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EP1602706A1 - Fuel additive composition suitable for control and removal of tenacious engine deposits - Google Patents

Fuel additive composition suitable for control and removal of tenacious engine deposits Download PDF

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Publication number
EP1602706A1
EP1602706A1 EP05252964A EP05252964A EP1602706A1 EP 1602706 A1 EP1602706 A1 EP 1602706A1 EP 05252964 A EP05252964 A EP 05252964A EP 05252964 A EP05252964 A EP 05252964A EP 1602706 A1 EP1602706 A1 EP 1602706A1
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EP
European Patent Office
Prior art keywords
composition according
fuel composition
carbon atoms
weight
parts per
Prior art date
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EP05252964A
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German (de)
English (en)
French (fr)
Inventor
Majid R. Ahmadi
Damon C. Vaudrin
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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Publication of EP1602706A1 publication Critical patent/EP1602706A1/en
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    • 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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • 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

Definitions

  • This invention relates to fuel compositions employing a hydrocarbyl-substituted polyoxyalkylene amine and a glycol ether component useful for the prevention and control of engine deposits. Moreover, said fuel additive composition of the present invention can be used for the control and removal of existing tenacious engine deposits, and is particularly suited for controlling and removing piston ring groove deposits.
  • aliphatic hydrocarbon-substituted phenols are known to reduce engine deposits when used in fuel compositions.
  • U.S. Patent No. 3,849,085, issued November 19, 1974 to Stamm et al. discloses a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range containing about 0.01 to about 0.25 volume percent of a high molecular weight aliphatic hydrocarbon-substituted phenol in which the aliphatic hydrocarbon radical has an average molecular weight in the range of about 500 to about 3,500.
  • This patent teaches that gasoline compositions containing minor amounts of an aliphatic hydrocarbon-substituted phenol not only prevent or inhibit the formation of intake valve and port deposits in a gasoline engine, but also enhance the performance of the fuel composition in engines designed to operate at higher operating temperatures with a minimum of decomposition and deposit formation in the manifold of the engine.
  • Polyether amine fuel additives are also well known in the art for the prevention and control of engine deposits. These polyether additives have a polyoxyalkylene "backbone", i.e., the polyether portion of the molecule consists of repeating oxyalkylene units.
  • U.S. Patent No. 4,191,537, issued March 4, 1980 to Lewis et al. discloses a fuel composition comprising a major portion of hydrocarbons boiling in the gasoline range and from 30 to 2,000 ppm of a hydrocarbyl polyoxyalkylene aminocarbamate having a molecular weight from about 600 to 10,000, and at least one basic nitrogen atom.
  • hydrocarbyl polyoxyalkylene moiety is composed of oxyalkylene units having from 2 to 5 carbon atoms in each oxyalkylene unit. These fuel compositions are taught to maintain the cleanliness of intake systems without contributing to combustion chamber deposits. Hydrocarbyl polyoxyalkylene aminocarbamate additives are further disclosed in U.S. Patent No. 4,881,945, issued November 21, 1989 to Buckley as well as U.S. Patent No.
  • U.S. Patent No. 5,660,601 issued August 26, 1997 to Oppenlander et al., discloses fuels for gasoline engines containing from 10 to 2,000 mg per kg of fuel (i.e., 10 to 2,000 parts per million) of an alkyl-terminated polyetheramine, therein the alkyl group contains from 2 to 30 carbon atoms and the polyether moiety contains from 12 to 28 butylene oxide units.
  • This patent further teaches that the polyetheramines are prepared by the reaction of an alcohol with butylene oxide, and subsequent amination with ammonia or an amine.
  • U.S. Patent No. 4,332,595 issued June 1, 1982 to Herbstman et al., discloses a gasoline detergent additive which is a hydrocarbyl-substituted polyoxypropylene diamine, wherein the hydrocarbyl substituent contains 8 to 18 carbon atoms.
  • This patent further teaches that the additive is prepared by reductive amination of a hydrocarbyl-substituted polyoxypropylene alcohol with ammonia to give a polyoxypropylene amine, which is subsequently reacted with acrylonitrile to give the corresponding N-2-cyanoethyl derivative. Hydrogenation in the presence of ammonia then provides the desired hydrocarbyl-substituted polyoxypropylene N-3-aminopropyl amine.
  • the additive is employed in concentrations in the fuel from 2,050 to about 10,000 parts per million by weight.
  • U.S. Patent No. 3,440,029 discloses a gasoline anti-icing additive which is a hydrocarbyl-substituted polyoxyalkylene amine, wherein the hydrocarbyl substituent contains 8 to 24 carbon atoms.
  • This patent teaches that the additive may be prepared by known processes wherein a hydroxy compound is condensed with an alkylene oxide or mixture of alkylene oxides and then the terminal amino group is attached by either reductive amination or by cyanoethylation followed by hydrogenation.
  • hydroxy compound or oxyalkylated derivative thereof may be reacted with bis(2-chloroethyl)ether and alkali to make a chlorine-terminated compound, which is then reacted with ammonia to produce the amine-terminated final product.
  • U.S. Patent No. 5,089,029 issued February 18, 1992 to Hashimoto et al., discloses a fuel oil additive prepared by condensing a alcohol with and alkylene oxide followed by cyanoethylation and hydrogenation.
  • U.S. Patent No. 4,247,301 discloses hydrocarbyl-substituted poly(oxyalkylene) polyamines, wherein the hydrocarbyl group contains from 1 to 30 carbon atoms and the polyamine moiety contains from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.
  • the additives may be prepared by the reaction of a suitable hydrocarbyl-terminated polyether alcohol with a halogenating agent such as HCl, thionyl chloride, or epichlorohydrin to form a polyether chloride, followed by reaction of the polyether chloride with a polyamine to form the desired poly(oxyalkylene) polyamine.
  • a halogenating agent such as HCl, thionyl chloride, or epichlorohydrin
  • This patent also teaches at Example 6 that the polyether chloride may be reacted with ammonia or dimethylamine to form the corresponding polyether amine or polyether dimethylamine.
  • U.S. Patent No. 5,749,929 issued May 12, 1998 to Cherpeck et al., discloses a fuel additive compositions containing an aromatic ester of polyalkyphenoxyalkanols with a poly(oxyalkylene) amine.
  • U.S. Patent No. 5,752,991 issued May 19, 1998 to Plavac, discloses fuel compositions containing from about 50 to about 2,500 parts per million by weight of a long chain alkylphenyl polyoxyalkylene amine, wherein the alkyl substituent on the phenyl ring has at least 40 carbon atoms.
  • the present invention is directed to fuel compositions employing a hydrocarbyl-substituted polyoxyalkylene amine and a glycol ether component useful for the prevention and control of engine deposits. Moreover, said fuel additive composition of the present invention can be used for the control and removal of existing tenacious engine deposits, and is particularly suited for controlling and removing piston ring groove deposits.
  • the present invention discloses a relatively high concentration of an additive package in a fuel, thus forming an effective deposit removing fuel composition. Accordingly, the present invention is directed to a fuel composition comprising a major amount of hydrocarbons boiling in the gasoline range and
  • an additional component can be added to the fuel in conjunction with the hydrocarbyl-substituted polyoxyalkylene amine and glycol ether component described above.
  • the present invention is directed to a fuel composition comprising a major amount of hydrocarbons boiling in the gasoline range, components a) and b) described herein above, and further comprising about 100 to 10,000 parts per million by weight of an aromatic ester compound of the formula: wherein:
  • the present invention is directed to a fuel composition
  • a fuel composition comprising a major amount of hydrocarbons boiling in the gasoline range, components a) and b) described herein above, and further comprising 100 to 15,000 parts per million by weight of a cyclic carbonate of the formula wherein:
  • the present invention is based on the surprising discovery that fuel compositions containing high concentrations of certain hydrocarbyl-substituted polyoxyalkylene amines and at least one glycol ether component provide excellent control of engine deposits and is particularly suited for removal of deposits, especially piston ring groove deposits, piston top deposits, piston bowl deposits, as well as intake valve deposits and fuel injectors. Accordingly, the fuel compositions of the present invention can be used for controlling or removing these deposits, especially piston ring deposits, by operating an engine with fuel compositions of the present invention.
  • amino refers to the group: --NH 2 .
  • N-alkylamino refers to the group: --NHR a wherein R a is an alkyl group.
  • N,N-dialkylamino refers to the group: --NR b R c , wherein R b and R c are alkyl groups.
  • hydrocarbyl refers to an organic radical primarily composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl or alkaryl. Such hydrocarbyl groups are generally free of aliphatic unsaturation, i.e., olefinic or acetylenic unsaturation, but may contain minor amounts of heteroatoms, such as oxygen or nitrogen, or halogens, such as chlorine.
  • alkyl refers to both straight- and branched-chain alkyl groups.
  • lower alkyl refers to alkyl groups having 1 to about 6 carbon atoms and includes primary, secondary, and tertiary alkyl groups.
  • Typical lower alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and the like.
  • alkylene refers to straight- and branched-chain alkylene groups having at least 2 carbon atoms.
  • Typical alkylene groups include, for example, ethylene (--CH 2 CH 2 --), propylene (--CH 2 CH 2 CH 2 --), isopropylene (--CH(CH 3 )CH 2 --), n-butylene (--CH 2 CH 2 CH 2 CH 2 --), sec-butylene (--CH(CH 2 CH 3 )CH 2 ) --), n-pentylene (--CH 2 CH 2 CH 2 CH 2 CH 2 --), and the like.
  • polyoxyalkylene refers to a polymer or oligomer having the general formula: wherein:
  • hydrocarbyl-substituted polyoxyalkylene amines employed in the present invention have the general formula hydrocarbyl-substituted polyoxyalkylene amine of the formula: wherein:
  • R is an alkyl or an alkylphenyl group, wherein the alkyl moiety is straight or branched chain.
  • one of R 1 and R 2 is lower alkyl of 1 to 4 carbon atoms, ant the other is hydrogen. More preferably, one of R 1 and R 2 is methyl or ethyl, and the other is hydrogen. Yet, even more preferably R 1 is hydrogen and R 2 is methyl or ethyl and more preferably ethyl.
  • A is amino, N-alkyl amino having from about 1 to about 20 carbon atoms in the alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms; N,N-dialkyl amino having from about 1 to about 20 carbon atoms in each alkyl group, preferably about 1 to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms; or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms, preferably about 2 to 12 amine nitrogen atoms and about 2 to 24 carbon atoms. More preferably, A is amino or a polyamine moiety derived from a polyalkylene polyamine, including alkylene diamine. Most preferably, A is amino or a polyamine moiety derived from ethylene diamine or diethylene triamine.
  • x is an integer from about 5 to about 50, more preferably from about 8 to about 30, and most preferably from about 10 to about 25.
  • the hydrocarbyl-substituted polyoxyalkylene amines of formula I will generally have a sufficient molecular weight so as to be non-volatile at normal engine intake valve operating temperatures (about 200 °C - 250 °C). Typically, the molecular weight of these compounds will range from about 600 to about 10,000.
  • Fuel-soluble salts of the compounds of formula I can be readily prepared for those compounds containing an amino or substituted amino group and such salts are contemplated to be useful for preventing or controlling engine deposits.
  • Suitable salts include, for example, those obtained by protonating the amino moiety with a strong organic acid, such as an alkyl- or arylsulfonic acid.
  • Preferred salts are derived from toluenesulfonic acid and methanesulfonic acid.
  • hydrocarbyl-substituted polyoxyalkylene amines employed in this invention may be prepared by the following general methods and procedures. It should be appreciated that where typical or preferred process conditions (e.g., reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions may also be used unless otherwise stated. Optimum reaction conditions may vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art by routine optimization procedures.
  • hydrocarbyl-substituted polyoxyalkylene amines employed in the present invention contain (A-1) a hydrocarbyl-substituted polyoxyalkylene component, and (A-2) an amine component; described herein below.
  • hydrocarbyl-substituted polyoxyalkylene polymers which are utilized in preparing the hydrocarbyl-substituted polyoxyalkylene amines employed in the present invention are monohydroxy compounds, i.e., alcohols, often termed hydrocarbyl "capped" polyoxyalkylene glycols and are to be distinguished from the polyoxyalkylene glycols (diols), which are not hydrocarbyl terminated, i.e., not capped.
  • the hydrocarbyl-substituted polyoxyalkylene alcohols are produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, or the butylene oxides, to the hydroxy compound, ROH, under polymerization conditions, wherein R is the hydrocarbyl group, as defined above, which caps the polyoxyalkylene chain.
  • Preferred polyoxyalkylene polymers are those derived from C 3 to C 4 oxyalkylene units. Methods of production and properties of these polymers are disclosed in U.S. Patent No. 2,841,479 and Kirk-Othmer's "Encyclopedia of Chemical Technology", Volume 19, page 507.
  • a single type of alkylene oxide may be employed, e.g., propylene oxide, in which case the product is a homopolymer, e.g., a polyoxypropylene alcohol.
  • copolymers are equally satisfactory and random copolymers are readily prepared by contacting the hydroxy-containing compound with a mixture of alkylene oxides, such as a mixture of propylene and butylene oxides.
  • Block copolymers of oxyalkylene units also provide satisfactory polyoxyalkylene units for the practice of the present invention.
  • the amount of alkylene oxide employed in this reaction will generally depend on the number of oxyalkylene units desired in the product. Typically, the molar ratio of alkylene oxide to hydroxy-containing compound will range from about 5:1 to about 100:1; preferably, from about 5:1 to about 50:1, more preferably from about 8:1 to about 30:1; even more preferably form about 10:1 to about 25:1.
  • Alkylene oxides suitable for use in this polymerization reaction include, for example, ethylene oxide; propylene oxide; and butylene oxides, such as 1,2-butylene oxide (1,2-epoxybutane) and 2,3-butylene oxide (2,3-epoxybutane).
  • Preferred alkylene oxides are propylene oxide and 1,2-butylene oxide, both individually and in mixtures thereof.
  • the hydrocarbyl moiety, R, which terminates the polyoxyalkylene chain will generally contain from about 1 to about 30 carbon atoms, preferably from about 2 to about 20 carbon atoms, and more preferably from about 4 to about 18 carbon atoms, and is generally derived from the monohydroxy compound, ROH, which is the initial site of the alkylene oxide addition in the polymerization reaction.
  • ROH monohydroxy compound
  • Such monohydroxy compounds are preferably aliphatic or aromatic alcohols having from about 1 to about 30 carbon atoms, more preferably and alkanol or an alkylphenol, and most preferably an alkylphenol wherein the alkyl substituent is a straight or branched chain alkyl of from about 1 to about 24 carbon atoms.
  • Preferred alkylphenols include those wherein the alkyl substituent contains from about 4 to about 24 carbon atoms, more preferably 12 to 16 carbon atoms.
  • An especially preferred alkylphenol is one wherein the alkyl group is obtained by polymerizing propylene to an average of 4 propylene units, that is, about 12 carbon atoms, having the common name of propylene tetramer. The resulting alkylphenol is commonly called tetrapropenylphenol or, more generically, dodecylphenol.
  • Preferred alkylphenol-initiated polyoxyalkylene compounds may be termed either alkylphenylpolyoxyalkylene alcohols or polyalkoxylated alkylphenols.
  • hydrocarbyl-substituted polyoxyalkylene amines employed in the present invention contain an amine component.
  • the amine component will contain an average of at least about one basic nitrogen atom per molecule.
  • a "basic nitrogen atom” is one that is titratable by a strong acid, for example, a primary, secondary, or tertiary amine nitrogen; as distinguished from, for example, an carbamyl nitrogen, e.g., --OC(O)NH--, which is not titratable with a strong acid.
  • at least one of the basic nitrogen atoms of the amine component will be primary or secondary amine nitrogen, more preferably at least one will be a primary amine nitrogen.
  • the amine component of the hydrocarbyl-substituted polyoxyalkylene amines employed in this invention is preferably derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom.
  • Primary alkyl monoamines useful in preparing compounds of the present invention contain 1 nitrogen atom and from about 1 to about 20 carbon atoms, more preferably about 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms.
  • suitable monoamines include N-methylamine, N-ethylamine, N-n-propylamine, N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butylamine, N-n-pentylamine, N-cyclopentylamine, N-n-hexylamine, N-cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzylamine, N-(2-phenylethyl)amine, 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoeth
  • the amine component of the presently employed fuel additive may also be derived from a secondary dialkyl monoamine.
  • the alkyl groups of the secondary amine may be the same or different and will generally each contain about 1 to about 20 carbon atoms, more preferably about 1 to about 6 carbon atoms, most preferably about 1 to about 4 carbon atoms.
  • One or both of the alkyl groups may also contain one or more oxygen atoms.
  • the alkyl groups of the secondary amine are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-methoxyethyl. More preferably, the alkyl groups are methyl, ethyl or propyl.
  • Typical secondary amines which may be used in this invention include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-di-sec-butylamine, N,N-di-n-pentylamine, N,N-di-n-hexylamine, N,N-dicyclohexylamine, N,N-dioctylamine, N-ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl-N-methylamine, N-methyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N,N-di(2-hydroxyethyl)amine, N,N-di(3-hydroxyprop
  • Cyclic secondary amines may also be used to form the additives employed in this invention.
  • the alkyl groups when taken together, form one or more 5- or 6-membered rings containing up to about 20 carbon atoms.
  • the ring containing the amine nitrogen atom is generally saturated, but may be fused to one or more saturated or unsaturated rings.
  • the rings may be substituted with hydrocarbyl groups of from 1 to about 10 carbon atoms and may contain one or more oxygen atoms.
  • Suitable cyclic secondary amines include piperidine, 4-methylpiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine and the like.
  • Suitable polyamines can have a straight- or branched-chain structure and may be cyclic or acyclic or combinations thereof. Generally, the amine nitrogen atoms of such polyamines will be separated from one another by at least two carbon atoms, i.e., polyamines having an aminal structure are not suitable.
  • the polyamine may also contain one or more oxygen atoms, typically present as an ether or a hydroxyl group. Polyamines having a carbon-to-nitrogen ratio of from about 1:1 to about 10:1 are particularly preferred.
  • polyalkylene polyamines including alkylene diamines.
  • Such polyalkylene polyamines will typically contain from about 2 to about 12 nitrogen atoms and from about 2 to about 40 carbon atoms, preferably about 2 to about 24 carbon atoms.
  • the alkylene groups of such polyalkylene polyamines will contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms.
  • suitable polyalkylene polyamines include ethylenediamine, propylenediamine, isopropylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, diisopropylenetriamine, dibutylenetriamine, di-sec-butylenetriamine, triethylenetetraamine, tripropylenetetramine, triisobutylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, and mixtures thereof.
  • polyalkylene polyamines are ethylenediamine, diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine. Most preferred are ethylenediamine and diethylenetriamine, especially ethylenediamine.
  • cyclic polyamines having one or more 5- to 6-membered rings.
  • Such cyclic polyamines compounds include piperazine, 2-methylpiperazine, N-(2-aminoethyl)piperazine, N-2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane, 3-aminopyrrolidine, N-(2-aminoethyl)pyrrolidine, and the like.
  • the piperazines are preferred.
  • polyamines suitable for use in the present invention are commercially available and others may be prepared by methods which are well known in the art.
  • methods for preparing amines and their reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's “Chemistry of Organic Compounds”, Saunders, Philadelphia, 2 nd edition, 1957; and Kirk-Othmer's "Encyclopedia of Chemical Technology", 2 nd edition., especially Volume 2, pp. 99-116.
  • the additives employed in this invention may be conveniently prepared by reacting a hydrocarbyl-substituted polyoxyalkylene alcohol, either directly or through an intermediate, with a nitrogen-containing compound, such as ammonia, a primary or secondary alkyl monoamine or a polyamine, as described herein.
  • a nitrogen-containing compound such as ammonia, a primary or secondary alkyl monoamine or a polyamine, as described herein.
  • hydrocarbyl-substituted polyoxyalkylene alcohols used to form the polyoxyalkylene amines employed in the present invention are typically known compounds that can be prepared using conventional procedures. Suitable procedures for preparing such compounds are taught, for example, in U.S. Patent Nos. 2,782,240 and 2,841,479, as well as U.S. Patent No. 4,881,945, the disclosures of which are incorporated herein by reference.
  • the polyoxyalkylene alcohols are prepared by contacting an alkoxide or phenoxide metal salt with from about 5 to about 100 molar equivalents of an alkylene oxide, such as propylene oxide or butylene oxide, or mixtures of alkylene oxides.
  • an alkylene oxide such as propylene oxide or butylene oxide, or mixtures of alkylene oxides.
  • the alkoxide or phenoxide metal salt is prepared by contacting the corresponding hydroxy compound with a strong base, such as sodium hydride, potassium hydride, sodium amide, and the like, in an inert solvent, such as toluene, xylene, and the like, under substantially anhydrous conditions at a temperature in the range from about -10 °C to about 120 °C for from about 0.25 to about 3 hours.
  • a strong base such as sodium hydride, potassium hydride, sodium amide, and the like
  • an inert solvent such as toluene, xylene, and the like
  • the alkoxide or phenoxide metal salt is generally not isolated, but is reacted in situ with the alkylene oxide or mixture of alkylene oxides to provide, after neutralization, the polyoxyalkylene alcohol.
  • This polymerization reaction is typically conducted in a substantially anhydrous inert solvent at a temperature of from about 30 °C to about 150 °C for from about 2 to about 120 hours. Suitable solvents for this reaction, include toluene, xylene, and the like.
  • the reaction is conducted at a pressure sufficient to contain the reactants and the solvent, preferably at atmospheric or ambient pressure.
  • the hydrocarbyl-substituted polyoxyalkylene alcohol may then be converted to the desired polyoxyalkylene amine by a variety of procedures known in the art.
  • the terminal hydroxy group on the hydrocarbyl-substituted polyoxyalkylene alcohol may first be converted to a suitable leaving group, such as a mesylate, chloride or bromide, and the like, by reaction with a suitable reagent, such as methanesulfonyl chloride.
  • a suitable reagent such as methanesulfonyl chloride.
  • the resulting polyoxyalkylene mesylate or equivalent intermediate may then be converted to a phthalimide derivative by reaction with potassium phthalimide in the presence of a suitable solvent, such as N,N-dimethylformamide.
  • the polyoxyalkylene phthalimide derivative is subsequently converted to the desired hydrocarbyl-substituted polyoxyalkylene amine by reaction with a suitable amine, such as hydrazine.
  • the polyoxyalkylene alcohol may also be converted to the corresponding polyoxyalkylene chloride by reaction with a suitable halogenating agent, such as HCl, thionyl chloride, or epichlorohydrin, followed by displacement of the chloride with a suitable amine, such as ammonia, a primary or secondary alkyl monoamine, or a polyamine, as described, for example, in U.S. Patent No. 4,247,301 to Honnen, the disclosure of which is incorporated herein by reference.
  • a suitable halogenating agent such as HCl, thionyl chloride, or epichlorohydrin
  • the hydrocarbyl-substituted polyoxyalkylene amines employed in the present invention may be prepared from the corresponding polyoxyalkylene alcohol by a process commonly referred to as reductive amination, such as described in U.S. Patent No. 5,112,364 to Rath et al. and U.S. Patent No. 4,332,595 to Herbstman et al., the disclosures of which are incorporated herein by reference.
  • the hydrocarbyl-substituted polyoxyalkylene alcohol is aminated with an appropriate amine, such as ammonia or a primary alkyl monoamine, in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst.
  • the amination reaction is typically carried out at temperatures in the range of about 160 °C to about 250 °C and pressures of about 1,000 to about 5,000 psig, preferably about 1,500 to about 3,000 psig.
  • Suitable hydrogenation-dehydrogenation catalysts include those containing platinum, palladium, cobalt, nickel, copper, or chromium, or mixtures thereof.
  • an excess of the ammonia or amine reactant is used, such as about a 5-fold to about 60-fold molar excess, and preferably about a 10-fold to about 40-fold molar excess, of ammonia or amine.
  • the amination is preferably conducted using a two-step procedure as described in European Patent Application Publication No. EP 0,781,793, published July 2, 1997, the disclosure of which is incorporated herein by reference in its entirety.
  • a polyoxyalkylene alcohol is first contacted with a hydrogenation-dehydrogenation catalyst at a temperature of at least 230 °C to provide a polymeric carbonyl intermediate, which is subsequently reacted with a polyamine at a temperature below about 190 °C in the presence of hydrogen and a hydrogenation catalyst to produce the polyoxyalkylene polyamine adduct.
  • a dodecylphenoxypoly(oxybutylene)poly(oxypropylene) amine was prepared by the reductive amination with ammonia of the random copolymer poly(oxyalkylene) alcohol, dodecylphenoxy poly(oxybutylene)poly(oxypropylene) alcohol, wherein the alcohol has a number average molecular weight of about 1598.
  • the poly(oxyalkylene) alcohol was prepared from dodecylphenol using a 75/25 weight/weight ratio of butylene oxide and propylene oxide, in accordance with the procedures described in U.S. Patent Nos.
  • a dodecylphenoxy poly(oxybutylene) amine was prepared by the reductive amination with ammonia of a dodecylphenoxy poly(oxybutylene) alcohol having an average molecular weight of about 1600.
  • the dodecylphenoxy poly(oxybutylene) alcohol was prepared from dodecylphenol and butylene oxide, in accordance with the procedures described in U.S. Patent Nos. 4,191,537; 2,782,240; and 2,841,479, as well as in Kirk Othmer, "Encyclopedia of Chemical Technology", 4 th edition, Volume 19, 1996, page 722.
  • the reductive amination of the dodecylphenoxy poly(oxybutylene) alcohol was carried out using conventional techniques as described in U.S. Patent Nos. 5,112,364; 4,609,377; and 3,440,029.
  • glycol ether employed in this invention can be represented by the formula: wherein:
  • R 4 is an alkylene group having 2 to 4 carbon atoms, and more particularly R 4 O is derived from ethylene oxide, propylene oxide or butylene oxide or mixtures thereof.
  • y is an integer from 1 to 50.
  • R 3 is alkyl, phenyl, or alkylphenyl. Particularly preferred alkyl groups for R 3 are straight and branched chain C 1 to C 15 alkyl groups.
  • Preferred alkylphenyl group include those wherein the alkyl substituent contains form about 4 to about 24 carbon atoms and more preferably 12 to 16 carbon atoms.
  • a particularly preferred alkylphenyl is dodecylphenyl.
  • a sub-group of glycol ether compounds useful in the present invention is comprised of one or a mixture of high molecular weight glycol ethers, wherein the molecular weight of the glycol ether compound is from about 750 to about 3,000; and more preferably having a molecular weight from about 900 to about 1,500.
  • These high molecular weight glycol ethers can be synthesized according to the description described hereinabove for the hydrocarbyl-substituted polyoxyalkylene component; and therefore, the number of oxyalkylene groups in formula B-I will be greater than 5, or stated in another fashion, in formula B-1, y is greater than 5.
  • y is an integer from 5-50, more preferably 8-30 and even more preferably from 10-25.
  • y in formula B-I is selected to be substantially the same range in value as x in formula I.
  • Preferred high molecular weight glycol ethers are characterized by having viscosities in their undiluted state of at least about 60 cSt, more preferably at least about 70 cSt, at 40 °C and at least about 11 cSt, more preferably at least about 13 cSt, at 100 °C.
  • these high molecular weight glycol ether compounds used in the practice of this invention preferably have viscosities in their undiluted state of no more than about 400 cSt at 40 °C and no more than about 50 cSt at 100 °C.
  • the high molecular weight (i.e. number average molecular weights from 750 to 3,000) are comprised of repeating units formed by reacting an alcohol or polyalcohol with an alkylene oxide, such as propylene oxide and/or butylene oxide with or without use of ethylene oxide, and especially products in which at least 80 mole % of the oxyalkylene groups in the molecule are derived from 1,2-propylene oxide.
  • a particularly preferred sub-group of the glycol ether compounds employed in the present invention is comprised of one or a mixture of low molecular weight glycol ethers compounds; wherein the molecular weight of each of the glycol ether compound is from 100 to 450, more preferably from 115 to about 350, and even more preferably from about 115 to about 250.
  • These low molecular weight glycol ethers are characterized by having viscosities in their undiluted state of less than about 40 cSt, more preferably less than about 30 cSt, at 25 °C.
  • the number of oxyalkylene units or y in the formula B-I above is an integer from 1 to 4, more preferably from 1 to 3, and even more particularly from 1 to 2.
  • these low molecular weight glycol ether compounds are synthesized by reacting one mole of an alcohol with one, two, three or four moles of an oxide (preferably ethylene or propylene) and are typically considered to be a derivative of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene gycol, and the like.
  • these low molecular weight glycol ethers include mono-glycol ethers, di-glycol ethers, and tri-glycol ethers.
  • mono-glycol ethers include ethylene glycol monomethyl ether (Methyl Cellosolve), ethylene glycol monoethyl ether (Cellosolve), ethylene glycol monopropyl ether (Propyl Cellosolve), ethylene glycol monobutyl ether (Butyl Cellosolve), ethylene glycol monohexyl ether (Hexyl Cellosolve), ethylene glycol monophenyl ether (Dowanol EPH), propylene glycol monomethyl ether (Methyl Propasol), propylene glycol monopropyl ether (Propyl Propasol), propylene glycol monobutyl ether (Butyl Propasol), propylene glycol t-butyl ether (Arcosolv PTB), and propylene glycol monophenyl monophen
  • di-glycol ethers include diethylene glycol monomethyl ether (Methyl Carbitol), diethylene glycol monoethyl ether (Carbitol), diethylene glycol monopropyl ether (Propyl Carbitol), diethylene glycol monobutyl ether (Butyl Carbitol), diethylene glycol monohexyl ether (Hexyl Carbitol), dipropylene glycol monomethyl ether (Arcosolv DPM), and dipropylene glycol n-butyl ether (Dowanol DPNB).
  • tri-glycol ethers include triethylene glycol monomethyl ether (Methoxytriglycol), triethylene glycol monoethyl ether (Ethoxytriglycol), tripropylene glycol monomethyl ether (Dowanol TPM), tripropylene glycol mono-n-propyl ether (Dowanol TPnP).
  • glycol ethers are ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, and dipropylene glycol monophenyl ether and the like; which accordingly are represented by the formula: wherein:
  • aromatic ester compound employed in the present invention can be represented by the formula: wherein:
  • aromatic esters of formula C-I and methods for synthesis are disclosed, for example, in U.S. Patent No. 5,749,929 incorporated by reference in its entirety.
  • the preferred aromatics ester compounds of formula C-I employed in the present invention are those wherein R 6 is nitro, amino, N-alkylamino, or --CH 2 NH 2 (aminomethyl). More preferably, R 6 is a nitro, amino or --CH 2 NH 2 group. Most preferably, R 6 is an amino or --CH 2 NH 2 group, especially amino.
  • R 7 is hydrogen, hydroxy, nitro or amino. More preferably, R 7 is hydrogen or hydroxy. Most preferably, R 7 is hydrogen.
  • R 10 is a polyalkyl group having an average molecular weight in the range of about 500 to 3,000, more preferably about 700 to 3,000, and most preferably about 900 to 2,500.
  • the aromatic ester compound has a combination of preferred substituents.
  • one of R 8 and R 9 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen. More preferably, one of R 8 and R 9 is hydrogen, methyl or ethyl, and the other is hydrogen. Most preferably, R 8 is hydrogen, methyl or ethyl, and R 9 is hydrogen.
  • R 6 and/or R 7 is an N-alkylamino group
  • the alkyl group of the N-alkylamino moiety preferably contains 1 to 4 carbon atoms. More preferably, the N-alkylamino is N-methylamino or N-ethylamino.
  • each alkyl group of the N,N-dialkylamino moiety preferably contains 1 to 4 carbon atoms. More preferably, each alkyl group is either methyl or ethyl.
  • particularly preferred N,N-dialkylamino groups are N,N-dimethylamino, N-ethyl-N-methylamino and N,N-diethylamino groups.
  • a further preferred group of aromatic ester compounds of formula C-I are those wherein R 6 is amino, nitro, or --CH 2 NH 2 and R 7 is hydrogen or hydroxy.
  • a particularly preferred group of compounds are those wherein R 6 is amino, R 7 , R 8 and R 9 are hydrogen, and R 10 is a polyalkyl group derived from polyisobutene.
  • the R 6 substituent is located at the meta or, more preferably, the para position of the benzoic acid moiety, i.e., para or meta relative to the carbonyloxy group.
  • R 7 is a substituent other than hydrogen, it is particularly preferred that this R 7 group be in a meta or para position relative to the carbonyloxy group and in an ortho position relative to the R 6 substituent.
  • R 7 is other than hydrogen, it is preferred that one of R 6 or R 7 is located para to the carbonyloxy group and the other is located meta to the carbonyloxy group.
  • the R 10 substituent on the other phenyl ring is located para or meta, more preferably para, relative to the ether linking group.
  • the aromatic ester compounds of formula C-I employed in the present invention will generally have a sufficient molecular weight so as to be non-volatile at normal engine intake valve operating temperatures (about 200 °C-250 °C). Typically, the molecular weight of the compounds employed in this invention will range from about 700 to about 3,500, preferably from about 700 to about 2,500.
  • the cyclic carbonate employed in the invention can be represented by the formula: wherein:
  • Preferred cyclic carbonates for use in this invention are those of formula 1 above where z is zero and where R 20 , R 21 , R 22 are hydrogen and R 23 is methyl, ethyl or hydroxymethyl.
  • R 21 , R 22 , R 23 , R 24 , R 25 are hydrogen.
  • Most preferred are ethylene carbonate, propylene carbonate and the butylene carbonates which are defined below.
  • 1,3-dioxolan-2-one also referred to as ethylene carbonate
  • 4-methyl-1,3-dioxolan-2-one also referred to as propylene carbonate
  • 4-hydroxymethyl-1,3-dioxolan-2-one 4,5-dimethyl-1,3-dioxolan-2-one
  • 4-ethyl-1,3-dioxolan-2-one 4,4-dimethyl-1,3-dioxolan-2-one (previous three also referred to as butylenes carbonates)
  • cyclic carbonates are commercially available such as 1,3-dioxolan-2-one or 4-methyl-1,3-dioxolan-2-one sold for example by Lyondell Chemical Company under the trade name ARCONATE.
  • Huntsman Performance Chemicals also sells, ethylene carbonate, propylene carbonate, 1,2 butylene carbonate as well as mixtures thereof under the trade name JEFFSOL.
  • Cyclic carbonates may be readily prepared by known reactions. For example although not preferred, reaction of phosgene with a suitable alpha alkane diol or an alkan-1,3-diol yields a carbonate for use within the scope of this invention as for instance in U.S. Patent No. 4,115,206 which is incorporated herein by reference.
  • the cyclic carbonates useful for this invention may be prepared by transesterification of a suitable alpha alkane diol or an alkan-1,3-diol with, e.g., diethyl carbonate under transesterification conditions.
  • a suitable alpha alkane diol or an alkan-1,3-diol with, e.g., diethyl carbonate under transesterification conditions.
  • Catalytic processes employing Cr(III)- and Co(III)-based catalyst system can also be used for synthesis of cyclic carbonates from the coupling of CO 2 and terminal epoxides under mild conditions.
  • propylene oxide reacts with CO 2 in the presence of these complexes to afford propylene carbonate quantitatively.
  • the reaction can be run with or without solvent, at modest temperatures (25-100°C), CO 2 pressures (1-5 atm), and low catalyst level (0.075 mol%).
  • alpha alkane diol means an alkane group having two hydroxyl substituents wherein the hydroxyl substituents are on adjacent carbons to each other.
  • alpha alkane diols include 1,2-propanediol, 2,3-butanediol and the like.
  • alkan-1,3-diol refers to an alkane group having two hydroxyl substituents wherein the hydroxyl substituents are beta substituted. That is, there is a methylene or a substituted methylene moiety between the hydroxyl substituted carbons.
  • alkan-1,3-diols include propan-1,3-diol, pentan-2,4-diol and the like.
  • the alpha alkane diols used to prepare the 1,3-dioxolan-2-ones employed in this invention, are either commercially available or may be prepared from the corresponding olefin by methods known in the art.
  • the olefin may first react with a peracid, such as peroxyacetic acid or hydrogen peroxide to form the corresponding epoxide which is readily hydrolyzed under acid or base catalysis to the alpha alkane diol.
  • the olefin is first halogenated to a dihalo derivative and subsequently hydrolyzed to an alpha alkane diol by reaction first with sodium acetate and then with sodium hydroxide.
  • the olefins so employed are known in the art.
  • alkan-1,3-diols used to prepare the 1,3-dioxan-2-ones employed in this invention, are either commercially available or may be prepared by standard techniques, e.g., derivatizing malonic acid.
  • 4-Hydroxymethyl 1,3-dioxolan-2-one derivatives and 5-hydroxy-1,3-dioxan-2-one derivatives may be prepared by employing glycerol or substituted glycerol in the process of U.S. Patent No. 4,115,206.
  • the mixture so prepared may be separated, if desired, by conventional techniques. Preferably the mixture is used as is.
  • 5,5-Dihydroxymethyl-1,3-dioxan-2-one may be prepared by reacting an equivalent of pentaerythritol with an equivalent of either phosgene or diethylcarbonate (or the like) under transesterification conditions.
  • 5-hydroxymethyl-5-methyl-1,3-dioxan-2-one may be prepared by reacting an equivalent of trimethylolethane with an equivalent of either phosgene or diethylcarbonate (or the like) under transesterification conditions.
  • the hydrocarbyl-substituted polyoxyalkylene amine and glycol ether components employed in the present invention are particularly useful as additives in hydrocarbon fuels in the prevention and control of piston ring grove deposits. Additionally, this combination and concentration of additive as a fuel composition exhibits superior intake valve deposit control, superior injector clean-up, as well as excellent combustion chamber deposit removal and is particularly suited for use in direct injection spark ignition engines for piston bowl clean-up.
  • the desired deposit control will be achieved by operating an internal combustion engine with a fuel composition containing a major amount of hydrocarbons boiling in the gasoline range and a deposit removing effective amount of the hydrocarbyl-substituted polyoxyalkylene amine and the glycol ether components.
  • the proper concentration of additive necessary to achieve the desired deposit control varies depending upon the type of fuel employed, the type of engine, operating conditions, and the presence of other fuel additives.
  • the concentration of the hydrocarbyl-substituted polyoxyalkylene amines of formula I employed in this invention in the hydrocarbon fuel will range from about 2,200 to about 30,000 parts per million (ppm) by weight, preferably from about 3,000 to about 20,000 ppm, more preferably from about 6,000 to about 15,000 ppm, and even more preferably from about 12,000 to about 15,000 ppm.
  • the present invention is directed to relatively high concentrations of the hydrocarbyl-substituted polyoxyalkylene amine thus the fuel composition will comprise greater than about 12,000 ppm of the hydrocarbyl-substituted polyoxyalkylene amine; and more preferably from 12,000 to 30,000 ppm, and even more preferably 15,000 to 25,000 ppm by weight in the fuel.
  • the glycol ether component of formula B-I of the present invention can be employed in the hydrocarbon fuel at concentrations as low as 100 ppm up to about 10 weight percent.
  • the glycol ether component is employed from 100 to about 60,000 ppm, and more preferably from about 1,500 to about 40,000 ppm, and even more preferably from about 3,000 to about 30,000 ppm based upon weight percent in the fuel composition and wherein the glycol ether component refers to sum of all glycol ethers in the composition.
  • the fuel composition of the present invention can further employ from about 100 to about 10,000 parts per million by weight of an aromatic ester compound of formula C-I.
  • the aromatic ester is employed from 150 to about 5,000 ppm, and even more preferably from 200 to about 3,000 ppm.
  • the fuel composition employing the hydrocarbyl-substituted polyoxyalkylene amine and the at least one glycol ether component described above can further employ from about 100 to about 15,000 parts per million by weight of a cyclic carbonate of formula D-I.
  • a cyclic carbonate of formula D-I Preferably the cyclic carbonate is employed from 200 to about 7,000 ppm, and even more preferably from 200 to about 3,000 ppm, with 500 to 1,000 ppm by weight of the cyclic carbonate in the fuel composition being particularly preferred.
  • propylene carbonate is especially preferred.
  • the hydrocarbyl-substituted polyoxyalkylene amine and at least one glycol ether component employed in the present invention, as well as other embodiments may be formulated using an inert stable oleophilic (i.e., dissolves in gasoline) organic solvent boiling in the range of from about 65 °C to about 210 °C.
  • an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene, or higher-boiling aromatics or aromatic thinners such as C 9 aromatic thinners being particularly preferred.
  • Aliphatic alcohols containing from about 6 to about 20 carbon atoms such-as isopropanol, isobutylcarbinol, n-butanol, 2-ethyl hexanol, dodecyl alcohol and the like, in combination with hydrocarbon solvents are also suitable for use with the present additives.
  • Particularly preferred are aralkyl alcohols such as benzyl alcohol, alpha and beta phenylethyl alcohol, and di- and tri-phenylmethanol; with benzyl alcohol being particularly preferred.
  • aralkyl alcohols such as benzyl alcohol, alpha and beta phenylethyl alcohol, and di- and tri-phenylmethanol; with benzyl alcohol being particularly preferred.
  • oleophilic organic solvent is employed it is less than 0.5 wt percent of the fuel composition, more preferable in a lower concentration than the glycol ether component, such as a 0.1 to .5:1 weight ratio.
  • additives of the present invention including, for example, oxygenates, such as t-butyl methyl ether, ethanol, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants/detergents, such as hydrocarbyl amines, Mannich reaction products, or succinimides. Additionally, antioxidants, metal deactivators, and demulsifiers may be present.
  • oxygenates such as t-butyl methyl ether
  • antiknock agents such as methylcyclopentadienyl manganese tricarbonyl
  • dispersants/detergents such as hydrocarbyl amines, Mannich reaction products, or succinimides.
  • antioxidants, metal deactivators, and demulsifiers may be present.
  • a fuel-soluble, nonvolatile carrier fluid or oil may also be used with the hydrocarbyl-substituted polyoxyalkylene amine and glycol ether component.
  • the carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle which substantially increases the nonvolatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing to octane requirement increase.
  • the carrier fluid may be a natural or synthetic fluid, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived fluids, such as those described, for example, in U.S. Patent No.
  • carrier fluids are believed to act as a carrier for the fuel additives of the present invention and to assist in removing and retarding certain deposits.
  • the carrier fluid may also exhibit synergistic deposit control properties when used in combination with fuel composition of this invention.
  • the carrier fluids may be employed in amounts ranging from about 50 to about 5,000 ppm by weight of the hydrocarbon fuel, preferably from about 400 to about 3,000 ppm of the fuel.
  • the ratio of carrier fluid to deposit control additive will range from about 0.01:1 to about 10:1, more preferably from about 0.1:1 to about 5:1.
  • a fuel composition of the present invention was prepared employing 20,000 ppma of a dodecylphenoxy poly(oxybutylene)amine and 5844 ppm 2-butoxy-ethanol and 5844 ppm of 2-phenoxy-ethanol in a base fuel.
  • the dodecylphenoxy poly(oxybutylene)amine was prepared in accordance as described in Example A-3.2.
  • Approximately 25 gallons of a fuel composition was prepared employing 5,000 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1 and 6,500 ppm of 2-(2-hexyloxy-ethoxy)-ethanol [or diethylene glycol hexyl ether] in a base fuel.
  • Approximately 25 gallons of a fuel composition was prepared employing 5,000 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1; 3823 ppm of 1-phenoxy-propan-2-ol [or propylene phenyl glycol ether]; 780 ppm of 2-butoxy-ethanol; 900 ppm propylene carbonate and 1000 ppm benzyl alcohol in a base fuel.
  • a comparative fuel composition was prepared employing 5,000 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1 and 5,450 ppm of an aromatic C 9 carrier fluid in a base fuel.
  • Performance Example using a 2.4 L Port Fuel Injected Dynamometer Test A 1996 four cylinder engine, having a displacement volume of 2.4 liter was used for the dynamometer test.
  • the performance evaluation program for the fuel compositions of Example 2, Example 3 and Comparative Example A was conducted by starting with a deposit-free engine and operating the engine for 100 hours to accumulate adequate level of engine deposits (referred to as dirty up phase). At the end of the dirty-up phase, the engine was disassembled and intake valve deposit weights were measured and recorded. At the end of this stage, the engine was again assembled and put through a clean up phase that included 25 gallons of the fuel compositions listed in Example 2, Example 3 and Comparative Example A.
  • Approximately 30 gallons of a fuel composition was prepared employing 3,000 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. land 4,700 ppm of 2-(2-hexyloxy-ethoxy)-ethanol [or diethylene glycol hexyl ether] in a base fuel.
  • a fuel composition was prepared employing 3,000 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1; 2,759 ppm of 1-phenoxy-propan-2-ol [or propylene phenyl glycol ether]; 566 ppm of 2-butoxy-ethanol; 652 ppm propylene carbonate and 724 ppm benzyl alcohol in a base fuel.
  • a comparative fuel composition was prepared employing 3,000 ppma of a of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1 and 4,700 ppm of an aromatic C 9 carrier fluid in a base fuel.
  • Approximately 20 gallons of a fuel composition was prepared employing 2,200 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1; 3,000 ppm of 2-phenoxy-ethanol; 220 ppma of 4-polyisobutyl phenoxyethyl para-amino benzoate and 620 ppm of a C 9 aromatic carrier fluid in base fuel.
  • the 4-polyisobutyl phenoxyethyl para-amino benzoate was prepared in accordance with Example C-1.
  • a fuel composition was prepared employing 2,200 ppma of the dodecylphenoxy poly(oxybutylene)amine employed in Ex. 1; 220 ppma of 4-polyisobutyl phenoxyethyl para-amino benzoate (as employed in Ex. 8) and 3620 ppm of a C 9 aromatic carrier fluid in base fuel.
  • Combustion chamber deposit data (piston top, cylinder head, and piston bowl) are based on deposit thickness and were acquired using similar procedure described above. Clean up data from these experiments are shown in Table 4. Injector and Combustion Chamber Clean Up Data from 1.8 L DISI Vehicle Fuel Composition Increase in Injector Flow (%) Piston Top Clean up (%) Cylinder Head Clean up (%) Piston Bowl Clean up (%) Comparative Example C 55 40.5 -8.5 68 Example 8 100 46 -8 100
  • Tables 2 and 3 demonstrate a synergistic effect and improved performance when employing a hydrocarbyl-substituted polyoxyalkylene amine with the glycol component and further with the cyclic carbonate of the present invention for removal of intake valve deposits. This is a dramatic improvement over the same type and concentration of the hydrocarbyl-substituted polyoxyalkylene amine employed by itself in a carrier. Furthermore, this same kind of dramatic improvement is illustrated in Table 4, evaluating the performance in intake valve, piston top and piston bowl clean-up.

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SG117622A1 (en) 2005-12-29

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