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
  • 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
  • C10L1/1983—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 polyesters
• • 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
  • C10L1/18—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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • 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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • 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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
• • 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
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • 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
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • 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
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • 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)

Definitions

• This invention relates to fuel compositions, more particularly to such compositions containing a fuel for an internal combustion engine, to their preparation and to their use in operation of internal combustion engines.
• US Patent No. 6,127,481 (assigned to DSM Copolymer, Inc.), and the corresponding published European patent application EP-A-818 525, discloses a branched polyolefin additive for use in fuel and/or lubricating oil in the form of a comb, star, nanogel and structural combinations thereof in which a plurity of polyolefin arms are attached to a backbone having repeating units containing aliphatic groups, aromatic groups, heteroatom- containing groups and combinations thereof, to provide a branched polymeric additive in which the properties of the additive can be conveniently tailored to a single or multi-functional performance criteria of a fuel and/or lubricating oil composition.
• dendrimers are used as the backbone, and the reactive terminal groups of the dendrimer are reacted with polyolefin prearms to provide a polymeric product in which the terminal groups are polyolefinic groups.
• the examples wherein dendrimers are used as the backbone are Examples 15, 17, 21 and 22.
• ethylene-propylene polymer arms are functionalised with an end group which will react with a reactive terminal group on a dendrimer, and the resulting polyolefin prearms are reacted with dendrimer such that each reactive terminal group reacts with a polyolefin prearm to form an ester, imide, amine, ether or urea linkage, thereby leaving no terminal amino, hydroxyl or carboxylate groups .
• WO 96/12755 discloses an oil soluble dendrimer-based cold flow improver comprising a central core linked through a plurality of polar groups to a dendritic body which is linked through a plurality of polar groups to a hydrocarbyl periphery, the periphery consisting of n-alkyl groups which contain from 8 to 1000 carbon atoms.
• dendrimer-based cold flow improvers are used in crude oil, lubricating oil or fuel oil (e.g. kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils) .
• fuel oil e.g. kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils
• concentration (w/w) is 0.0001 to 1% (1 to 10,000 ppmw), preferably 0.1 to 0.2% (1000 to 2000 ppmw) (page 7, lines 5 to 17, of WO 96/12755), although the examples employ 100 to 200 ppmw (0.01 to 0.02 %w/w) .
• WO 02/102928 Shell International Research
• Maatschappij B.V. discloses a method for solubilising asphaltenes in an asphaltenes-containing hydrocarbon mixture by adding thereto an effective amount of a dendrimeric compound; and a hydrocarbon mixture comprising (in addition to hydrocarbons), asphaltenes and at least one dendrimeric compound.
• Asphaltenes are aromatic hydrocarbons which are insoluble in n-heptane, and are generally determined in accordance with ASTM D 6560. Asphaltenes cause problems in oil recovery and oil refining processes, by forming solid desposits or dark sludge, e.g. in oil formations, in oil-well equipment or in oil pipelines.
• WO 97/41092 (Shell Internationale Research Maatschappij B.V.) discloses alkoxy acetic acid derivatives of general formula
• R is the residue of an amine, an aminoalcohol or a polyol linked to the or each -CHR " -CO- moiety via an amide or ester linkage:
• R' is hydrogen or C]__4 alkyl
• RA is an optionally substituted hydrocarbyl group of 1 to 300 carbon atoms; one of R ⁇ and R ⁇ is independently selected from hydrogen and optionally substituted hydrocarbyl of 1 to 10 carbon atoms, the other of R ⁇ and R ⁇ being independently selected from optionally substituted hydrocarbyl of 1 to 10 carbon atoms; m is from 3 to 200; n is from 0 to 20, provided that m/n is at least 1; and p is from 1 to 5, their preparation and their use as fuel additives .
• “Starburst” (trade mark) dendrimers may be used, e.g. the compound of formula [CH 2 N ( (CH 2 ) 2CONH (CH 2 ) 2 NH 2 ) 2 ] 2 .
• This latter compound, “Starburst” (PAMAM, generation O) dendrimer is used in Example 25 resulting in a compound of formula I wherein R is a dendrimer backbone having 3 remaining terminal amino groups .
• R(H)p is selected from the group consisting of pentaerythritol, triethylenetetramine and tris (2-aminoethyl ) amine.
• Example 25 is not among the most active of the materials tested, and the person skilled in the art would not have been encouraged to pursue further derivatives of dendrimers instead of polyalkylene glycol derivatives of pentaerythritol, triethylenetetramine and tris (2-aminoethyl) amine, in the quest for advantageous gasoline additives .
• a fuel composition comprising a major amount of a fuel for an internal combustion engine and a minor amount of a fuel-compatible dendrimer containing from 4 to 64 terminal functional groups independently selected from amino, hydroxyl and carboxylate groups .
• dendrimers as three-dimensional highly-ordered oligomers or polymers . They are obtainable by reiterative reaction sequences starting from an initiator core having one or more reactive sites. To each reactive site is attached one functional group only of a polyfunctional reactant. The reactant is then caused to react through its remaining functional group or groups with additional molecules either the same as the original core if it is polyfunctional or a different, polyfunctional, molecule or molecules, and so on, in each case under reaction conditions such that unwanted side reactions, for example, crosslinking, are avoided.
• steps A and B produce higher generations which after Generation 4 result in concentric spheres of cells, the outermost sphere carrying external reactive groups .
• Other dendrimers described by Tomalia include polyethylenimine, hydrocarbon, polyether, polythioether, polyamide, polyamdo-alcohol and polyarylamine dendrimers. Synthesis of such dendrimers are variously desscribed, for example, in US Patents 4,435,548, 4,507,466, 4,558,120 and 4,568,737, all of Tomalia et_ ⁇ (assigned to The Dow Chemical Company) .
• GB-A-1575507 describes star-shaped polymers and their use as viscosity improvers, these polymers being based on a cross-linked divinylbenzene core and isoprene branches; in EP-A-368395 such a hydrocarbon polymer is functionalized through a sulphonamide linkage to provide carboxyl terminal groups .
• PAMAM dendrimers have a large internal surface area which, in proportion to the external surface area, increases with the number of generations.
• polyether dendrimers have very little proportional internal surface, which reaches a maximum at Generations 3 to 4.
• the successive layers of cells may be the same or different, and mixtures of two or more reactants, for example as described by Tomalia, Angew
• the dendrimer is at least one fuel- compatible dendrimer independently selected from DAB-Am, PAMAM and PAMAM-OH dendrimers.
• the terminal functional groups are preferably individually selected from -NH2, -OH and COOX groups, where X represents H, K or Na.
• the dendrimer contains from 4 to 32 terminal functional groups and more conveniently 8 to 16 terminal functional groups, independently selected from amino, hydroxyl and carboxylate groups .
• the dendrimer is preferably present in the fuel composition in a concentration in the range from 5 ppmw to 500 ppmw, more preferably in the range from 10 ppmw to 200 ppmw, based on total composition. It may be found useful for the fuel composition additionally to contain a fuel-compatible oxygenate co- solvent selected from C ⁇ -_ to C]_4 alkanols and 2- ethylhexanoic acid.
• a fuel composition according to the invention preferably additionally contains a nitrogen-containing detergent containing a hydrocarbyl group having a number average molecular weight (Mn) the range 750 to 6000, in a concentration in the range 25 to 2500 ppmw based on total composition .
• the fuel composition preferably contains 50 to 1500 ppmw of the nitrogen-containing detergent, and more preferably 50 to 500 ppmw thereof. Quantities in the range 80 to 250 ppmw, e.g. 100 to 150 ppmw, are very suitable .
• the nitrogen-containing detergent containing a hydrocarbyl group having a number average molecular weight (Mn) in the range 750 to 6000 may be an amine, e.g.
• a polyisobutylene mono-amine or polyamine such as a polyisobutylene ethylene diamine, or N-polyisobutenyl- N' , N' -dimethyl-1, 3-diaminopropane, or amide e.g. a polyisobutenyl succinimide, and are variously described, for example, in US Patent 5,855,629 and WO 0132812.
• the nitrogen-containing detergent may be a Mannich amine detergent, for example a Mannich amine detergent as described in US Patent 5,725,612.
• a particularly preferred nitrogen-containing detergent is hydrocarbyl amine of formula R.I-NH2, wherein RA represents a group R ⁇ or a group R2-CH2 ⁇ and R ⁇ represents a hydrocarbyl group having a number average molecular weight in the range 750 to 6000, preferably in the range 900 to 3000, more preferably 950 to 2000, and most preferably in the range 950 to 1350, e.g. a polybutenyl or polyisobutenyl group having a number average molecular weight in the range 950 to 1050.
• the nitrogen-containing detergents are known materials and may be prepared by known methods or by methods analogous to known methods.
• US Patent 4,832,702 describes the preparation of polybutenyl and polyisobutenyl amines from an appropriate polybutene or polyisobutene by hydroformylation and subsequent amination of the resulting oxo product under hydrogenating conditions.
• Suitable hydrocarbyl amines are obtainable from BASF A. G., under the trade mark “Kerocom” .
• the fuel for an internal combustion engine may be gasoline, diesel fuel, aviation gasoline or aviation gas turbine fuel, the fuel is preferably gasoline or diesel fuel, most preferably gasoline.
• a fuel composition according to the invention is a gasoline composition
• the gasoline composition may additionally contain one or more carrier fluids, corrosion inhibitors, anti-oxidants, dyes, dehazers, metal deactivators, detergents other than a nitrogen- containing detergent containing a hydrocarbyl group as defined above (e.g. a polyether amine), friction modifiers, diluents and markers.
• Particularly suitable carrier fluids are polyolefins, e.g.
• Carrier fluids may conveniently be employed in total concentrations in the range 20 to 8000 ppmw, e.g. 50 to 500 ppmw.
• Polyalphaolefin carrier fluids are primarily trimers, tetramers and pentamers, and synthesis of such materials is outlined in Campen e_t al. "Growing use of synlubes", Hydrocarbon Processing, February 1982, Pages 75 to 82.
• the polyalphaolefin may be unhydrotreated, but it is preferably a hydrogenated oligomer.
• the polyalphaolefin is preferably derived from an alphaolefinic monomer containing from 8 to 12 carbon atoms. Furthermore, it preferably has viscosity at 100 0 C in the range 6xlO ⁇ 6 to lxl ⁇ ⁇ 5 m ⁇ /s (6 to 10 centistokes) . Polyalphaolefins derived from decene-1 are very suitable. Polyalphaolefins having a viscosity at 100 0 C of 8xlO ⁇ 6 m ⁇ /s (8 centistokes) are very suitable.
• Polyoxyalkylene carrier fluids which are very effective, preferably have the formula II '-Mt- ( i i ;
• R ⁇ and R ⁇ independently represent hydrogen atoms or hydrocarbyl, preferably C ] __4Q hydrocarbyl, e.g. alkyl, cycloalkyl, phenyl or alkyl-phenyl groups, each R ⁇ independently represents an alkylene, preferably C2-8 alkylene, group, and p is such that Mn of the polyoxyalkylene compound is in the range 400 to 3000, preferably 700 to 2000, more preferably 1000 to 2000.
• R ⁇ represents a Cg-20 alkyl group and R 4 represents a hydrogen atom.
• R ⁇ preferably represents a Cg_]_g alkyl group, more preferably a Cg_]_5 alkyl group.
• R3 may conveniently be a mixture of Cg_]_5 alkyl groups.
• each group R ⁇ are preferably 1,2 alkylene groups .
• each group R ⁇ independently represents a C2-4 alkylene group, e.g. an ethylene, 1,2- propylene or 1,2-butylene group. Very effective results have been obtained when each group R ⁇ represents a 1,2- propylene group.
• Number average molecular weights e.g. of hydrocarbons such as polyalkenes, may be determined by several techniques which give closely similar results. Conveniently Mn may be determined by vapour phase osmometry (VPO) (ASTM D 3592) or by modern gel permeation chromatography (GPC), e.g. as described for example in W. W. Yau, J.J. Kirkland and D. D. BIy, "Modern Size
• gasolines suitable for use in spark ignition engines are mixtures of hydrocarbons having boiling points in the range from 25°C to 232°C and comprising mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons .
• Preferred are gasoline blends having a saturated hydrocarbon content ranging from 40 to 80 per cent volume, an olefinic hydrocarbon content ranging from 0 to 30 per cent volume and an aromatic hydrocarbon content ranging from 10 to 60 per cent volume.
• the gasoline can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer- or trimerised olefins, synthetically produced aromatic hydrocarbon mixtures from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, or mixtures thereof.
• the hydrocarbon composition and octane level of the gasoline are not critical.
• the octane level, (R+M)/2, will generally be above 85.
• Any conventional gasoline can be used.
• hydrocarbons can be replaced by up to substantial amounts of conventional alcohols or ethers conventionally known for use in gasoline, including biofuel components, or of ester biofuel components such as ethyl levulinate.
• the gasoline is preferably lead-free, and this may be required by law. Where permitted, lead-free antiknock compounds and/or valve-seat recession protectant compounds (e.g. known potassium salts, sodium salts or phosphorous compounds) may be present.
• Modern gasolines are inherently low-sulphur fuels, e.g. containing less than 200 ppmw sulphur. In this specification, amounts (concentrations) (%v) (ppmw) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
• a gasoline composition in accordance with the invention may be prepared by a process which comprises bringing into admixture the gasoline and the fuel- compatible dendrimer, and any other components, such as nitrogen-containing detergent.
• the fuel-compatible dendrimer, and any additional components such as nitrogen-containing detergent, fuel-compatible oxygenate co-solvent, corrosion inhibitors, anti-oxidants, etc., as listed above, may be co-mixed, preferably together with suitable diluent (s), in an additive concentrate, and the additive concentrate may be dispersed into gasoline, in suitable quantity to result in a gasoline composition of the invention .
• a fuel composition according to the invention is a diesel fuel composition
• the fuel for an internal combustion engine is a diesel fuel, which may typically comprise liquid hydrocarbon middle distillate gas oil(s), for instance petroleum derived gas oils.
• liquid hydrocarbon middle distillate gas oil(s) for instance petroleum derived gas oils.
• Such fuels will typically have boiling points with the usual diesel range of 150 to 400 0 C, depending on grade and use. They will typically have a density from 750 to
• 900 kg/m 3 preferably from 800 to 860 kg/m 3 , at 15°C (e.g. ASTM D4502 or IP 365) and a cetane number (ASTM D613) of from 35 to 80, more preferably from 40 to 75. They will typically have an initial boiling point in the range 150 to 230 0 C and a final boiling point in the range 290 to 400 0 C. Their kinematic viscosity at 40 0 C (ASTM
• D445) might suitably be from 1.5 to 4.5 mm ⁇ /s.
• non-mineral oil based fuels such as bio-fuels or Fischer-Tropsch derived fuels, may also form or be present in the diesel fuel composition.
• the amount of Fischer-Tropsch derived fuel used in a diesel fuel composition may be from 0.5 to 100%v of the overall diesel fuel composition, preferably from 5 to 75%v. It may be desirable for the composition to contain 10%v or greater, more preferably 20%v or greater, still more preferably 30%v or greater, of the Fischer-Tropsch derived fuel. It is particularly preferred for the composition to contain 30 to 75%v, and particularly 30 or 70%v, of the Fischer-Tropsch derived fuel.
• the balance of the fuel composition is made up of one or more other fuels .
• the Fischer-Tropsch product will suitably contain more than 80 wt% and more suitably more than 95 wt% iso and normal paraffins and less than 1 wt% aromatics, the balance being naphthenics compounds. The content of sulphur and nitrogen will be very low and normally below the detection limits for such compounds. For this reason the sulphur content of a diesel fuel composition containing a Fischer-Tropsch product may be very low.
• the diesel fuel composition preferably contains no more than 5000ppmw sulphur, more preferably no more than 500ppmw, or no more than 350ppmw, or no more than
• the base diesel fuel may itself be additivated (additive-containing) or unadditivated (additive-free). If additivated, e.g. at the refinery, it will contain minor amounts of one or more additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) and wax anti- settling agents (e.g. those commercially available under the Trade Marks "PARAFLOW” (e.g. PARAFLOWTM 450, ex Infineum) , "OCTEL” (e.g. OCTELTM W 5000, ex Octel) and "DODIFLOW” (e.g. DODIFLOWTM V 3958, ex Hoechst).
• additives selected for example from anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic an
• Detergent-containing diesel fuel additives are known and commercially available, for instance from Infineum (e.g. F7661 and F7685) and Octel (e.g. OMA 4130D). Such additives may be added to diesel fuels at relatively low levels (their "standard" treat rates providing typically less than 100 ppmw active matter detergent in the overall additivated fuel composition) intended merely to reduce or slow the build up of engine deposits.
• the additive may contain other components in addition to the nitrogen-containing detergent. Examples are lubricity enhancers; dehazers, e.g.
• alkoxylated phenol formaldehyde polymers such as those commercially available as NALCOTM EC5462A (formerly 7D07) (ex Nalco) and TOLADTM 2683 (ex Petrolite); anti-foaming agents (e.g. the polyether-modified polysiloxanes commercially available as TEGOPRENTM 5851 and Q 25907 (ex Dow Corning), SAGTM TP-325 (ex OSi) and RHODORSILTM (ex Rhone Poulenc)); ignition improvers (cetane improvers) (e.g.
• the pentaerythritol diester of polyisobutylene-substituted succinic acid ; corrosion inhibitors; reodorants; anti-wear additives; anti-oxidants (e.g. phenolics such as 2,6-di-tert- butylphenol, or phenylenediamines such as N, N ' -di-sec-butyl-p-phenylenediamine) ; and metal deactivators .
• the diesel fuel additive include a lubricity enhancer, especially when the fuel composition has a low (e.g. 500 ppmw or less) sulphur content.
• the lubricity enhancer is conveniently present at a concentration between 50 and 1000 ppmw, preferably between 100 and 1000 ppmw.
• Suitable commercially available lubricity enhancers include EC 832 and PARADYNETM 655 (ex Infineum) , HITECTM E580 (ex Ethyl Corporation), VEKTRONTM 6010 (ex Infineum) and amide-based additives such as those available from the Lubrizol Chemical Company, for instance LZ 539 C.
• Other lubricity enhancers are described in the patent literature, in particular in connection with their use in low sulphur content diesel fuels, for example in:
• diesel fuel additive contain an anti-foaming agent, more preferably in combination with an anti-rust agent and/or a corrosion inhibitor and/or a lubricity additive.
• the (active matter) concentration of each such additional component in the additivated diesel fuel composition is preferably up to 10000 ppmw, more preferably in the range from 5 to 1000 ppmw, advantageously from 75 to 300 ppmw, such as from 95 to 150 ppmw.
• the (active matter) concentration of any dehazer in the diesel fuel composition will preferably be in the range from 1 to 20 ppmw, more preferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw, advantageously from 1 to 5 ppmw.
• the (active matter) concentration of any ignition improver present will preferably be 600 ppmw or less, more preferably 500 ppmw or less, conveniently from 300 to 500 ppmw.
• the additive components may be co-mixed, preferably together with suitable diluent (s), in a diesel fuel additive concentrate, and the additive concentrate may be dispersed into the fuel, in suitable quantity to result in a composition of the present invention.
• the additive will typically contain a detergent, optionally together with other components as described above, and a diesel fuel-compatible diluent, which may be a carrier oil (e.g. a mineral oil), a polyether, which may be capped or uncapped, a non-polar solvent such as toluene, xylene, white spirits and those sold by companies of the Shell Group under the trade mark "SHELLSOL", and/or a polar solvent such as an ester and, in particular, an alcohol, e.g.
• a carrier oil e.g. a mineral oil
• a polyether which may be capped or uncapped
• a non-polar solvent such as toluene, xylene, white spirits and those sold by companies of the Shell Group under the trade mark "SHELLSOL”
• a polar solvent such as an ester and, in particular, an alcohol, e.g.
• LINEVOL LINEVOLTM 79 alcohol which is a mixture of C ⁇ _9 primary alcohols, or the C]_2-i4 alcohol mixture commercially available from Sidobre Sinnova, France under the trade mark "SIPOL”.
• the total content of the additives may be suitably between 0 and 10000 ppmw and preferably below 5000 ppmw.
• the present invention further provides a method of operating an internal combustion engine which comprises introducing into the combustion chambers of said engine or fuel composition according to the invention, as defined above.
• the present invention also provides use of a fuel composition of the invention, preferably a gasoline composition, as fuel in an internal combustion engine (in the case of gasoline, a spark-ignition engine) for controlling combustion chamber deposits.
• a fuel composition of the invention preferably a gasoline composition
• an internal combustion engine in the case of gasoline, a spark-ignition engine
• base gasoline was an unleaded gasoline (95 ULG) of RON 95.3, MON 85.3 and having sulphur content (ASTM D 2622 - 94) of 48 ppmw, aromatics content of 33.2% v/v and olefins content of 11.9% v/v (ASTM D 6623-01 (procedure C)), density (DIN 51757/V4)
• Detergent-containing gasoline was the above base gasoline into which was incorporated, at a package concentration of 380 ppmw, a standard commercial gasoline additive package, containing a polyisobutyleneamine detergent, a synthetic carrier oil and a conventional corrosion inhibitor, corresponding closely to additive package PI of Example 3 of DE-A-19955651.
• the polyisobutyleneamine detergent was a polyisobutylene monoamine (PIPBA) ex BASF, in which the polyisobutylene (PIB) chain has a number average molecular weight of approximately 1000.
• the synthetic carrier oil was a polyether carrier being a polyoxypropylene glycol hemiether, containing 15 to 30 propylene oxide units prepared using a mixture of alkanols in the C5_]_5 range as initiators, and having Mn in the range 1000 to 2000.
• the additive package contained about 68% non-volatile matter, about 27%w of the package being the PIBA and 40%w of the package being carrier fluid.
• Base diesel fuel had sulphur content (IP 373) of 39 ppmw, cloud point -6°C, cetane number (IP 380/94) of 55.9, density at 15 0 C 831 kg/m 3 , distillation (IP 123) IBP 171°C, 10% 211°C, 50% 277°C, 90% 328°C and FBP 359°C.
• Detergent-containing diesel fuel contained the above base diesel fuel together with a commercial performance package containing detergent, anti-foam, anti-oxidant and anti-corrosion additives, in addition to necessary commercial cold-flow improver, cetane improver (2- ethylhexyl nitrate), anti-static agent, lubricating improver and pipeline drag reducer. Examples 1 to 19
• the dendrimer was tested for compatibility with base gasoline and/or base diesel fuel, using fuel-soluble oxygenate co-solvents. Where an Aldrich Number is given, the dendrimer is obtainable from Aldrich companies, e.g. Aldrich Chemical Co., Milwaukee, Wisconsin, USA or Sigma-Aldrich Company Ltd., Gillingham, Dorset, UK (Source: Aldrich Handbook of Fine Chemicals and Laboratory Equipment 2003-2004 United Kingdom) .
• DAB-Am dendrimers A: Aldrich No. 46,069-9; DAB-Am-4, Polypropylenimine tetraamine Dendrimer, Generation 1.0; [-CH 2 CH 2 Nt (CH 2 )3NH 2 ] 2] 2; Formula weight 316. Contains 4 surface primary amino groups.
• Formula weight 1429 Contains 8 surface primary amino groups .
• G Aldrich No. 41,242-2; PAMAM Dendrimer, Generation 3; Formula weight 6909; contains 32 surface primary amino groups .
• H Aldrich No. 41,237-6; PAMAM Dendrimer, Generation 0.5; [-CH 2 N[CH 2 CH 2 CONHCH 2 CH 2 N(CH 2 CH 2 COONa) 2 ] 2 ] 2 ;
• Formula weight 1269 contains 8 surface carboxylate groups .
• Formula weight 2935 contains 16 surface carboxylate groups .
• K Aldrich No. 47,784-2; PAMAM-OH Dendrimer, Generation 3; Formula weight 6941; contains 32 surface hydroxyl groups .
• L Aldrich No. 47,785-0; PAMAM-OH Dendrimer, Generation
• Dendrimer M 250 ml of a 25% w/w solution of M in methanol was passed through a chromatography column
• Dendritech, Inc. having relative proportions of -NH 2 to -OH surface groups, as determined by NMR, of 50% -NH 2 and 50%-OH, by number.
• P Mixed amino/hydroxyl group dendrimer prepared by partial oxidation of PAMAM Dendrimer, Generation 2, available as special order ex Dentritech, Inc., having relative proportions of -NH2 to -OH surface groups, as determined by NMR of 85% -NH2 and 15% - OH, by number .
• Cyclotriphosphazene dendrimers (comparative examples) Q: Aldrich No. 55201-1; Cyclotriphosphazene - PMMH -6 Dendrimer, Generation 0.5; N3P3 (OC5N4CHO) 5 ; Formula weight 861; contains 6 surface aldehyde (-CHO) groups .
• N 3 P 3 (OCgH 4 CH NN(CH 3 )P(S) (OCgH 4 CHO ) 2 ) 6 ; Formula weight 2853; contains 12 surface aldehyde (-CHO) groups .
• Dendrimer, Generation 0.5; S P (OCgH 4 CHO) 3 ; Formula weight 426; contains 3 surface aldehyde (-CHO) groups .
• Fuel-soluble oxygenate co-solvents used were methanol (for gasoline), 2-ethylhexanol (for gasoline and diesel fuel) and 2-ethylhexanoic acid (for diesel fuel) .
• Co-solvent: dendrimer ratios from 5:1 to 400:1 by weight were used.
• Combustion chamber deposit tests were run using Mercedes Benz C200 saloon cars with M 111-945, 1998 cc, 4-cylinder, 16 valve engines, compression ratio 10.4:1, 100 Kw at 5500 rpm, of accumulated mileage in the range 25,000 to 50,000 miles.
• Mileage was accumulated on a standard 250 mile (400 km) circuit of 64 miles (102 km) at constant 60 mph (96 kph) followed by 78 miles (125 km) of urban driving at 30 to 60 mph (48 to 96 kph), followed by 108 miles (173 km) at constant 60 mph (96 kph).
• Combustion chamber deposits were assessed by measuring average piston centre combustion chamber deposits thickness through sparking plug aperture at piston top dead centre (TDC) , using a Fischer Isoscope MP2 Probe, standardised prior to use against manufacturer-supplied standard films of known thickness. Average piston centre combustion chamber deposit thickness has been found previously to correlate closely to average total combustion chamber deposit weight, and therefore is a meaningful parameter.
• Dendrimer N was used in (ii), at 200 ppmw, 50 ppmw and 10 ppmw, in different vehicles, and one vehicle was run using detergent-containing gasoline for comparison purposes . Dendrimer N was dosed into base gasoline as a 1:80 w/w solution of Dendrimer N in methanol. Results are given in Table 3 following.
• combustion chamber deposit thickness increased by more than 11% over 1000 miles (1600 kilometres), whereas for base gasoline containing Dendrimer N, combustion chamber deposit thicknesses reduced according to concentration of Dendrimer N.
• combustion chamber deposit thickness reduced by over 51% for 200 ppmw concentration, by over 30% for 50 ppmw concentration and by over 14% for 10 ppmw concentration. In each case, combustion chamber deposit thickness reverted towards Start levels upon switching back to base gasoline.
• Examples 24 to 26 Vehicles were run (i) for 2500 miles (4000 kilometres) on detergent-containing gasoline, followed by (ii) 1250 miles (2000 kilometres on test gasoline, followed by (iii) a further 750 miles (1200 kilometres) on detergent-containing gasoline.
• Average combustion chamber deposit thickness was measured after (i) (Start), at 750 miles (1200 kilometres) and 150 miles (2000 kilometres) in (ii) and after (iii) (End).
• Dendrimers N, O and P dosed as 1:80 w/w solutions of dendrimer in methanol, were dosed into detergent-containing gasoline (DTG) at a concentration of dendrimer of 100 ppmw, in different vehicles, and one vehicle was run throughout on detergent-containing gasoline, for comparison purposes. Results are given in Table 4 following:-
• the deposit thickness increase by at least 11% (11% where no dendrimer had previously been used, 17.6% where Dendrimer N had previously been used, 12.8% where dendrimer O had previously been used and 20.4% where Dendrimer P had previously been used) .
• Gasoline samples containing test materials at a concentration of 50 parts per million by weight (ppmw) of dendrimer in base gasoline, are prepared, and 100 ml portions of the gasoline samples are delivered at a rate of 0.6 ml/minute from glass syringes fitted with 20 gauge steel hypodermic Luer lock needles into the groove at the top end of each plate. Once delivery is complete, after about 2 hours and 40 minutes, the plates are allowed to cool to ambient temperature (20 0 C) and are washed with n- heptane until the run-off liquid is clear, and are then left to dry before assessment of any deposit present.
• ppmw parts per million by weight
• the image analyser divides, pixel by corresponding pixel, the deposit image by the clean image and automatically measures the area and optical density of deposit at the pixels contained within overall measuring frame, and calculates an integrated optical density for the image, the numerical value of which is recorded as a test rating. Results of this test are given in Table 5 as follows : - Table 5
• Dendrimers A and C were dosed as 1:10 w/w solutions of dendrimer in 2-ethylhexanol; and Dendrimers F, J, K, N, O and P were dosed as 1:80 w/w solutions of dendrimer in methanol .

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