generated in the early part of the DV4 test masked the ultraviolet performance of the dye, being reduced by 0.05% by weight soot and effectively completely masked at 0.3 % by weight soot, but this was avoided by using dialysis to remove the soot from the samples.
• the potential masking of the dye by soot might be overcome by using higher concentrations of dye.
• the lubricating oil samples showed a stronger response to ultraviolet light when the oil composition was irradiated with ultra-violet light having a wavelength of at 366nm compared to ultra-violet light of wavelength 254 nm following the DV4 test.
• the rotaxane dye showed generally poorer overall response than known dyes (Uniglow and Oil Sol (trade marks), both of which showed strong response to uv radiation of 254 nm)
• the presence of an underlying uv response up to and after 72 hours of operation shows that the rotaxane dye had useful resistance to degradation under the engine operating conditions, whereas the uv response for Oil Sol dye in lubricating oil composition generally falls away after about 48 hours operation of the internal combustion engine.
• the response of the oil-soluble dye may be enhanced by using higher
• the oil-soluble dye which has at least one chromophore which is incarcerated, at least partially, within at least one macrocycle has good resistance to degradation in the lubricating oil composition when used to lubricate the crankcase of an internal combustion engine.
• the oil-soluble dye may be used in a method of detecting leakage of a lubricating oil composition in a lubricated apparatus which method comprises lubricating the apparatus with a non-aqueous lubricating oil composition, supplying to the lubricating oil composition at least one oil-soluble dye as hereindefined and detecting the presence of leaked lubricating oil composition by detecting the presence of the dye.
• the dye may be supplied to the lubricating composition as a component in a liquid fuel composition which is used to operate the internal combustion engine, at least a portion of said liquid fuel composition comprising dye passing into the lubricating oil composition in the crankcase of the engine during operation of the engine.
• the dye may be present in the lubrication oil composition and/or in an additive concentrate for a lubricating oil composition or for a liquid fuel composition.
• the dye may be used for marking a non-aqueous lubricating oil composition and/or a liquid fuel composition.
• the oil-soluble dye may be used to 8

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Lubricants (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
• Examining Or Testing Airtightness (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46201664

Family Applications (1)

Country Status (2)

Cited By (7)

Citations (15)

• 2012
  • 2012-06-01 WO PCT/EP2012/060368 patent/WO2012168151A1/en active Application Filing
  • 2012-06-01 IN IN136DEN2014 patent/IN2014DN00136A/en unknown

Patent Citations (15)

Non-Patent Citations (6)

Also Published As

Similar Documents

Legal Events