EP0534551B1 - Composition d'essence - Google Patents

Composition d'essence Download PDF

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Publication number
EP0534551B1
EP0534551B1 EP92202889A EP92202889A EP0534551B1 EP 0534551 B1 EP0534551 B1 EP 0534551B1 EP 92202889 A EP92202889 A EP 92202889A EP 92202889 A EP92202889 A EP 92202889A EP 0534551 B1 EP0534551 B1 EP 0534551B1
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Prior art keywords
polyamine
molecular weight
aminocarbamate
range
gasoline
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German (de)
English (en)
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EP0534551A1 (fr
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Leonard Baldine Graiff
Herbert Dale Millay
Kevin Wayne Poindexter
Robert Peter Aiello
Michael Joseph Riley
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
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    • C10L1/14—Organic compounds
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • 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
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    • 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
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    • 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
    • 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
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    • 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)
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    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

  • the present invention relates to a gasoline composition for use in an internal combustion engine and a gasoline additive concentrate.
  • Gasoline compositions have traditionally been formulated to improve the performance of carburettor and throttle body injected engines.
  • electronic port fuel injected engines were commonly introduced by automobile manufacturers.
  • problems began to be reported with intake valve deposits in electronic port fuel injected engines characterised by hard starting, stalls, and stumbles during acceleration and rough engine idle.
  • Intake valve detergency is generally defined by the BMW NA standard of intake valve cleanliness for unlimited mileage, which is an established correlation of good driveability with average intake valve deposit weight of 100 milligrams/valve or less.
  • Oil-soluble polyalkylene polyamines containing an olefinic polymer chain are known to improve detergent properties of fuels used in carburettor and throttle body type engines. These polyalkylene polyamines, particularly when used at high concentrations, can result in valve sticking and an increase in octane requirement. Various materials have been added to these polyalkylene polyamines to improve their performance. Thus, U.S. Patent No.
  • 5,006,130 discloses as a gasoline additive (a) polyalkylene polyamine and (b) at least one component selected from (i) a polymer of a C 2 to C 6 monoolefin, (ii) a copolymer of a C 2 to C 6 monoolefin, (iii) the corresponding hydrogenated polymer or copolymer, and (iv) an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or a mono- or di- ether thereof.
  • Mannich polyamines comprising the condensation product of a high molecular weight alkyl-substituted hydroxyaromatic compound, an amine which contains an amino group having at least one active hydrogen atom, and an aldehyde have been disclosed in U.S. Patent No. 4,231,759 and are said to be useful for importing detergency properties to an automotive fuel in order to keep intake valves clean.
  • WO 91/12303 describes a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 400 to about 1,200 parts per million (ppm) of a homogenous fuel additive composition comprising:
  • a gasoline composition comprising a major amount of a gasoline and from 5 ppmw to 1,000 ppmw based on the gasoline composition of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and/or a carbon atom of the alkylene radical(s) connecting the amino nitrogen atoms and said polyamine having a number average molecular weight in the range from 600 to 10,000, (ii) a Mannich polyamine comprising the condensation product of a high molecular weight sulphur-free alkyl-substituted hydroxyaromatic compound wherein the or each alkyl group has a number average molecular weight in the range from 600 to 10,000, an amine which contains an amino group having at least one active hydrogen atom, and an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1
  • Component (a) may be selected from either an aliphatic alkylene polyamine, a Mannich polyamine or mixtures of an aliphatic alkylene polyamine and a Mannich polyamine.
  • the oil soluble aliphatic alkylene polyamine component detergent (a)(i) has at least one polymer chain having from 500 to 9,900 M n (number average molecular weight) and preferably from 550 to 4,900 M n , and particularly from 600 to 1,300 M n , and which may be saturated or unsaturated and straight or branched chain and attached to a nitrogen atom and/or a carbon atom of the alkylene radicals connecting the amino nitrogen atoms.
  • the aliphatic alkylene polyamine is a compound of the general formula: where x is 0 to 5; R is selected from the group consisting of a hydrogen atom and a polyolefin group having a M n from 500 to 9,900, at least one R being a polyolefin group; each R' independently represents a C 1 -C 8 , preferably C 1 -C 4 , alkylene group; and each R'' independently represents a hydrogen atom or a lower alkyl group.
  • R is preferably 550 to 4,900 M n , with a range of 600 to 1,300 M n being particularly preferred.
  • the olefinic polymers (R) which are reacted with polyamines to form the aliphatic alkylene polyamines used in the present invention include olefinic polymers derived from alkanes or alkenes with straight or branched chains, which may or may not have aromatic or cycloaliphatic substituents, for instance, groups derived from polymers or copolymers of olefins which may or may not have a double bond.
  • Examples of unsubstituted alkenyl and alkyl groups are polyethylene groups, polypropylene groups, polybutylene groups, polyisobutylene groups, polyethylene-polypropylene groups and the corresponding groups without double bonds.
  • Examples of substituted alkenyl and alkyl groups are polyethylene-poly-alpha-methyl styrene groups and the corresponding groups without double bonds. Particularly preferred are polypropylene and especially polyisobutylene groups.
  • the R'' group may be hydrogen but is preferably lower alkyl, i.e., containing up to 7 carbon atoms, and more preferably is selected from methyl, ethyl, propyl and butyl groups.
  • the polyamines used to form the aliphatic alkylene polyamines used in this invention include primary and secondary aliphatic polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, butylene diamine, tetramethylene diamine, diaminopentane or pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, diaminooctane, decamethylene diamine, and higher homologues up to 18 carbon atoms, N-methyl ethylene diamine, N-propyl ethylene diamine, N,N-dimethyl-1,3-propane diamine, N-2-hydroxypropyl ethylene diamine, penta-(1-methylpropylene)hexamine, tetrabutylene-pentamine, hexa-(1,1-dimethylethylene)heptane, di-(1-methylamylene)-triamine, tetra-(1,3-dimethyl
  • the polyamine can be a cyclic polyamine, for instance, the cyclic polyamines formed when aliphatic polyamines with nitrogen atoms separated by ethylene groups are heated in the presence of hydrogen chloride.
  • An example of a suitable process for the preparation of an aliphatic alkylene polyamine employed according to the invention is the reaction of a halogenated polyhydrocarbon having at least one halogen atom as a substituent and a hydrocarbon chain as defined hereinbefore for R, with a polyamine.
  • the halogen atom is replaced by a polyamine group, while hydrogen halide is formed.
  • the hydrogen halide can then be removed in any suitable way, for instance, as a salt with excess polyamine.
  • the reaction between halogenated hydrocarbon and polyamine is preferably effected at elevated temperature in the presence of a solvent; particularly a solvent having a boiling point of at least 160 o C.
  • the reaction between polyhydrocarbon halide and a polyamine having more than one nitrogen atom available for this reaction is preferably effected in such a way that cross-linking is reduced to a minimum, for instance, by applying an excess of polyamine.
  • the number average molecular weight of the aliphatic alkylene polyamine will range from 600 to 10,000 M n , preferably from 600 to 5,000 M n , and most preferably from 600 to 1,500 M n .
  • the oil soluble Mannich polyamine component detergent (a)(ii) comprises a condensation product of a high molecular weight alkyl-substituted hydroxyaromatic compound, an amine which contains an amino group having at least one active hydrogen atom, preferably a polyamine, and an aldehyde.
  • condensation products can be prepared by condensing in the usual manner under Mannich reaction conditions:
  • Mannich polyamines useful in the present invention are described in U.S. Patent No. 4,231,759.
  • the foregoing high molecular weight products employed in this invention are preferably prepared according to the conventional methods heretofore employed for the preparation of Mannich condensation products, using the above-named reactants in the respective molar ratios of high molecular weight alkyl-substituted hydroxyaromatic compound (1), amine (2) and aldehyde (3) of 1 : 0.1-10 : 0.1-10.
  • a suitable condensation procedure involves adding, at a temperature ranging from ambient temperature (20°C) to 93°C, the aldehyde reagent (3), e.g.
  • the preferred detergent additives employed in this invention are high molecular weight Mannich condensation products, formed by reacting (1) an alkylphenol, whose alkyl group has 600 to 3,000 M n ; (2) an ethylene polyamine, an amine reactant; and (3) a formaldehyde affording reactant in the respective molar ratio of 1 : 0.5-2.0 : 1.0-3.0.
  • high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol and other polyalkylphenols. These polyalkylphenols may be obtained by the alkylation, in the presence of an alkylating catalyst such as BF 3 , of phenol with high molecular weight polypropylene, polybutylene and other polyalkylene compounds to give one or more alkyl substituents on the benzene ring of phenol, each alkyl substituent having 600 to 10,000 M n .
  • an alkylating catalyst such as BF 3
  • the 600 M n and higher M n alkyl substituents on the hydroxyaromatic compounds may be derived from high molecular weight polypropylenes, polybutenes and other polymers of mono-olefins, principally 1-monoolefins. Also useful are copolymers of mono-olefins with monomers copolymerisable therewith wherein the copolymer contains at least 90%, by weight, of mono-olefin units. Specific examples are copolymers of propylene or butenes (butene-1, butene-2 and isobutylene) with monomers copolymerisable therewith wherein the copolymer contains at least 90% by weight, of propylene and butene units, respectively.
  • Said monomers copolymerisable with propylene or said butenes include monomers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ether, aldehyde, which do appreciably lower the oil-solubility of the polymer.
  • the comonomers polymerised with propylene or said butenes may be aliphatic and can also contain non-aliphatic groups, e.g., styrene, methylstyrene, p-dimethylstyrene and divinylbenzene.
  • others which may be used include, exclusive of sulphurised derivatives, high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy diphenyl, benzylphenol, phenethylphenol, naphthol and tolylnaphthol.
  • Preferred for the preparation of such preferred Mannich condensation products are the polyalkylphenol reactants, e.g., polypropylphenol and polybutylphenol whose alkyl groups have 600 to 3,000 M n , the more preferred alkyl groups having 740 to 1,200 M n , while the most preferred alkyl group is a polypropyl group having 800 to 850 M n , especially 825 M n .
  • polyalkylphenol reactants e.g., polypropylphenol and polybutylphenol whose alkyl groups have 600 to 3,000 M n , the more preferred alkyl groups having 740 to 1,200 M n , while the most preferred alkyl group is a polypropyl group having 800 to 850 M n , especially 825 M n .
  • alkyl-substituted hydroxyaromatic compound is that of a para-substituted mono-alkylphenol.
  • any alkylphenol readily reactive in the Mannich condensation reaction may be employed. Accordingly, ortho mono-alkylphenols and dialkylphenols are suitable for use in this invention.
  • amine reactants may be utilised including mono and polyamines.
  • the preferred amine reactants are alkylene polyamines, principally polyethylene polyamines.
  • Other representative organic compounds containing at least one >NH group suitable for use in the preparation of Mannich condensation products are well known and include the mono- and di-amino alkanes and their substituted analogues, e.g., ethylamine, dimethylamine, dimethylaminopropylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogues.
  • Suitable alkylene polyamine reactants include ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, octaethylene nonamine, nonaethylene decamine, decaethylene undecamine and mixtures of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula (II) mentioned before, where A is divalent ethylene and n is an integer from 1 to 10.
  • propylene polyamines such as propylene diamine and di-, tri-, tetra-, penta-propylene tri-, tetra-, penta- and hexa-amines are also suitable reactants.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
  • the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloro alkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.
  • aldehydes for use in the preparation of the high molecular products used in this invention include the aliphatic aldehydes such as formaldehyde (including paraformaldehyde), acetaldehyde and aldol (b-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred.
  • Mixtures of components (a)(i) and (a)(ii) may also be suitably combined with component (b) to prepare the gasoline compositions according to the present invention.
  • the amine moiety of the hydrocarbyl-terminated poly(oxyalkylene) aminocarbamate is preferably derived from a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.
  • the polyamine is preferably reacted with a hydrocarbyl poly(oxyalkylene) chloroformate to produce the hydrocarbyl poly(oxyalkylene) aminocarbamate component (b).
  • the chloroformate is itself derived from hydrocarbyl poly(oxyalkylene) alcohol by reaction with phosgene.
  • the polymer encompassing diamines, provides the product poly(oxyalkylene) aminocarbamate with, on average, at least one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by strong acid.
  • the polyamine preferably has a carbon-to-nitrogen ratio in the range from 1:1 to 10:1.
  • the polyamine may be substituted with substituents selected from hydrocarbyl groups having from 1 to 10 carbon atoms, acyl groups having from 2 to 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups having from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. Examples of suitable polyamines are those described in U.S. Patent No. 4,191,537.
  • Hydrocarbyl denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combination thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation.
  • the more preferred polyamine for the aminocarbamate component is a polyalkylene polyamine, including alkylenediamine, and including substituted polyamines,e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
  • the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms.
  • polyamines include ethylenediamine, diethylene triamine, triethylene tetramine, dipropylene triamine and tetraethylene pentamine.
  • polyethylene polyamines and polypropylene polyamines containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred, with the lower polyethylene/polypropylene polyamines, e.g. ethylenediamine and dipropylene triamine, being most preferred.
  • the hydrocarbyl-terminated poly(oxyalkylene) polymers which are utilised in preparing the aminocarbamates are monohydroxy compounds, e.g., alcohols, often termed monohydroxy polyethers, or polyalkylene glycol monocarbyl ethers, or "capped" poly(oxyalkylene) glycols, and are to be distinguished from the poly(oxyalkylene) glycols (diols), or polyols, which are not hydrocarbyl-terminated, i.e., are not capped.
  • the hydrocarbyl-terminated poly(oxyalklylene) alcohols are produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide and butylene oxide to the hydroxy compound ROH under polymerisation conditions, wherein R is the hydrocarbyl group which caps the poly(oxyalkylene) chain.
  • R is the hydrocarbyl group which caps the poly(oxyalkylene) chain.
  • the group R will contain from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms and is aliphatic or aromatic, i.e. an alkyl or alkylphenyl wherein the alkyl is a straight or branched-chain of from 1 to 24 carbon atoms.
  • the oxyalkylene units in the poly(oxyalkylene) component preferably contain from 2 to 5 carbon atoms but one or more units of a larger carbon number may also be present.
  • Each poly(oxyalkylene) polymer contains at least 5 oxyalkylene units, preferably 8 to 100 oxyalkylene units, more preferably 10 to 100 units and most preferably 10 to 25 such units.
  • the poly(oxyalkylene) component is more fully described and exemplified in U.S. Patents Nos. 4,191,537 and 4,197,409.
  • the hydrocarbyl poly(oxyalkylene) aminocarbamate used in the compositions of the present invention is obtained by linking the amine component and the poly(oxyalkylene) component together through a carbamate linkage, i.e., wherein the oxygen may be regarded as the terminal hydroxyl oxygen of the poly(oxyalkylene) alcohol component, and the carbonyl group, -C(O)-, is preferably provided by a coupling agent, e.g., phosgene.
  • a coupling agent e.g., phosgene
  • the hydrocarbyl poly(oxyalkylene) alcohol is reacted with phosgene to produce a chloroformate and the chloroformate is reacted with the polyamine.
  • the carbamate linkages are formed as the poly(oxyalkylene) chains are bound to the nitrogen of the polyamine through the oxycarbonyl group of the chloroformate. Since there may be more than one nitrogen atom of the polyamine which is capable of reacting with the chloroformate, the aminocarbamate contains at least one hydrocarbyl poly(oxyalkylene) polymer chain bonded through an oxycarbonyl group to a nitrogen atom of the polyamine, but the carbamate may contain 1, 2 or more such chains.
  • the hydrocarbyl poly(oxyalkylene) aminocarbamate product contains, on average, 1 poly(oxyalkylene) chain per molecule (i.e., is a monocarbamate), although it is understood that this reaction route may lead to mixtures containing appreciable amounts of di- or higher poly(oxyalkylene) chain substitution on a polyamine containing several reactive nitrogen atoms.
  • Several especially preferred aminocarbamates are butyl-poly(oxyalkylene)-N-(2-aminoethyl) carbamate and alkylphenyl-poly(oxyalkylene)-N-(2-aminoethyl) carbamate.
  • a particularly preferred carbamate can be expressed by the following formula: wherein R is a hydrogen atom or an alkyl group and m is greater than 5.
  • Aminocarbamates suitable for use in the present invention can be obtained from the Oronite Additives Division of Chevron Chemical Company.
  • the number average molecular weight of the aminocarbamate will range from 600 to 10,000 M n , preferably from 600 to 5,000 M n and most preferably from 600 to 2,000 M n .
  • the total amount of component (a) plus component (b) present in the gasoline compositions of the invention will range from 5 to 1,000, preferably from 50 to 1,000, more preferably from 50 to 500 and even more preferably from 100 to 400 and most preferably from 200 to 300 parts per million by weight (ppmw) based on the gasoline composition.
  • the weight ratio, component (a):component (b), will range from 3:1 to 1:1 and preferably from 2:1 to 1:1. In a particularly preferred embodiment the weight ratio is 1:1.
  • Suitable liquid hydrocarbon fuels in the gasoline boiling range are mixtures of hydrocarbons having a boiling point in the range from 25°C to 232°C and comprise 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 base fuel 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 of these.
  • the hydrocarbon composition and octane level of the base fuel are not critical.
  • the octane level, (R+M)/2, will generally be above 85.
  • Any conventional motor fuel base may be employed in the practice of this invention.
  • hydrocarbons can be replaced by up to substantial amounts of conventional alcohols, or ethers, conventionally known for use in fuels.
  • the base fuels are desirably substantially free of water, since water could impede a smooth combustion.
  • the gasolines used in the present invention are lead-free, but can contain minor amounts of blending agents such as methanol, ethanol and methyl tertiary butyl ether e.g., from 0.1 to 15% volume of the base fuel.
  • the gasolines can also contain antioxidants such as phenolics, e.g., 2,6-di-tert-butylphenol or phenylenediamines, e.g., N,N'-di-sec-butyl-p-phenylenediamine, dyes, metal deactivators and dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins.
  • Corrosion inhibitors such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having 20 to 500 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group having a number average molecular weight of 950, in an amount of 1 to 1,000 ppmw.
  • the gasolines may also contain antiknock compounds such as a methyl cyclopentadienylmanganese tricarbonyl and ortho-azidophenol as well as co-antiknock compounds such as benzoylacetone.
  • the additive mixture (a) plus (b) used in the present invention can be added to the gasoline neat or in the form of a concentrate.
  • the agent can be added separately to the gasoline or blended with other additives.
  • the present invention further provides a gasoline additive concentrate comprising a major amount of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and/or a carbon atom of the alkylene radical(s) connecting the amino nitrogen atoms and said polyamine having a number average molecular weight in the range from 600 to 10,000, (ii) a Mannich polyamine comprising the condensation product of a high molecular weight sulphur-free alkyl-substituted hydroxyaromatic compound wherein the or each alkyl group has a number average molecular weight in the range from 600 to 10,000, an amine which contains an amino group having at least one active hydrogen atom,
  • the present invention still further provides the use of from 5 ppmw to 1,000 ppmw based on total composition of a mixture of (a) an oil soluble polyamine selected from the group consisting of (i) an aliphatic alkylene polyamine containing at least one olefinic polymer chain attached to a nitrogen atom and/or a carbon atom of the alkylene radical(s) connecting the amino nitrogen atoms and said polyamine having a number average molecular weight in the range from 600 to 10,000, (ii) a Mannich polyamine comprising the condensation product of a high molecular weight sulphur-free alkyl-substituted hydroxyaromatic compound wherein the or each alkyl group has a number average molecular weight in the range from 600 to 10,000, an amine which contains an amino group having at least one active hydrogen atom, and an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1-10 : 0.1-10, and (iii) mixtures of (
  • This example illustrates the beneficial effect on intake valve deposits of a gasoline additive comprising a mixture of an aliphatic alkylene polyamine and a hydrocarbyl poly(oxyalkylene) aminocarbamate.
  • Intake valve deposit tests were conducted in a BMW 325 car equipped with the 2.7-litre, six-cylinder engine with port fuel injection, and was operated for 8,050 kilometres on the test fuel. Before the test started, deposits were removed from the cylinder head, intake manifold and piston tops and new intake valves were weighed and installed. The oil and filter were changed, new spart plugs installed and the fuel injectors flow checked. Mileage was accumulated on a road simulation dynamometer. A four minute test cycle was employed. It consisted of a 2 minute acceleration from 54 to 75 km/hr, a 1 minute acceleration to 112 km/hr and a 1 minute deceleration to 54 km/hr. The average speed was 79 km/hr and the cycle was repeated until 8050 kilometres were accumulated (almost 102 hrs).
  • Table 1 lists the additive compositions A to C, 1 and 2 used in premium unleaded base gasolines and the average (of six) intake valve deposit weights at the end of the test (8,050 kilometres).
  • Compositions A, B and C are comparative compositions whilst compositions 1 and 2 are in accordance with the present invention.
  • Table 1 Composition Component (a) (i) 1 ppmw Component (b) 2 ppmw Ratio (a)/(b) BMW 325 Results Avg.
  • Intake valve deposit tests were conducted in a BMW 318i car equipped with the 1.8-litre, four-cylinder engine which was operated for 10,000 miles (16,093.4 kilometres) on the test fuel. Before the test started, deposits were removed from the cylinder head, intake manifold and piston tops and new intake valves were weighed and installed. The oil and filter were changed, new spark plugs installed and the fuel injectors flow checked. Mileage was accumulated on public roads using trained drivers. The test route consisted of about 10% city driving, 20% on secondary roads and 70% highway driving (maximum speed of 65 mph (104.6 km/h)).
  • the primary test data was the intake valve deposit (IVD) weights at the end of the 10,000-mile (16.093.4-kilometre) test.
  • BMW's pass criteria are as follows: an average deposit weight of 100 milligrams/valve or less at the conclusion of the test meets BMW requirements for unlimited mileage acceptance; an average deposit weight of 250 mg/valve or less at the conclusion of the test meets BMW's requirement for 50,000-mile (80,467-kilometre) service.

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Claims (9)

  1. Composition d'essence comprenant une proportion majeure d'une essence et de 5 ppmp à 1000 ppmp, sur base de la composition d'essence, d'un mélange de (a) une polyamine oléosoluble choisie dans le groupe constitué de (i) une alkylènepolyamine aliphatique contenant au moins une chaîne polymérique oléfinique attachée à un atome d'azote et/ou un atome de carbone du ou des radicaux alkylène reliant les atomes d'azote amino et ladite polyamine, possédant un poids moléculaire moyen en nombre qui varie de 600 à 10 000, (ii) une polyamine de Mannich constituée par le produit de la condensation d'un composé hydroxy-aromatique à substitution alkylique, dépourvu de soufre, de poids moléculaire élevé, où le ou chaque groupe alkyle possède un poids moléculaire moyen en nombre qui varie de 600 à 10 000, une amine qui contient un groupe amino comportant au moins un atome d'hydrogène actif et un aldéhyde, où le rapport molaire respectif des réactifs est de 1:0,1-10:0,1-10 et (iii) des mélanges de (i) et (ii); et de (b) un hydrocarbylpoly(oxyalkylène)aminocarbamate oléosoluble possédant un poids moléculaire moyen en nombre qui varie de 600 à 10 000, possédant au moins un atome d'azote basique, où ledit groupe hydrocarbyle contient de 1 à 30 atomes de carbone, et où le rapport pondéral de ladite polyamine (a) audit hydrocarbylpoly(oxyalkylène)aminocarbamate (b) varie de 3:1 à 1:1.
  2. Composition suivant la revendication 1, caractérisée en ce que l'alkylènepolyamine aliphatique possède un poids moléculaire qui varie de 600 à 5000, le ou chaque groupe alkyle de la polyamine de Mannich possède un poids moléculaire qui fluctue de 600 à 3000 et l'aminocarbamate possède un poids moléculaire qui varie de 600 à 5000.
  3. Composition suivant la revendication 1 ou la revendication 2, caractérisée en ce que l'alkylènepolyamine aliphatique possède un poids moléculaire qui varie de 600 à 1500, le ou chaque groupe alkyle de la polyamine de Mannich possède un poids moléculaire qui fluctue de 1000 à 1100, et l'aminocarbamate possède un poids moléculaire qui varie de 600 à 2000.
  4. Composition suivant l'une quelconque des revendications 1 à 3, caractérisée en ce que la quantité du mélange de polyamine et d'aminocarbamate varie de 50 ppmp à 500 ppmp, sur base de la composition d'essence.
  5. Composition suivant la revendication 4, caractérisée en ce que la quantité du mélange de polyamine et d'aminocarbamate varie de 100 ppmp à 400 ppmp, sur base de la composition d'essence.
  6. Composition suivant la revendication 5, caractérisée en ce que la quantité du mélange de polyamine et d'aminocarbamate varie de 200 ppmp à 300 ppmp, sur base de la composition d'essence.
  7. Composition suivant l'une quelconque des revendications précédentes, caractérisée en ce que le rapport pondéral de la polyamine à l'aminocarbamate varie de 2:1 à 1:1.
  8. Composition suivant la revendication 7, caractérisée en ce que le rapport pondéral de la polyamine à l'aminocarbamate est de 1:1.
  9. Additif concentré pour l'essence comprenant une proportion majeure d'un mélange de (a) une polyamine oléosoluble choisie dans le groupe formé par (i) une alkylènepolyamine aliphatique contenant au moins une chaîne polymérique oléfinique attachée à un atome d'azote et/ou un atome de carbone du ou des radicaux alkylène reliant les atomes d'azote amino et ladite polyamine possédant un poids moléculaire en nombre qui varie de 600 à 10 000, (ii) d'une polyamine de Mannich constituée par le produit de la condensation d'un composé hydroxy-aromatique à substitution alkylique, dépourvu de soufre, de poids moléculaire élevé, où le ou chaque groupe alkyle possède un poids moléculaire en nombre qui varie de 600 à 10 000, d'une amine qui contient un groupe amino possédant au moins un atome d'hydrogène actif, et d'un aldéhyde, où le rapport molaire respectif des réactifs varie de 1:0,1-10:0,1-10 et (iii) des mélanges de (i) et de (ii); et de (b) un hydrocarbylpoly(oxyalkylène)aminocarbamate oléosoluble possédant un poids moléculaire moyen en nombre qui varie de 600 à 10 000 et qui possède au moins un atome d'azote basique, où le radical hydrocarbyle précité contient de 1 à 30 atomes de carbone et où le rapport pondéral de ladite polyamine (a) audit hydrocarbylpoly(oxyalkylène)aminocarbamate (b) varie de 3:1 à 1:1, et une proportion mineure d'un diluant compatible avec l'essence.
EP92202889A 1991-09-23 1992-09-21 Composition d'essence Expired - Lifetime EP0534551B1 (fr)

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US5951723A (en) * 1996-12-30 1999-09-14 Chevron Chemical Company Method to remedy engine intake valve sticking
US6203584B1 (en) * 1998-03-31 2001-03-20 Chevron Chemical Company Llc Fuel composition containing an amine compound and an ester
US6723141B1 (en) * 1999-11-04 2004-04-20 Shell Oil Company Additive concentration
US20030029077A1 (en) * 2001-08-07 2003-02-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Fuel composition containing detergent combination and methods thereof

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US4231759A (en) * 1973-03-12 1980-11-04 Standard Oil Company (Indiana) Liquid hydrocarbon fuels containing high molecular weight Mannich bases
US4191537A (en) * 1976-06-21 1980-03-04 Chevron Research Company Fuel compositions of poly(oxyalkylene) aminocarbamate
US4166726A (en) * 1977-12-16 1979-09-04 Chevron Research Company Diesel fuel containing polyalkylene amine and Mannich base
US5006130A (en) * 1989-06-28 1991-04-09 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
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