WO2003070860A1 - Modificateur de coefficient de frottement pour combustibles hydrocarbones - Google Patents

Modificateur de coefficient de frottement pour combustibles hydrocarbones Download PDF

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Publication number
WO2003070860A1
WO2003070860A1 PCT/GB2003/000643 GB0300643W WO03070860A1 WO 2003070860 A1 WO2003070860 A1 WO 2003070860A1 GB 0300643 W GB0300643 W GB 0300643W WO 03070860 A1 WO03070860 A1 WO 03070860A1
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WIPO (PCT)
Prior art keywords
friction
friction modifier
group
fuel
composition
Prior art date
Application number
PCT/GB2003/000643
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English (en)
Inventor
Anthony Michael Cooney
Andrea Sneddon
John Martin Trainor
Alan Norman Ross
Simon Mulqueen
Original Assignee
The Associated Octel Company Limited
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 The Associated Octel Company Limited filed Critical The Associated Octel Company Limited
Priority to CA002475601A priority Critical patent/CA2475601A1/fr
Priority to EP03702764A priority patent/EP1481040A1/fr
Priority to AU2003205886A priority patent/AU2003205886A1/en
Priority to KR10-2004-7013027A priority patent/KR20040111359A/ko
Priority to US10/505,078 priority patent/US20050223630A1/en
Priority to JP2003569757A priority patent/JP2005517797A/ja
Publication of WO2003070860A1 publication Critical patent/WO2003070860A1/fr

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Classifications

    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • This invention relates to multi-functional friction modifiers and friction modifying compositions for hydrocarbon fuels, especially gasoline.
  • the invention relates to alkenylsuccinimide-based friction modifiers and friction modifying compositions for hydrocarbon fuels and especially gasoline.
  • Additive compositions for gasoline have to satisfy a large number of criteria, amongst the most important of which are: i) reduction of engine friction to increase fuel economy; ii) good lubrication to reduce wear; iii) elimination of carburettor and injector fouling; iv) good detergency in the intake port and intake valve regions of the engine; v) elimination of valve stick, a problem often associated with the use of high molecular weight detergents; vi) corrosion protection; vii) good demulsifying characteristics.
  • WO-A-98/11175 discloses an additive package comprising an ashless friction modifier, a deposit inhibitor and a carrier fluid.
  • current practice in the supply of gasoline is generally to pre-mix the fuel additives into a concentrate in a hydrocarbon solvent base, and then inject the concentrate into gasoline pipelines used to fill tankers prior to delivery to the customers.
  • the maximum amount of concentrate that can be incorporated into a tanker of gasoline is typically about 2000ppm based on the weight of the gasoline.
  • WO-A-93/20170 discloses a composition comprising succinimide detergents and mono end-capped polypropylene glycol. Each of the specifically disclosed detergents is derived from a polyalkylene polyamine comprising two primary amine groups. The resultant succinimide detergent comprises a terminal amine group.
  • the present invention provides a friction modifier of the formula R 1 -L- N(R 2 )(R 3 ) wherein R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group, with the proviso that if one of R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H, the hydrocarbyl group does not contain a terminal amine.
  • the present invention provides a friction modifying composition
  • a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
  • these new friction modifiers and friction modifying compositions are multi-functional and exhibit, in addition to their friction modifying characteristics, good intake valve detergency, good valve stick performance and good packagability.
  • the multi-functional nature of the friction modifiers and friction modifying compositions according to the present invention enables them to be used in the substantial absence of any additional friction modifier or detergent. This is advantageous, for example, because of the need to conform to limits on the amount of fuel additive incorporated into fuel.
  • the term “friction modifier” it is meant a substance capable of modifying friction.
  • the term “friction modifier” it is meant a substance capable of reducing friction.
  • the term “friction modifier” refers to a substance which is capable of reducing friction, when dosed into a fuel which is subsequently combusted in a combustion engine.
  • the term "friction modifier” refers to a substance which, at a treat rate of 120mg/l in unleaded gasoline generates a Wear Scar Diameter in the High Frequency Reciprocating Rig test at 20°C of less than 500 microns, preferably less than 450 microns, more preferably less than 400 microns.
  • hydrocarbyl group it is meant a group comprising at least C and H and may optionally comprise one or more other suitable substituents.
  • substituents may include alkoxy-, nitro-, a hydrocarbon group, an N- acyl group, a cyclic group etc.
  • a combination of substituents may form a cyclic group.
  • the hydrocarbyl group comprises more than one C then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group.
  • the hydrocarbyl group may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for instance, nitrogen and oxygen.
  • R 1 is a hydrocarbon group.
  • hydrocarbon group it is meant a group comprising only C and H.
  • the hydrocarbon group may be saturated or unsaturated.
  • the hydrocarbon group may be straight chained or branched.
  • R 1 is a branched or straight chain alkyl group. More preferably R 1 is a branched alkyl group.
  • R 1 is polyisobutene.
  • High reactivity polyisobutenes are suitable for use in the invention.
  • High reactivity is defined as a polyisobutene wherein at least 50%, preferably 70% or more of the terminal olefinic double bonds are of the vinylidene type.
  • polyisobutenyl substituted succinic anhydrides PIBSA
  • Suitable processes include thermally reacting polyisobutenes with maleic anhydride (see for example US-A-3,361,673 and US-A-3,018,250), and reacting a halogenated, in particular a chlorinated, polyisobutene (PIB) with maleic anhydride (see for example US-A-3, 172,892).
  • PIB chlorinated, polyisobutene
  • the polyisobutenyl succinic anhydride can be prepared by mixing the polyolefin with maleic anhydride and passing chlorine through the mixture (see for example GB-A-949,981 ).
  • reaction product of these processes will be a complex mixture of unreacted polymer as well as the product polyisobutenyl succinic acid anhydride, the polyisobutenyl substituent being connected to either one or both of the alpha carbon atoms of the succinic acid group.
  • R 1 may have a molecular weight selected to provide the required properties of the detergent compound.
  • R 1 has a molecular weight of from 800 to 1300.
  • R 1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
  • R 1 may have from 10 to 200 carbons or from 10 to 100 carbons.
  • the friction modifier of the formula R 1 -L-N(R 2 )(R 3 ) may or may not comprise optional linker L. If L is present it may be any suitable group. Suitable groups include • Ci- ⁇ hydrocarbyl groups optionally including one or more, preferably two, carbonyl groups, • C 1-6 hydrocarbon groups optionally including one or more, preferably two, carbonyl groups,
  • e and f are independently an integer of from 0 to 6.
  • the friction modifier of the present invention contains a nitrogen moiety N(R 2 )(R 3 ) attached to the hydrocarbyl group R 1 via optional linker L.
  • the groups and R 2 and R 3 of the nitrogen moiety are independently H or a hydrocarbyl group.
  • R 2 and R 3 may be H and the other of R 2 and R 3 may be hydrocarbyl
  • R 2 and R 3 may be hydrocarbyl.
  • R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group.
  • the nitrogen may contain either a double bond to a single atom of the group L or may be bonded to two different moieties of group L to form a cyclic group.
  • optional group L is not present these explanations equally apply to the connection between R 1 and N(R 2 )(R 3 ).
  • R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H
  • the hydrocarbyl group does not contain a terminal amine.
  • the hydrocarbyl group is an amine or polyamine the amine or amine units are selected from secondary and tertiary amines.
  • Suitable derivatives include esters and ethers.
  • the hydrocarbyl group R 2 and/or R 3 does not contain a terminal amine.
  • R 2 and/or R 3 is a hydrocarbyl group selected from an amine or polyamine, the amine or amine units are selected from secondary and tertiary amines.
  • a preferred hydrocarbyl group for each of R 2 and R 3 is a group of the formula
  • a preferred hydrocarbyl group for each of R 2 and R 3 is a group of the formula
  • X is -CH 3 , or -OH.
  • the friction modifiers of the present invention may be derived from a wide range of precursors.
  • Embodiments of the present invention include compounds derived from amines selected from ammonia, butylamine, aminoethylethanolamine, aminopropan-2-ol, 5-aminopentan-1-ol, 2-(2-aminoethoxy)ethanol, monoethanolamine, 3-aminopropan-1-ol, 2-((3-aminopropyl)amino)ethanol, dimethylaminopropylamine, and N-(alkoxyalkyl)- alkanediamines including N-(octyloxyethyl)-1,2-diaminoethane and N-(decyloxypropyl)- N-methyl-1,3-diaminopropane.
  • R 2 and R 3 are groups of the formula -(CH 2 ) 3 CH 3 ; • one of R 2 and R 3 is a group of the formula -(CH 2 ) 3 CH 3l and the other of R 2 and R 3 is H;
  • R 2 and R 3 are a group of the formula -(CH 2 ) 2 NH(CH 2 ) 2 OH;
  • R 2 and R 3 are a group of the formula -(CH 2 ) 2 NH(CH 2 ) 2 OH, and the other of R 2 and R 3 is H; and • the friction modifier is a polyisobutenyl succinimide.
  • the friction modifier of formula R 1 -L-N(R 2 )(R 3 ) comprises the optional linker L, and L, when bonded to N(R 2 )(R 3 ), provides a cyclic group of formula:
  • R 3 is preferably a hydrocarbyl group.
  • R 3 is a hydrocarbyl group of formula:
  • R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R ? is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein R 4 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; wherein R 5 is an alkylene group having from 1 to 10 carbons, preferably from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons; and wherein p is an integer from 0 to 10.
  • R 3 is a hydrocarbyl group of formula:
  • R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; wherein L' is an optional linker group; wherein R 2" is independently selected from H, a hydrocarbyl group and a bond to optional group L'; wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2; and wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
  • R 1 is a hydrocarbon group.
  • R 1' is a branched or straight chain alkyl group. More preferably R 1' is a branched alkyl group. In a particulariy preferred embodiment R 1 is polyisobutene.
  • R 1' may have a molecular weight selected to provide the required properties of the friction modifier.
  • R 1 has a molecular weight of from 800 to 1300.
  • R 1 is polyisobutene having a molecular weight of from 800 to 1300. The molecular weights are as determined by vapour phase osmometry or by gel permeation chromatography, on the originating polymer.
  • R 1' may have from 10 to 200 carbons or from 10 to 100 carbons.
  • L' is present it may be any suitable group. Suitable groups include
  • the present invention provides a friction modifying composition
  • a friction modifying composition comprising a friction modifier as herein defined and a carrier oil comprising an optionally esterified polyether.
  • the carrier oil may have any suitable molecular weight.
  • a preferred molecular weight is in the range 500 to 5000.
  • the polyether carrier oil is a mono end-capped polypropylene glycol.
  • the end cap is a group consisting of or containing a hydrocarbyl group having up to 30 carbon atoms. More preferably the end cap is or comprises an alkyl group having from 4 to 20 carbon atoms or from 12 to 18 carbon atoms.
  • the alkyl group may be branched or straight chain. Preferably it is a straight chain group.
  • hydrocarbyl end capping groups include alkyl-substituted phenyl, especially where the alkyl substituent(s) is or are alkyl groups of 4 to 20 carbon atoms, preferably 8 to 12, preferably straight chain.
  • the hydrocarbyl end capping group may be attached to the polyether via a linker group.
  • R ⁇ is straight chain CrC ⁇ alkyl, preferably C 4 -C 20 alkyl, preferably C 12 -C 18 alkyl; and n is an integer of from 10 to 50, preferably 10 to 30, more preferably 12 to 20.
  • alkyl polypropyleneglycol monoethers are obtainable by the polymerisation of propylene oxide using an aliphatic alcohol, preferably a straight chain primary alcohol of to 20 carbon atoms, as an initiator. If desired a proportion of the propyleneoxy units may be replaced by units derived from other C ⁇ -Ce alkylene oxides, e.g. ethylene oxide or isobutylene oxide, and are to be included within the term "polypropyleneglycol".
  • the initiator may also be a phenol or alkyl phenol of the formula R 7 OH, a hydrocarbyl amine or amide of the formula R 7 NH 2 or R 7 CONH, respectively, where R 7 is C Cr ⁇ hydrocarbyl group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as alkyl, phenyl or phenalkyl etc.
  • R 7 is C Cr ⁇ hydrocarbyl group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as alkyl, phenyl or phenalkyl etc.
  • Preferred initiators include long chain alkanols giving rise to the long chain polypropyleneglycol monoalkyl ethers.
  • polypropyleneglycol may be an ester (R 6 COO) group where R ⁇ is defined above.
  • the carrier oil may be a polypropyleneglycol monoester of the formula
  • R ⁇ and n are as defined above and R8 is a C ⁇ Oso hydrocarbyl group, preferably an aliphatic hydrocarbyl group, and more preferably C do alkyl.
  • the friction modifier may be present in the friction modifying composition in an amount to provide the necessary and/or required handling and/or functional properties.
  • the friction modifier including solvent of production
  • the friction modifier is present in an amount of from 10 to 60% by weight, preferably 30 to 60% by weight, based on the total composition.
  • the friction modifier (excluding solvent of production) is present in an amount of from 6 to 36% by weight, preferably 18 to 36% by weight, based on the total composition.
  • the carrier oil may be present in an amount of from 10 to 40% by weight, based on the total composition.
  • the weight ratio of active friction modifier to carrier oil in the friction modifying composition may be from 0.2:1 to 5:1.
  • the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 0.2:1 to 5:1, or 0.6:1 to 5:1, typically about 5:1, 2:1, 1:1, 0.9:1, 0.8:1, or 0.6:1.
  • the weight ratio of active friction modifier to carrier oil in the friction modifying composition will be in the range 1:0.2 to 1:1.8, or 1:0.3 to 1:1.7, or 1:0.4 to 1:1.6, or 1:0.5 to 1:1.5, or 1:0.6 to 1:1.4, or 1:0.7 to 1:1.3, or 1:0.8 to 1:1.2 or 1:0.9 to 1:1.1, typically approximately 1:0.2, 1:0.5, 1:0.7, 1:1, 1:1.1, 1:1.2 or 1:1.6, such as 1:1.
  • the friction modifying composition of the present invention further comprises a solvent.
  • the solvent may be a hydrocarbon solvent having a boiling point in the range 66 to 320°C.
  • Suitable solvents include xylene, toluene, white spirit, mixtures of aromatic solvents boiling in the range 180°C to 270°C (including aromatic solvent mixtures sold under the trade marks Shellsol AB, Shellsol R, Solvesso 150, Aromatic 150), and environmentally friendly solvents such as the low aromatic content solvents of the FINALAN range.
  • the amount of solvent to be incorporated will depend upon the desired final viscosity of the friction modifying composition. Typically the solvent will be present in an amount of from 20 to 70% of the final composition on a weight basis.
  • the friction modifying composition of the present invention comprises a solvent and a co-solvent.
  • the co-solvent may be typically present in an amount of 1-2 wt.%. Suitable co-solvents include aliphatic alcohols (such as CAS no 66455-17-2)
  • the friction modifying compositions of the present invention may contain a number of minor ingredients, often added to meet specific customer requirements. Included amongst these are dehazers, usually an alkoxylated phenol formaldehyde resin, added to minimise water adso ⁇ tion and to prevent a hazy or cloudy appearance, and a corrosion inhibitor, usually of the type comprising a blend of one or more fatty acids and amines. Either or both may be present in the compositions of the present invention in amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of the composition.
  • dehazers usually an alkoxylated phenol formaldehyde resin, added to minimise water adso ⁇ tion and to prevent a hazy or cloudy appearance
  • a corrosion inhibitor usually of the type comprising a blend of one or more fatty acids and amines. Either or both may be present in the compositions of the present invention in amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of the composition.
  • anti-oxidants include anti-oxidants, anti-icing agents, metal deactivators, dehazers, corrosion inhibitors, dyes, lubricity additives, additional friction modifiers, and the like. These may be added in amounts ranging from a few parts per million, up to 2 or 3% by weight, according to conventional practice.
  • no lubricity additives or friction modifiers other than the friction modifier as herein defined are added to the friction modifying composition.
  • the total amount of such minor functional ingredients in the friction modifying composition will not exceed about 10% by weight, more usually not exceeding about 5% by weight.
  • the present invention provides a fuel additive composition
  • a fuel additive composition comprising a friction modifier as herein defined and a carrier, diluent or solvent, wherein the fuel additive composition is substantially free of any detergent and/or friction modifier other than the friction modifier as herein defined.
  • fuel additive composition refers to a composition which will undergo no modification before it is dosed into a fuel. In particular the term refers to a composition to which no further components are added before it is dosed into a fuel.
  • substantially free of a given substance means that the substance is present in the fuel additive composition in an amount of less than 1% by weight of the composition, preferably less than 0.5%, preferably less than 0.1%, preferably less than 0.05%.
  • the fuel additive composition is substantially free of any detergent other than the friction modifier as herein defined.
  • the fuel additive composition is substantially free of any friction modifier other than the friction modifier as herein defined.
  • the fuel additive composition is substantially free of any detergent and any friction modifier other than the friction modifier as herein defined.
  • the carrier, diluent or solvent is a carrier oil comprising an optionally esterified polyether.
  • the carrier, diluent or solvent is a polyether carrier oil as herein defined.
  • the carrier, diluent or solvent of the fuel additive composition is a polypropyleneglycol monoether of the formula:
  • R e is straight chain C12-C 18 alkyl; and n is an integer of from 10 to 30.
  • the friction modifier of the present invention may be inco ⁇ orated in fuel to provide a fuel composition.
  • the present invention provides a fuel composition comprising a fuel and a friction modifier as herein defined.
  • the friction modifying composition of the present invention may be incorporated in fuel to provide a fuel composition.
  • the present invention provides a fuel composition comprising a fuel and a friction modifying composition as herein defined.
  • the fuel additive composition of the present invention may be incorporated in fuel to provide a fuel composition.
  • the present invention provides a fuel composition comprising a fuel and a fuel additive composition as herein defined.
  • the friction modifier is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm.
  • the friction modifying composition is present in the fuel in an amount to provide on a weight basis, from 50 to 500 ppm friction modifier and 30 to 500 ppm carrier oil.
  • the fuel composition is substantially free of any detergent other than the friction modifier as herein defined.
  • the fuel composition is substantially free of any friction modifier other than the friction modifier as herein defined.
  • the fuel composition is substantially free of any detergent other than the friction modifier as herein defined and substantially free of any friction modifier other than the friction modifier as herein defined.
  • substantially free of a given substance means that the substance is present in the fuel composition in an amount of less than 10 ppm, preferably less than 5 ppm, preferably less than 1 ppm.
  • the fuel is a gasoline.
  • gasoline it is meant a liquid fuel for use with spark ignition engines
  • the term includes blends of distillate hydrocarbon fuels with oxygenated components such as ethanol, as well as the distillate fuels themselves.
  • the fuels may contain, in addition to the additive composition of the invention, any of the other additives conventionally added to gasoline as, for example, antiknock additives, anti-icing additives, octane requirement additives, lubricity additives etc.”
  • the present invention provides an oil composition comprising an engine oil and a friction modifier or friction modifying composition as herein defined.
  • the present invention provides an oil composition
  • an oil composition comprising (i) an oil, preferably an engine oil and (ii) a friction modifier of the formula R 1 -L-N(R 2 )(R 3 ) wherein R 1 is a hydrocarbyl group and has a number average molecular weight (Mn) of from 500 to 5000; L is an optional linker group; R 2 and R 3 are independently selected from H, a hydrocarbyl group and a bond to optional group L, wherein at least one of R 2 and R 3 is H or a hydrocarbyl group, with the proviso that if one of R 2 and R 3 is a hydrocarbyl group and the other of R 2 and R 3 is H, the hydrocarbyl group does not contain a terminal amine.
  • the present invention provides a process for the reduction of friction in a combustion engine comprising the steps of (i) dosing a fuel with a friction modifier as herein defined, or a friction modifying composition as herein defined, or a fuel additive composition as herein defined, to provide a fuel composition; (ii) combusting the fuel composition in a combustion engine.
  • the present invention provides use of a friction modifier as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifier as herein defined for reducing friction and improving detergency in a combustion engine.
  • the present invention provides use of a friction modifying composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a friction modifying composition as herein defined for reducing friction and improving detergency in a combustion engine.
  • the present invention provides use of a fuel additive composition as herein defined for reducing friction and/or improving detergency in a combustion engine. In one preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction in a combustion engine. In one highly preferred aspect the present invention provides use of a fuel additive composition as herein defined for reducing friction and improving detergency in a combustion engine.
  • the procedure was as follows. A steel ball was attached to an oscillating arm assembly and mated to a steel disk specimen in the HFRR sample cell.
  • the fuel reservoir contained 6ml of the fuel composition being tested.
  • a load of 200 grams was applied to the ball/disk interface by dead weights.
  • the ball assembly was oscillated over a 1000 ⁇ path at a rate of 50 Hertz. After a prescribed period of time, the steel ball assembly was removed. Wear, and hence the lubricity of the fuel composition, was assessed by measuring the wear scar diameter on the ball resulting from oscillating contact with the disk. The lower the value of the wear scar diameter the better the performance of the additive in the fuel composition. A wear scar diameter of below 500 ⁇ is particularly desirable. The results are set out in the tables below.
  • friction modifiers such as polyisobutenyl succinimide (PIBSI) and carrier fluids are incompatible without the addition of a suitable solvent. Many packages require additional solvent above the amount already present due to the manufacture of the friction modifier.
  • PIBSI polyisobutenyl succinimide
  • Carrier A is a C 13- ⁇ 5 initiated polyether having 12 propylene oxide units attached
  • Carrier B is a C ⁇ s initiated polyether having 14 propylene oxide units attached
  • Carrier C is a C 13-15 initiated polyether having 17 propylene oxide units attached
  • Carrier D is a nonylphenol initiated polyether having 17 propylene oxide units attached
  • the intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed below were measured using industry standard CEC-F-05-A93 test procedure on a bench engine.
  • the test engine was a Mercedes-Benz M 102.982 four cylinder, four stroke 2.3 litre gasoline-injection engine with a standard KE-Jettonic injection system.
  • the test carried out involved a cyclic procedure, each cycle including the following four operating states:
  • each test was exactly 60 h with the cycle repeated 800 times.
  • the engine was fitted with new inlet valves which were weighed before fitting.
  • residues were cleaned carefully from the valve surface facing the combustion space.
  • the valves were then immersed in n-heptane for 10 seconds and swung dry. After drying for 10 minutes, the valves were weighed and the increase in valve weight caused by deposits was measured in mg.
  • the sticky or non-sticky appearance of the deposits formed on the valve tulip and valve stem was also evaluated. The tendency to form deposits of sticky appearance could indicate, ultimately, a tendency to the appearance of the valve stick phenomenon which is desirable to avoid.
  • the fuel employed in the test procedure was an unleaded gasoline meeting EN228 specification.
  • the test compositions were added to the fuel so as to obtain a concentration of active substance (friction modifier and carrier oil) in the fuel in the amounts indicated.
  • Test running was carried out on a single roll distance accumulation dynamometer manufactured by Labeco.
  • the test engine is a regular Volkswagen Transporter 1.9-liter, 44 kW water-cooled-boxer Otto engine type 2 series with hydraulic valve filter. It is a flat four cylinder engine mounted at the rear, with a three-speed automatic transmission.
  • the valve guides and valve stems are measured before each test.
  • the fuel used in these tests is an unleaded gasoline meeting EN228 specification.
  • an engine compression test is carried out to highlight any valve which is not functioning correctly. If compression at one or more of the cylinders is less than 8 bar then the inlet valve is deemed to have been sticking in the valve guide. For the final result, with a pass at -18°C, the same cycle is used except the soak temperature is -18°C rather than 5°C.
  • test compositions are added to the fuel so as to obtain a concentration of active substance in the fuel containing additives which is specified for each example in the Table below, which gives the results obtained.
  • the intake valve detergency properties exhibited by the friction modifier and carrier oil combinations listed have been measured using the CEC F-20-A-98 test procedure on a bench engine.
  • the test engine is a Mercedes Benz M111 four cylinder, four-stroke 2.0 litre gasoline-injection engine with four valves per cylinder and an electronically controlled ignition and fuel injection system.
  • the test carried out involves a cyclic procedure, each cycle including the following four operating states:
  • each test is 60 hours.
  • the engine is fitted with new inlet valves, which are weighed before fitting.
  • residues are cleaned carefully from the valve surface facing the combustion space.
  • the valves are then immersed in n-heptane for 10 seconds and air dried for at least 10 minutes and a maximum of 2 hours.
  • Each valve is then weighed on a precision scale to an accuracy of at least one milligram, to determine the total weight of the valve and all its deposits.
  • the inlet valve deposit weight is determined by subtracting the weight of the clean intake valve that was determined before commencement of test and expressed in mg/valve.
  • the fuel employed was an unleaded gasoline meeting EN228 specification.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un modificateur de coefficient de frottement représenté par la formule générale R1-L-N(R2)(R3), dans laquelle R1 désigne un groupe hydrocarbyle ayant un poids moléculaire moyen en nombre (Mn) compris entre 500 et 5000, L désigne un groupe de liaison facultatif et R2 et R3 désignent chacun un élément sélectionné indépendamment dans l'ensemble comprenant H, un groupe hydrocarbyle et une liaison vers le groupe de liaison facultatif L. Dans cette formule, R2 et/ou R3 désignent H ou un groupe hydrocarbyle. Toutefois, si R2 ou R3 désigne un groupe hydrocarbyle et que l'autre R2 ou R3 désigne H, le groupe hydrocarbyle ne contient pas d'amine terminale.
PCT/GB2003/000643 2002-02-22 2003-02-13 Modificateur de coefficient de frottement pour combustibles hydrocarbones WO2003070860A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002475601A CA2475601A1 (fr) 2002-02-22 2003-02-13 Modificateur de coefficient de frottement pour combustibles hydrocarbones
EP03702764A EP1481040A1 (fr) 2002-02-22 2003-02-13 Modificateur de coefficient de frottement pour combustibles hydrocarbones
AU2003205886A AU2003205886A1 (en) 2002-02-22 2003-02-13 Friction modifier for hydrocarbon fuels
KR10-2004-7013027A KR20040111359A (ko) 2002-02-22 2003-02-13 탄화수소 연료용 마찰 개질제
US10/505,078 US20050223630A1 (en) 2002-02-22 2003-02-13 Friction modifier for hydrocarbon fuels
JP2003569757A JP2005517797A (ja) 2002-02-22 2003-02-13 炭化水素燃料用の摩擦調整剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0204241.4 2002-02-22
GBGB0204241.4A GB0204241D0 (en) 2002-02-22 2002-02-22 Compound

Publications (1)

Publication Number Publication Date
WO2003070860A1 true WO2003070860A1 (fr) 2003-08-28

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Country Status (9)

Country Link
US (1) US20050223630A1 (fr)
EP (1) EP1481040A1 (fr)
JP (1) JP2005517797A (fr)
KR (1) KR20040111359A (fr)
CN (1) CN1643115A (fr)
AU (1) AU2003205886A1 (fr)
CA (1) CA2475601A1 (fr)
GB (1) GB0204241D0 (fr)
WO (1) WO2003070860A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007070360A2 (fr) * 2005-12-09 2007-06-21 Envirofuels, Llc Compositions favorisant l’onctuosite et procedes d’amelioration de l’onctuosite de combustibles hydrocarbones
EP1970430A3 (fr) * 2007-03-09 2009-10-21 Afton Chemical Corporation Composition de carburant contenant un succinimide substitué d'hydrocarbyle
US7708904B2 (en) 2005-09-09 2010-05-04 Saint-Gobain Ceramics & Plastics, Inc. Conductive hydrocarbon fluid
WO2012072723A2 (fr) 2010-12-02 2012-06-07 Basf Se Utilisation du produit réactionnel d'un acide dicarbonique à substitution hydrocarbyle et d'un composé azote pour réduire la consommation de carburant
US8353740B2 (en) 2005-09-09 2013-01-15 Saint-Gobain Ceramics & Plastics, Inc. Conductive hydrocarbon fluid
US8690968B2 (en) 2008-04-04 2014-04-08 Afton Chemical Corporation Succinimide lubricity additive for diesel fuel and a method for reducing wear scarring in an engine
WO2015058992A1 (fr) 2013-10-24 2015-04-30 Basf Se Utilisation d'un polytétrahydrofurane alcoxylé en tant qu'additif dans un carburant
EP3144371A1 (fr) * 2015-09-16 2017-03-22 Afton Chemical Corporation Succinimides substitués d'hydroxyalkyle et combustibles les contenant

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4142060B2 (ja) * 2006-04-17 2008-08-27 新日本石油株式会社 自動変速機用潤滑油組成物
GB0909351D0 (en) * 2009-06-01 2009-07-15 Innospec Ltd Improvements in efficiency
GB2486255A (en) 2010-12-09 2012-06-13 Innospec Ltd Improvements in or relating to additives for fuels and lubricants

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EP0020037A1 (fr) * 1979-05-18 1980-12-10 Edwin Cooper Inc. Additif soluble dans l'huile, réduisant la friction, procédé pour sa préparation, et huile lubrifiante ou combustible contenant cet additif
WO1983003616A1 (fr) * 1981-01-26 1983-10-27 Cooper Edwin Inc Carburant et compositions lubrifiantes contenant des succinimides de n-hydroxymethyl
WO1996025473A1 (fr) * 1995-02-17 1996-08-22 Bp Chemicals (Additives) Limited Carburants diesel
WO1998011175A1 (fr) * 1996-09-12 1998-03-19 Exxon Research And Engineering Company Concentre d'additifs destine a des compositions de carburant
EP0950704A1 (fr) * 1998-04-14 1999-10-20 The Lubrizol Corporation compositions contenant une amine substituée par un polyakene et un polyether alcool
WO2000002978A1 (fr) * 1998-07-09 2000-01-20 Basf Aktiengesellschaft Compositions de carburant contenant du propoxilate
WO2000015739A1 (fr) * 1998-09-14 2000-03-23 The Lubrizol Corporation Compositions de carburant diesel
EP1151994A1 (fr) * 2000-05-01 2001-11-07 Ethyl Corporation Acides de succinimide et leurs derivatives
WO2002022765A2 (fr) * 2000-09-13 2002-03-21 The Associated Octel Company Limited Composition

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8353740B2 (en) 2005-09-09 2013-01-15 Saint-Gobain Ceramics & Plastics, Inc. Conductive hydrocarbon fluid
US7708904B2 (en) 2005-09-09 2010-05-04 Saint-Gobain Ceramics & Plastics, Inc. Conductive hydrocarbon fluid
WO2007070360A3 (fr) * 2005-12-09 2007-08-02 Envirofuels Llc Compositions favorisant l’onctuosite et procedes d’amelioration de l’onctuosite de combustibles hydrocarbones
WO2007070360A2 (fr) * 2005-12-09 2007-06-21 Envirofuels, Llc Compositions favorisant l’onctuosite et procedes d’amelioration de l’onctuosite de combustibles hydrocarbones
EP1970430A3 (fr) * 2007-03-09 2009-10-21 Afton Chemical Corporation Composition de carburant contenant un succinimide substitué d'hydrocarbyle
US9011556B2 (en) 2007-03-09 2015-04-21 Afton Chemical Corporation Fuel composition containing a hydrocarbyl-substituted succinimide
US8690968B2 (en) 2008-04-04 2014-04-08 Afton Chemical Corporation Succinimide lubricity additive for diesel fuel and a method for reducing wear scarring in an engine
WO2012072723A2 (fr) 2010-12-02 2012-06-07 Basf Se Utilisation du produit réactionnel d'un acide dicarbonique à substitution hydrocarbyle et d'un composé azote pour réduire la consommation de carburant
WO2012072723A3 (fr) * 2010-12-02 2012-07-26 Basf Se Utilisation du produit réactionnel d'un acide dicarbonique à substitution hydrocarbyle et d'un composé azote pour réduire la consommation de carburant
WO2015058992A1 (fr) 2013-10-24 2015-04-30 Basf Se Utilisation d'un polytétrahydrofurane alcoxylé en tant qu'additif dans un carburant
EP3241882A1 (fr) 2013-10-24 2017-11-08 Basf Se Composition de carburant
US9951288B2 (en) 2013-10-24 2018-04-24 Basf Se Use of an alkoxylated polytetrahydrofuran to reduce fuel consumption
EP3144371A1 (fr) * 2015-09-16 2017-03-22 Afton Chemical Corporation Succinimides substitués d'hydroxyalkyle et combustibles les contenant

Also Published As

Publication number Publication date
AU2003205886A1 (en) 2003-09-09
CA2475601A1 (fr) 2003-08-28
US20050223630A1 (en) 2005-10-13
CN1643115A (zh) 2005-07-20
KR20040111359A (ko) 2004-12-31
EP1481040A1 (fr) 2004-12-01
JP2005517797A (ja) 2005-06-16
GB0204241D0 (en) 2002-04-10

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