WO2000020537A1 - Additif pour essence destinee a un moteur a essence a injection directe - Google Patents

Additif pour essence destinee a un moteur a essence a injection directe Download PDF

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Publication number
WO2000020537A1
WO2000020537A1 PCT/JP1999/005446 JP9905446W WO0020537A1 WO 2000020537 A1 WO2000020537 A1 WO 2000020537A1 JP 9905446 W JP9905446 W JP 9905446W WO 0020537 A1 WO0020537 A1 WO 0020537A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
general formula
represented
hydrogen
Prior art date
Application number
PCT/JP1999/005446
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English (en)
Japanese (ja)
Inventor
Katsuhiko Haji
Masaki Nagao
Jun Akimoto
Masahiro Yoshida
Original Assignee
Nippon Mitsubishi Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP10284068A external-priority patent/JP2000109861A/ja
Priority claimed from JP10342308A external-priority patent/JP2000144157A/ja
Application filed by Nippon Mitsubishi Oil Corporation filed Critical Nippon Mitsubishi Oil Corporation
Priority to EP99970110A priority Critical patent/EP1122295A4/fr
Priority to AU60018/99A priority patent/AU6001899A/en
Publication of WO2000020537A1 publication Critical patent/WO2000020537A1/fr
Priority to US09/826,282 priority patent/US20010020345A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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

Definitions

  • the present invention relates to a gasoline additive excellent in solubility in gasoline, particularly excellent in cleanliness in a combustion chamber of a direct injection gasoline engine, and a gasoline composition containing the additive.
  • Conventional gasoline engines form a uniform premixed gasoline and air by injecting gasoline into the intake port.
  • the direct injection gasoline engine has the function of injecting gasoline directly into the combustion chamber. This makes it possible to form a stratified mixture that is rich in the vicinity of the spark plug but is super-lean in the entire combustion chamber. By forming such a stratified mixture, combustion in a super-lean state (stratified combustion) becomes possible, and it is possible to improve fuel efficiency up to the level of a diesel engine.
  • gasoline is directly injected into the combustion chamber, gasoline evaporation delays that occur with conventional engines are eliminated, enabling more accurate fuel injection amount control.
  • direct injection gasoline engines inject gasoline into the combustion chamber, which may present new problems that differ from conventional gasoline engines.
  • deposits that accumulate in the combustion chamber, especially in the cavity. There is a bird.
  • stratified charge combustion a characteristic of a direct injection gasoline engine, fuel is sprayed into the piston cavity while the piston is rising, and the rebounded fuel forms a rich mixture near the spark plug and burns. .
  • deposits accumulate in the piston cavity, part of the sprayed fuel will be adsorbed on the deposits, and the amount of fuel near the spark plug will decrease or the arrival time will be delayed.
  • the fuel ratio is disturbed, which affects the drivability, deteriorates the exhaust gas, and produces smoke.
  • an object of the present invention is to provide a gasoline additive made of a special nitrogen-containing compound having excellent cleanliness in a combustion chamber, particularly in a cavity of a direct injection gasoline engine.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a nitrogen-containing compound having a specific structure is excellent in cleanliness in a combustion chamber of a direct injection gasoline engine, particularly in a cavity. I found that.
  • one of the gasoline additives according to the present invention comprises a nitrogen-containing compound represented by the following general formula (la).
  • R 1 represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms
  • R 2 , RR 4, and R 5 each independently represent hydrogen, 1 to 16 carbon atoms.
  • R 6 represents a hydrocarbon group having 1 to 10 carbon atoms
  • b represents 0 or 1
  • Z represents a group selected from the group A
  • c represents 0 or
  • X is a group selected from the following group B
  • d is an integer of 1 to 3
  • e is an integer of 0 to 2
  • d + e 3.
  • R 7 and R 8 each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and R 9 represents a carbon number.
  • R 9 represents a carbon number.
  • R 1 () represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and f represents an integer of 0 to 50.
  • R 11 represents an alkylene group having 1 to 6 carbon atoms
  • R 12 represents an alkylene group having 1 to 6 carbon atoms
  • R 13 represents an alkylene group having 1 to 6 carbon atoms
  • B 2 hydrocarbon group having 1 to 30 carbon atoms
  • R 14 represents an alkylene group having 1 to 6 carbon atoms.
  • R 15 represents an alkylene group having 2 to 6 carbon atoms
  • R 16 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group represented by the above general formula (3a).
  • R 17 represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or a group represented by the general formula (3a), and g represents an integer of 1 to 5.
  • R 18 represents an alkylene group having 2 to 6 carbon atoms
  • R 19 , R 2 °, R 21 and R 22 each independently represent hydrogen, a carbon atom having 1 to 10 carbon atoms.
  • Y represents a methylene group, a methylene group, a methylene group substituted with a hydroxyl group having 1 to 10 carbon atoms or a hydroxyl group, an imino group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms;
  • Another one of the gasoline additives according to the present invention is a polybutenylamine compound.
  • This compound is a compound obtained by modifying at least one end of polybutene obtained by polymerizing at least one C4 hydrocarbon selected from n-butene, 2-butene and isopthene with an amine. It is expressed by the formula (lb).
  • R 25 represents a n- butyl group, sec- heptyl group or tert- butyl group
  • R 26, R 27, R 28 and R 2 9 are water Atom, a methyl group or Echiru group
  • an R 2 G, R 27, the total number of carbon atoms of R 28 and R 2 9 are 2
  • R 3 Q and R 31 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkanol group having 1 to 8 carbon atoms, or the following general formula ( 8 b) represents a group
  • m represents an integer of 1 to 100.
  • the R 32 may indicates alkylene group having 1 to 4 carbon atoms, R 3 3 represents hydrogen or an alkyl group having a carbon number. 1 to 4, R 34 were hydrogen or carbon The hydrocarbon group represented by the formulas 1 to 10, and n represents an integer of 1 to 5.
  • the R 1 is a hydrogen or a hydrocarbon group of carbon number 1 to 30 or R 1 is hydrogen, or a carbon number 1 to 24 linear or branched alkyl groups, 2 to 24 carbon atoms, linear or branched alkenyl groups, 5 to 13 cycloalkyl or alkylcycloalkyl groups, 6 carbon atoms Any of an aryl group or an arylalkyl group having up to 18 carbon atoms or an arylalkyl group having 7 to 19 carbon atoms. Preferably, there is.
  • Preferred alkyl groups for R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a linear or branched pentyl group, Straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched nonyl group, straight or branched decyl group, straight or branched decyl group, Straight or branched decyl group, Straight or branched dodecyl, straight or branched tridecyl, straight or branched tetradecyl, straight or branched pendecyl, straight or branched hexadecyl, straight or branched Branched heptyl decyl group, straight or branche
  • Preferred alkenyl groups for R 1 include vinyl, propenyl, isopropenyl, linear or branched butenyl, butenyl, linear or branched pentenyl, linear or branched Xenyl, linear or branched heptenyl, linear or branched octenyl, linear or branched nonenyl, linear or branched decenyl, linear or branched undecenyl, linear or branched dodecenyl , Linear or branched tridecenyl group, linear or branched tetradecenyl group, linear or branched pendecenyl group, linear or branched hexadecenyl group, linear or branched hepdecenyl decenyl group, oleyl group Linear or branched octenyl decenyl groups, linear or branched nonadecenyl groups, linear or branched icos
  • Preferred cycloalkyl groups as R 1 include cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
  • preferred alkyl cycloalkyl groups include methylcyclopentyl group, dimethylcyclopentyl group (all substituted isomers) ), Ethylcyclopentyl group (including all substituted isomers), linear or branched propylcyclopentyl group (including all substituted isomers), ethylmethylcyclopentyl group (including all substituted isomers) ), Trimethylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers), straight chain Or branched propylmethyl cyclopentyl group (including all substituted isomers), linear or branched propylethylcyclopentyl group (including all
  • Preferred aryl groups for R 1 include phenyl, naphthyl and the like, and similarly preferred alkylaryl groups include tolyl (including all substituted isomers), xylyl (including all substituted isomers). (Including substituted isomers), ethylphenyl group (including all substituted isomers), linear or branched propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers) ), Trimethylphenyl (including all substituted isomers), linear or branched butylphenyl (including all substituted isomers), linear or branched propylmethylphenyl (including all substituted isomers) Dimethyl group (including all substituted isomers), dimethyl group (including all substituted isomers), tetraethyl group (including all substituted isomers) Tylphenyl groups (including all substituted isomers), linear or branched pentylphenyl groups (including
  • arylalkyl groups include benzyl and methylbenzyl groups (including all substituted isomers). ), Dimethylbenzyl group (including all substituted isomers), phenethyl group, methylphenethyl group (including all substituted isomers), dimethylamine; II netyl group (including all substituted isomers) Can be
  • R 1 is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkyl group
  • a reel group is more preferable, and in particular, a hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or a linear or branched alkyl group having 7 to 15 carbon atoms. More preferably, it is a branched alkylaryl group, most preferably, hydrogen.
  • R 2 , R ⁇ R 4 and R 5 in the general formula (la) each independently represent hydrogen, a hydrocarbon group having 1 to 16 carbon atoms or a group represented by the general formula (2a).
  • the hydrocarbon group having 1 to 16 carbon atoms includes a linear or branched alkyl group having 1 to 16 carbon atoms, and a linear or branched alkyl group having 2 to 16 carbon atoms.
  • Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, straight-chain or Branched hexyl, straight or branched heptyl, straight or branched octyl, straight or branched nonyl, straight or branched decyl, straight or branched undecyl, straight or branched
  • a branched dodecyl group, a linear or branched tridecyl group, a linear or branched tetradecyl group, a linear or branched pendecyl group, a linear or branched hexadecyl group, and the like are also preferable alkenyl groups.
  • preferred cycloalkyl groups include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like.
  • alkylcycloalkyl group include a methylcyclopentyl group (including all substituted isomers), Dimethylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), linear or branched propylcyclopentyl group (including all substituted isomers), ethyl Methylcyclopentyl group All substituted isomers), trimethylcyclopentyl group (including all substituted isomers), getylcyclopentyl group (including all substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers) ), Linear or branched propylmethylcyclopentyl group (including all substituted isomers), linear or branched propyle
  • Preferred aryl groups include a phenyl group and a naphthyl group.
  • Preferred alkylaryl groups include a tolyl group (including all substituted isomers) and a xylyl group (including all substituted isomers).
  • Ethylphenyl group (including all substituted isomers), linear or branched propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers), Limethylphenyl group (including all substituted isomers), linear or branched butylphenyl group (including all substituted isomers), linear or branched propylmethylphenyl group (including all substituted isomers), Jetylph Xnil group
  • arylalkyl groups include benzyl, methylbenzyl (including all substituted isomers), dimethylbenzyl (including all substituted isomers), phenethyl, and methylphenethyl (including all substituted isomers). Dimethylphenethyl group (including all substituted isomers).
  • hydrocarbon groups having 1 to 16 carbon atoms a linear or branched alkyl group having 1 to 8 carbon atoms is even more preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is particularly preferable. Alkyl groups are most preferred.
  • 2 , R 3 , R 4 and R 5 in the general formula (la) may be a group represented by the general formula (2a), but in the general formula (2a), R 7 and R 8 Each independently represents hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 1 ° carbon atoms.
  • the hydrocarbon group having 1 to 10 carbon atoms includes a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkenyl group having 2 to 10 carbon atoms.
  • Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, straight-chain or A branched hexyl group, a straight-chain or branched heptyl group, a straight-chain or branched octyl group, a straight-chain or branched nonyl group, a straight-chain or branched decyl group, and the like.
  • preferred cycloalkyl groups include cyclopentyl and Examples include a chlorohexyl group and a cycloheptyl group.
  • alkylcycloalkyl group examples include a methylcyclopentyl group (including all substituted isomers), a dimethylcyclopentyl group (including all substituted isomers), and ethylcyclopentyl.
  • a tyl group (including all substituted isomers), a linear or branched propylcyclopentyl group (including all substituted isomers), an ethylmethylcyclopentyl group (including all substituted isomers), Trimethylcyclopentyl group (including all substituted isomers), getylcyclopentyl group (including all substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers), linear or Branched propylmethylcyclopentyl group (including all substituted isomers), straight-chain or branched propylethylsilyl Lopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers) Isomer), linear or branched propylcyclohexyl group (including all
  • Preferred aryl groups include a phenyl group and a naphthyl group.
  • Preferred alkylaryl groups include a tolyl group (including all substituted isomers) and a xylyl group (including all substituted isomers).
  • Ethylphenyl group (including all substituted isomers), linear or branched propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers) ), Trimethylphenyl (including all substituted isomers), linear or branched butylphenyl (including all substituted isomers), linear or branched propylmethylphenyl (including all substituted isomers) ), Jethyl phenyl group (including all substituted isomers), ethyl dimethyl phenyl group (including all substituted isomers), tetramethyl phenyl group (including all substituted isomers) Included).
  • Preferred arylalkyl groups include a benzyl group, a methylbenzyl group (including all substituted isomers), a dimethylpentyl group (including all substituted isomers), a phenethyl group, and a methylphenethyl group (including all substituted isomers). And dimethylphenethyl group (including all substituted isomers).
  • the alkoxyalkyl group having 2 to 10 carbon atoms includes, for example, methoxymethyl group, ethoxymethyl group, ⁇ -propoxymethyl group, isopropoxymethyl group, ⁇ -butoxymethyl group, isobutoxymethyl group, sec-butoxy group.
  • R 7 and R 8 in the general formula (2a) be, or individually, hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms. More preferably, it is an alkyl group of 3 to 3.
  • R 9 in the general formula (2a) represents an alkylene group having 2 to 6 carbon atoms, or an alkylene group having 4 to 10 carbon atoms in total having an alkoxyalkylene group as a substituent.
  • alkylene group having 2 to 6 carbon atoms include, for example, ethylene group, propylene group (1-methylethylene group, 2-methylethylene group), trimethylene group, and butylene group (1-ethylethylene group, 2-methylethylene group).
  • Examples of the alkylene group having a total number of carbon atoms of 4 to 10 containing the alkoxyalkylene group for R 9 as a substituent include 1- (methoxymethyl) ethylene, 2- (methoxymethyl) ethylene, and 1- (methoxymethyl) ethylene.
  • a preferable example is an alkoxyalkylene group-substituted ethylene group having a total of 2 to 8 carbon atoms such as a 2-ethylethylene group.
  • R 9 in the general formula (2a) is particularly preferably an alkylene group having 2 to 4 carbon atoms or an ethylene group substituted with an alkoxyalkylene group having 2 to 6 carbon atoms in total.
  • R 1G represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, but R 1Q is hydrogen or a straight-chain having 1 to 24 carbon atoms described above for R 1.
  • Chain or branched alkyl group linear or branched alkenyl group having 2 to 24 carbon atoms, cycloalkyl group or alkyl group having 5 to 13 carbon atoms It is preferably any of an alkyl group having 6 to 18 carbon atoms, an alkyl group or an alkylaryl group, and an arylalkyl group having 7 to 19 carbon atoms.
  • R 1G is more preferably an alkyl group having 1 to 24 carbon atoms, and particularly preferably an alkyl group having 1 to 12 carbon atoms.
  • F in the general formula (2a) may be any integer selected from the range of 0 to 50, but is preferably an integer of 0 to 30 and more preferably an integer of 0 to 20.
  • a group represented by the general formula (2 a) is an alkoxyalkyl group of R 7 and R 8 it it independently hydrogen, alkyl or a carbon number from 1 to 6 carbon.
  • R 9 Is an alkylene group having 2 to 6 carbon atoms or an alkylene group substituted with an alkylene alkylene group having 2 to 8 carbon atoms
  • R 1 (1 is an alkyl group having 1 to 24 carbon atoms
  • f is 0 It is preferably an integer of up to 30.
  • R 7 and R 8 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms
  • R 9 is an alkylene group having 2 to 4 carbon atoms
  • R 10 is an alkyl group having 1 to 12 carbon atoms.
  • f is an integer of 0 to 20.
  • R 2 , R ⁇ R 4 and R 5 in the general formula (la) are hydrogen or is preferably the alkyl group or the carbon number of 1 to 8, "preferred substituent group (PF 1)".
  • R 2, R 3, R 4 and R 5 are hydrogen or the number 1 of 3 carbon More preferably, it is an alkyl group or the above-mentioned “more preferred substituent group (PF 2).”
  • R 6 in the general formula (la) represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon is The group is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 3 to 6 carbon atoms, specifically, a trimethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, pentamethylene group And a 1-methylpentamethylene group, a 2-methylpentamethylene group, a 3-methylpentamethylene group, a 4-methylpentamethylene group, a 5-methylpentamethylene group, and a hexamethylene group.
  • R 11 represents an alkylene group having 1 to 6 carbon atoms
  • R 12 represents an alkylene group having 1 to 6 carbon atoms
  • R 11 R 12, R 13 of the group A is an alkylene group of from 1 to 6 carbon, the alkylene groups of that, for example, methylene Group, ethylene group, propylene group (1-methylethylene group, 2-methylethylene group), trimethylene group, butylene group (1-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2, 2-dimethylethylene group, 1-methyltrimethylene group,
  • 2-trimethylethylene group 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 3-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1, 2-dimethyltrimethylene group, 1,
  • II 11 , R 12 , and R 13 are preferably an alkylene group having 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group). ), Trimethylene group, butylene group (1-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3- A methyl trimethylene group and a tetramethylene group are preferred.
  • an alkylene group having 1 to 3 carbon atoms specifically, a methylene group, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group) or a trimethylene group Is most preferred.
  • Z in the general formula (la) is preferably A1, A2 or A4 in the above-mentioned A group.
  • a is an integer of 1 to 200, preferably 2 to 100.
  • b and c are each independently 0 or 1.
  • R 4 in the general formula (6 a) R 3, R 4, R 5 and X are, RR 2, in the general formula (la) R 3, shows the R 4, R 5 and X and the same radical, a , D and e are the same integers as a, d and e in the general formula (la).
  • RR 2 , R 3 , R 4 , RR 6 and X in the general formula (8a) represent the same groups as RR 2 , R 3 , R 4 , R 5 , R 6 and X in the general formula (la)
  • A, d, and e are the same integers as a, d, and e in the general formula (la).
  • RRR 3 , R 4 , R 5 , R 6 and X, Z in the general formula (9a) are the same as R 1 RR ⁇ R 4 , R 5 , R 6 and X, Z in the general formula (la)
  • A, d, and e are the same integers as a, d, and e in the general formula (1a).
  • the compound has two groups represented by the following general formula (10a) in one molecule. In such a case, those groups may have the same structure or different structures.
  • R ′, R 2 , R 3 , R 4 , R 5 , R 6 and Z in the general formula (10a) are represented by I 1 , R 2 , RR 4 , RR 6 and Z in the general formula (la) Represents the same group, and a, b and c are also the same integers as a, b and c in the general formula (la).
  • X represents a group selected from the following group B.
  • B 2 a hydrocarbon group having 1 to 30 carbon atoms
  • R represents an alkylene group having 1 to 6 carbon atoms.
  • R 15 represents an alkylene group having 2 to 6 carbon atoms
  • R 16 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group represented by the above general formula (3a).
  • R 17 represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or a group represented by the above general formula (3a), and g represents an integer of 1 to 5.
  • B 5 a group represented by the following general formula (5a)
  • R 18 represents an alkylene group having 2 to 6 carbon atoms
  • R ig , R 2 °, R 21 and R 22 each independently represent hydrogen, carbon atoms having 1 to 10 carbon atoms.
  • Y represents a methylene group, a methylene group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, an imino group, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group.
  • N (nitrogen) in corresponds to the general formula (1) in the N (nitrogen)) in preferred as the hydrocarbon group of the B 2 carbon atoms from 1 to 30 are previously attached to R 1 described Linear or branched alkyl group having 1 to 24 carbon atoms, linear or branched alkenyl group having 2 to 24 carbon atoms, and cycloalkyl having 5 to 13 carbon atoms Or Arukirushiku port alkyl group, ⁇ Li Ichiru or alkyl ⁇ aryl group of carbon number 6-18, etc. ⁇ reel alkyl group having 7 to 1 9 carbon atoms, and the like.
  • R 14 represents an alkylene group having 1 to 6 carbon atoms. Examples of such an alkylene group include R ′ R 12 include the groups described above as R '3.
  • R 14 is preferably an alkylene group having 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group (a monomethylethylene group, a 2-methylethylene group), a trimethylene group, and a butylene group.
  • an alkylene group having 1 to carbon atoms 3, specifically a methylene group, an ethylene group, propylene alkylene groups (1 one methylethylene, 2-methylethylene) or preparative Rimechire emissions group is most preferred.
  • R 15 is an alkylene group having 2 to 6 carbon atoms, examples of such alkylene groups, in particular above as R 9 The groups described are mentioned.
  • R 15 is preferably an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group), a trimethylene group, and a butylene group ( 1-ethylethylene group, 21-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group And the like, and an alkylene group having 2 to 3 carbon atoms, specifically, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group) and a trimethylene group are more preferable.
  • R 16 in the general formula (4a) represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group represented by the general formula (3a).
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • an alkyl group having 1 to 3 carbon atoms and more preferably a methyl group or an ethyl group.
  • R 17 in the general formula (4a) represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, or a group represented by the general formula (3a).
  • Carbon number here 1 ⁇ Preferred as the 30 hydrocarbon groups are the linear or branched alkyl groups having 1 to 24 carbon atoms described above for R 1 , and the linear or branched alkyl groups having 2 to 24 carbon atoms.
  • R 17 is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group having 6 to 12 carbon atoms, or a compound represented by the general formula (3a ) Is more preferable.
  • R 17 is hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, and a carbon number?
  • G in the general formula (4a) is an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.
  • the group represented by the following general formula (11a), which is included in the group represented by the general formula (4a), has a structural unit represented by the following general formula (12a). It has 1 to 5, preferably 1 to 4, more preferably 1 to 3.
  • the group represented by the general formula (11a) represents a group obtained by bonding the structural units represented by the general formula (12a) as follows.
  • R 15 is an alkylene group having a carbon number of 2 to 4
  • R 16 is hydrogen, an alkyl group having 1 to 3 carbon atoms Or a group represented by the general formula (3a), wherein R 17 is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or It is preferably an alkylaryl group or a group represented by the general formula (3a), and g is preferably 1 to 4.
  • R 15 is an ethylene group, a propylene group (a monomethyl ethylene group, a 2-methyl group).
  • R 16 is hydrogen, a methyl group, an ethyl group or a group represented by the general formula (3a), R 17 is hydrogen, and a straight-chain having 1 to 6 carbon atoms. Most preferably, it is an alkyl or phenyl group, an alkylaryl group having 7 to 9 carbon atoms or a group represented by the general formula (3a), and g is 1 to 3.
  • R 1 8 represents an alkylene group having 2-6 carbon atoms. Specific examples of the alkylene group include the same groups as those described above as R 15 .
  • R 18 is preferably an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group), a trimethylene group, Butylene group (1-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group And a tetramethylene group, etc., and more preferably an alkylene group having 2 to 3 carbon atoms, specifically, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group) or a trimethylene group.
  • the hydrocarbon group having 1 to 10 carbon atoms includes the linear or branched alkyl group having 1 to 10 carbon atoms described above for R 7 and R 8 , and 2 to 10 carbon atoms.
  • R 1 9, R 2 Q , R 2 1 and R 22 it it independently hydrogen, It is preferably a group represented by an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group.
  • Y represents a methylene group, a methylene group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a group represented by a hydroxyl group, an imino group, or a hydrocarbon having 1 to 10 carbon atoms. Indicates an amino group or oxygen substituted with a group or a hydroxyl group.
  • the hydrocarbon group having 1 to 10 carbon atoms referred to herein includes the linear or branched alkyl group having 1 to 10 carbon atoms described above for R 7 and R 8 , and the carbon group having 2 to 1 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • Y represents a methylene group, an alkyl group having 1 to 6 carbon atoms or a methylene group substituted with a hydroxyl group, an imino group, an alkyl group having 1 to 6 carbon atoms, or an amino group substituted with a hydroxyl group.
  • oxygen and most preferably an amino group, an amino group substituted with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, or oxygen.
  • R 1 8 is an alkylene group having 2 to 4 carbon atoms
  • R 1 9, R 2 G , R 2 1 and R 22 is Each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group
  • Y is a methylene group, a methylene group substituted with an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, an imino group, or a 1 to 6 carbon atoms.
  • N (nitrogen) in the general formula (5a) is also N (nitrogen) in the general formula (la)
  • R 18 is an ethylene group or a propylene group ( 1-methylethylene group, 2-methylethylene) or a trimethylene group, R 1 9, R 2 ° , R 2 1 and R 22 it it independently hydrogen, carbon 1 to 3 alkyl groups or hydroxyl groups
  • X can be arbitrarily selected from the above B 1 to B 5. Also, in the case of e-2, that is, when two Xs are selected, the two may be the same or different.
  • X is preferably B1, B3, B4 or B5.
  • substituents of the general formula (1a) that generally represent the nitrogen-containing compound of the present invention have been individually described.
  • R 1 in the general formula (la) is hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
  • R 2 , RR 4 and R 5 are hydrogen or an alkyl group having 1 to 8 carbon atoms or a group represented by the general formula (2a),
  • R 7 and R 8 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms, and R 9 is an alkylene having 1 to 6 carbon atoms.
  • R 1 is an alkyl group having 1 to 24 carbon atoms, and is an integer of 0 to 30;
  • R 6 is an alkylene group having 1 to 6 carbon atoms
  • Z is a group selected from group A
  • R 11 R 12 s R 13 is an alkylene group having 1 to 4 carbon atoms
  • X is a group selected from group B
  • B2 is a linear or branched alkyl group having 1 to 12 carbon atoms or an aryl group or an arylalkyl group having 6 to 12 carbon atoms, and corresponds to B3.
  • formula (3 a) in R 14 is an alkylene group having 1 to 4 carbon atoms
  • the general formula corresponding to B 4 (4 a) in R 1 5 is an alkylene group having 2 to 4 carbon atoms
  • R 16 Is hydrogen, an alkyl group having 1 to 3 carbon atoms or a group represented by the general formula (3a)
  • R 17 is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, 6 to 12 aryl groups or arylalkyl groups, or a general formula
  • nitrogen-containing compounds as the first gasoline additive of the present invention are those wherein R 1 in the general formula (la) is hydrogen or an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkyl aryl having 7 to 15 carbon atoms.
  • R 2 , R: 4 and R 5 are hydrogen, an alkyl group having 1 to 3 carbon atoms or a group represented by the general formula (2a);
  • R 7 and R 8 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms
  • R 9 is an alkylene group having 2 to 4 carbon atoms
  • R lfl is 1 carbon atom.
  • An alkyl group of from 12 to 12, and f is an integer of 0 to 20,
  • R 6 is an alkylene group having 3-6 carbon atoms, a is filed an integer. 2 to 100, b and c are independently 0 or 1, d is 1, e is a 2,
  • Z is a group selected from among A l, A 2, A 4 , R 12 is an alkylene group having 1 to 3 carbon atoms, X is selected from B l, B 3, B4, B 5 Group,
  • R 14 is Ri der alkylene group having 1 to 3 carbon atoms
  • R 16 is hydrogen, a methyl group, an ethyl group or a group represented by the general formula (3a)
  • R 17 is hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, Phenyl group, carbon number?
  • the nitrogen-containing compound represented by the general formula (la) can be produced by any method.
  • the nitrogen-containing compound represented by the general formula (la) can be synthesized through the following (A) ketimination step, (B) polymerization step and (C) hydrolysis step.
  • the ketimine compound is obtained by heating and dehydrating ton.
  • Compounds having two or more amino groups in the molecule include diamines such as ethylenediamine, propylenediamine (1,2-diaminopropane), trimethylenediamine (1,3-diaminopropane), diethylenetriamine, and the like.
  • Polyamines (three or more N atoms), such as ethylene hexamine and pen-propylene hexamine.
  • Compounds having an amino group and an alkanol group in the molecule include monomethanolamine, monoethanolamine, mono-n-propanolamine, monoisopropanolamine, and mono (linear or branched) compounds.
  • Noramine position of hydroxyl group is arbitrary
  • mono (linear or branched) penylamine position of hydroxyl group is arbitrary
  • mono (linear or branched) hexanolamine linear The position of the hydroxyl group is arbitrary
  • 2- (2-aminoethylamino) ethanol such as ethanol.
  • Examples of the compound having an amino group and an imino group in the molecule include the above-mentioned amine and 4-aminomethylpiperidine.
  • Compounds having an amino group and a carboxyl group in the molecule include: Amino acids such as nin, 5-alanine, and N- (2-aminoethyl) glycine.
  • Amino acids such as nin, 5-alanine, and N- (2-aminoethyl) glycine.
  • As the ketone one represented by the following general formula (14a) is usually used.
  • R 23 and ⁇ 2 ⁇ independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
  • ketones having a branched alkyl group and having large steric hindrance are preferable, and isobutylmethylketone, isobutylethylketone, and diisobutylketone are preferable. Etc. are preferably used.
  • a ketimine compound represented by the following general formula (15a) can be obtained.
  • R 6 represents the same group as R 6 in the general formula (la), R 23 and R 24 in the general formula (14 a) R 23 and R 24 identical to the group
  • a ketimine compound represented by the following general formula (16a) can be obtained.
  • R 11 represents the same group as R 1 1 in Group A A 3
  • R 23 and R 24 have the general formula (14 a) the same group as R 23 and R 24 in
  • a ketimine compound represented by the following general formula (17a) can be obtained.
  • R 15 is formula (represent the same group as R 15 in 4 a)
  • R 23 and R 24 have the general formula (14 a) the same group as R 23 and R 24 in
  • a ketimin compound represented by the general formula (18a) or (19a) can be obtained by reacting a polyamine (having 3 or more N atoms) with a ketone.
  • R 15 and R iU represent the same group, and g, g, and g "represent one group.
  • the reaction temperature in the ketimination step is optional, but is usually preferably 40 to 180 ° C, more preferably 80 to 150 ° C.
  • a compound represented by the general formula (20a) is used.
  • the polymerization product (in the form of metal alkoxide) obtained by polymerizing the epoxy compound to be used is used as it is, or after the reaction is stopped with a halogen compound represented by the general formula (21a), By treating this with an acid or a solid acid, a polyoxyalkylene glycol derivative having a ketimine compound at a terminal represented by the general formulas (22a) to (26a) is obtained.
  • I 1 , RR 3 , R 4, and R ⁇ 5 ⁇ are the same as RR ⁇ ', RR in the formula ((1l aa)).
  • RR °, the same group as R 4 and R 5, and T represents chlorine, bromine or iodine.
  • R 15 is the same as R "in the general formula (4a)
  • R ⁇ RR 3, R 4 and R 5, a in the general formula (la), is identical to R ⁇ RR 3, R 4 and R 5, R 15, R 1 6 sg, and g "are R 15, R 16 in the general formula (4 a), and are identical
  • R 23, R 24 is identical to R 23, R 24 in the general formula (14 a)
  • Preferred examples of the epoxy compound represented by the general formula (20a) include ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, Trimethyl ethylene oxide, tetramethyl ethylene oxide, 1,2-epoxy hexane, 1,2-epoxy heptane, 1,2-epoxy octane, 1,2-epoxy decane, 1,2-epoxy dodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyhexadecane, methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopguchi pyrglycidyl ether, n-butyl glycidyl ether Ter, isobutyldaricidyl ether, sec-butylglycidyl Tert-butyl glycid
  • the molar ratio can be arbitrarily selected.
  • the epoxy compound is used in an amount of 5 to 10 moles per mole of the ketimine compound. It is preferable to make 0 mole reaction.
  • the reaction temperature in the polymerization step is also optional, but is usually preferably from 60 to 180 ° C, more preferably from 80 to 150 ° C.
  • the nitrogen-containing compound of the present invention represented by the general formula (1a) is obtained. Obtainable.
  • the reaction temperature in the hydrolysis step is also arbitrary, but is usually preferably from 40 to 150 ° C, more preferably from 50 to 100 ° C.
  • an epoxy compound of the general formula (20a) to the terminal amino group obtained by hydrolyzing a polyoxyalkylene glycol derivative having a ketimine compound at the terminal, an alkanolamine type terminal is obtained. Nitrogen-containing compounds can also be obtained.
  • the polymerization step can be performed, and the nitrogen-containing compound of the present invention represented by the general formula (la) can be obtained.
  • the nitrogen-containing compound of the present invention represented by the general formula (la) is synthesized through the following (D) polymerization step, (E) chromate formation step, and (F) olebamate formation step. can do.
  • a polymerization product (in the form of a metal alkoxide) is obtained by polymerizing an epoxy compound represented by the following formula, and then neutralized with an acid such as hydrochloric acid to obtain a compound represented by the general formula (28a)
  • an acid such as hydrochloric acid
  • R ⁇ RR 3, R 4 Contact and R 5 are the same as a, R ⁇ RRR 4 and R 5 in the general formula (la).
  • the molar ratio of the reaction of the oxygen-containing compound of the general formula (27a) with the epoxy compound of the general formula (20a) can be arbitrarily selected, but is usually performed with respect to 1 mole of the oxygen-containing compound. It is preferable to make 5 to 100 moles of the epoxy compound react.
  • the reaction temperature in the polymerization step is also arbitrary, but is usually preferably from 60 to 180, more preferably from 80 to 150 ° C.
  • the polyoxyalkylene glycol derivative of the general formula (28a) obtained in the above polymerization step or the metal alkoxide compound before its neutralization is converted into chloroformate with an excess amount of phosgene at room temperature, for example.
  • a chlorine-containing compound represented by (29a) is obtained.
  • A, RR 3 , R 4 and R 5 in the general formula (29a) are the same as a, R ⁇ R 2 , R 3 , R 4 and R 5 in the general formula (la).
  • the nitrogen-containing compound of the present invention is obtained by reacting the chlorine-containing compound of the general formula (29a) obtained in the above-mentioned closing mouth forming step with an amine compound represented by the general formula (30a). A compound can be obtained.
  • the amine compound represented by the general formula (30a) includes ethylenediamine, propylenediamine (1,2-diaminopropane), trimethylenediamine (1,1-diaminopropane) and dimethylaminopropylamine.
  • the position of the hydroxyl group is arbitrary), dihydroxyvirazolidine (the position of the hydroxyl group is arbitrary), dihydroxyvirazoline (the position of the hydroxyl group is arbitrary), dihydroxypyrazole (the position of the hydroxyl group is arbitrary) ), Dihydroxymidazolidine (the position of the hydroxyl group is arbitrary), dihydroxymidazoline (the position of the hydroxyl group is arbitrary), dihydroxymidazolyl (the position of the hydroxyl group is arbitrary), Dihydroxyfuroxan (the position of the hydroxyl group is arbitrary), dihydroxypiperidine (the position of the hydroxyl group is arbitrary), dihydroxypiperazine (the position of the hydroxyl group is arbitrary), dihydroxymorpholine (the position of the hydroxyl group is arbitrary) The position is arbitrary), dihydroxyindrin (the position of the hydroxyl group is arbitrary), dihydroxyxin Indole (The position of the hydroxyl group is optional.
  • Dihydroxyisoindole (the position of the hydroxyl group is arbitrary), dihydroxypurine (the position of the hydroxyl group is arbitrary), dihydroxycarbazole (the position of the hydroxyl group is arbitrary), dihydroxy-1-carboline ( The position of the hydroxyl group is arbitrary), dihydroxyphenoxazine (the position of the hydroxyl group is arbitrary), dihydroxyperimidine (the position of the hydroxyl group is arbitrary), trimethanolamine, methyldimethanol Min, ethyl dimethanol amine, triethanolamine, methyl ethyl amine, ethyl ethyl amine, tri n-propanolamine, methyl di-n-propanolamine, ethyl di-n-propanolamine , Triisopronolanamine, methyldiisoprononol Min, etyldiisopropanolamine, tri (linear or branched) butylamine,
  • the molar ratio in the case of reacting the chlorine-containing compound of the general formula (29a) with the amide compound of the general formula (30a) in the carbamate formation step can be arbitrarily selected.
  • the amide compound is preferably reacted with at least 1 mol or more, more preferably 1 to 20 mol, with respect to 1 mol of the chlorine-containing compound.
  • the reaction temperature in the carbamate formation step is also optional, but is usually preferably from 120 to 150 ° C, more preferably from 110 to 80 ° C.
  • the second nitrogen-containing compound of the present invention is a polybutenylamine compound.
  • the polymerized portion of the compound may be a homopolymer composed of one selected from n-butene, 2-butene and isobutene, or a copolymer composed of two or more. In the case of a copolymer, any of a random copolymer, an alternating copolymer and a block copolymer may be used.
  • the polymerized portion of the polyptenylamine compound is n-butene, 2 -It is obtained by polymerizing one or more of butene and isobutene as raw materials, and the raw materials include n-butene and 2-butene as long as the performance of the polybutenylamine compound is not impaired.
  • a nitrogen atom in the amine portion of the polybutenylamine compound is bonded to a hydrogen atom, an oxygen-containing group such as a hydrocarbon group and an alkanolamine group, and a nitrogen-containing group such as an aminoalkyl group. May be.
  • polybutenylamine-based compound of the present invention examples include a compound represented by the aforementioned general formula (lb).
  • R 25 represents an n-butyl group, a sec-butyl group or a tert-butyl group, but R 25 is preferably a tert-butyl group from the viewpoint of better cleanability.
  • the repeating unit in the general formula (lb) has a structure derived from 1-butene, 2-butene or isobutene.
  • the series of m repeating units may be a homopolymerization chain of any one of 1-butene, 2-butene and isobutene, and may be two or more kinds selected from 1-butene, 2-butene and isopthene. It may be a copolymer chain. When the copolymer chain is a copolymer chain, it does not matter whether the copolymer form is random polymerization or alternating polymerization.
  • R 26 and R 2 8 are hydrogen, or R 2 7 and R 2 9 is a methyl group, or
  • R 2 6 and R 2 8 is a methyl group, arbitrariness preferred that R 2 7 and R 2 9 are hydrogen.
  • M which indicates the number of repeating units, must be at least 1 in order to ensure dispersibility and cleanliness in gasoline, and is preferably at least 5; Is more preferable.
  • m is 100 or less. It is preferably at most 40, more preferably at most 40.
  • Q is any one of the above formulas (2b) to (7b), but because of its excellent cleanability, Q is the formula (2b) or the formula (6b) And more preferably the formula (6b).
  • R 3 1 shows that it independently hydrogen, carbon number 1-1 0 hydrocarbon group, a group represented by the alkanol group or the one general formula of carbon number 1 ⁇ 8 (8 b).
  • the hydrocarbon group having 1 to 10 carbon atoms includes a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkenyl group having 2 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, Straight or branched pentyl group, straight or branched hexyl group, straight or branched heptyl group, straight or branched octyl group, straight or branched nonyl group, straight or branched decyl group, etc. Are listed.
  • alkenyl group having 2 to 10 carbon atoms examples include, for example, ethenyl group, n-propenyl group, isopropenyl group, n-butenyl group, isoptenyl group, sec-butenyl group, tert-butenyl group Group, straight or branched pentenyl group, straight or branched hexenyl group, straight or branched heptenyl group, Examples include a straight-chain or branched octenyl group, a straight-chain or branched nonenyl group, a straight-chain or branched decenyl group, and the like.
  • cycloalkyl group having 5 to 1 ° carbon atoms or the alkyl group having a cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a methylcyclopentyl group, and a dimethylcyclopentyl group.
  • Ethylcyclopentyl group (including all substituted isomers), linear or branched propylcyclopentyl group (including all substituted isomers), ethylmethylcyclopentyl group (including all substituted isomers) ), Trimethylcyclopentyl group (including all substituted isomers), acetylcyclopentyl group (including all substituted isomers), and ethyldimethylcyclopentyl group (including all substituted isomers) , Linear or branched propyl methylcyclopentyl group (including all substituted isomers) , Linear or branched propylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers) ), Ethylcyclohexyl group (including all substituted isomers), linear or branched propylcyclohexy
  • Examples of the aryl or alkylaryl group having 6 to 10 carbon atoms include phenyl, tolyl (including all substituted isomers), xylyl (including all substituted isomers), and ethyl.
  • alkylaryl group having 7 to 10 carbon atoms include a benzyl group, a methylbenzyl group (including all substituted isomers), and a dimethylbenzyl group (including all substituted isomers).
  • alkynol group having 1 to 8 carbon atoms include, for example, a hydroxymethyl group, a hydroxyxetyl group, a linear or branched hydroxypropyl group, a linear or branched hydroxybutyl group, and a linear group.
  • a branched or branched hydroxypentyl group a straight or branched hydroxyhexyl group, a straight or branched hydroxyheptyl group, a straight or branched hydroxyoctyl group, and the like.
  • an alkynol group having 1 to 4 carbon atoms is preferable.
  • R 3 ° and R 31 may be groups represented by the above general formula (8b).
  • R 3 2 is an alkylene group having 1-4 carbon atoms, examples of such alkylene groups, specifically, for example, methylene group, ethylene group, propylene group (1-methyl Ethylene group, 2-methylethylene group, trimethylene group, butylene group (1-ethylethylene group, 2-ethyl) Ethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group and the like.
  • R 33 in the general formula (8b) represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • R8 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms because it is more excellent in cleanliness, more preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom. Most preferred.
  • R 34 in the general formula (8b) represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the hydrocarbon group having a carbon number of 1-10 here include those described above for R 30 and R 3 1.
  • R 34 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms because it is more excellent in cleanliness, more preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom. Is most preferred.
  • the number of repeating units n in the general formula (8b) may be any integer in the range of 1 to 5, but is preferably 1 to 3, and more preferably 1 to 2, because of its excellent cleanability. It is an integer, most preferably 1.
  • the repeating unit n is 2 or more, the individual repeating units may have the same or different structures.If the structures are different, plural types of repeating units may be randomly bonded, alternately bonded or block bonded. You can do it.
  • R 3 and R 31 in the general formula (lb) are hydrogen, an alkanol group having 1 to 4 carbon atoms, or It is preferably a group represented by the general formula (8b). There is no particular limitation on the number average molecular weight of the polybutenylamine compound represented by the general formula (lb).
  • the number average molecular weight of the polybutenylamine compound represented by the general formula (lb) is preferably 200 or more, and more preferably 400 or more, since the dispersion in gasoline is good and the cleanliness is excellent. More preferably, it is more preferably 700 or more. Further, in order to suppress the generation of deposits in the combustion chamber due to the deterioration of the thermal decomposition property, the number average of the polybutenylamine compound represented by the general formula (lb) is required.
  • the molecular weight is preferably at most 6,000, more preferably at most 3,000, even more preferably at most 2,400.
  • the nitrogen-containing compound represented by the general formula (1a) or (1b) is mixed with an appropriate amount of the nitrogen-containing compound together with other gasoline additives, if necessary, into the base gasoline, thereby enabling direct injection in a cylinder.
  • a fuel oil (gasoline composition) suitable for a gasoline engine can be obtained.
  • the gasoline composition for a direct injection gasoline engine proposed by the present invention contains 0.001 to 10% by mass of the above-mentioned nitrogen-containing compound based on the total amount of the gasoline composition.
  • the lower limit of the content is 0.001% by mass, preferably 0.03% by mass.
  • the upper limit of the content is 10% by mass, preferably 5% by mass, more preferably 4% by mass, because it does not adversely affect the performance of gasoline and the effect cannot be expected to be increased even if it is added more.
  • % Most preferably 3% by weight.
  • the base gasoline of the above-mentioned gasoline composition is usually composed of a plurality of types of gasoline. It is prepared by blending the substrate.
  • the gasoline base material for example, light naphtha having a desired property and obtained by distilling crude oil under normal pressure; cracked gasoline obtained by catalytic cracking, hydrocracking, etc .; Modified gasoline; polymerized gasoline obtained by polymerization of olefin; alkylene obtained by adding (alkylation) lower olefin to hydrocarbon such as isobutane; light naphtha isomerizer Isomerized gasoline obtained by conversion to isoparaffin with n-paraffinic oil; butane; aromatic hydrocarbon compound; propylene, which is dimerized and then hydrogenated to obtain a paraffin fraction. Can be used.
  • Modified gasoline 0 to 70% by volume
  • butane 0 to 10% by volume
  • one measure is to reduce the blending ratio of the modified gasoline used in preparing the base gasoline. This is because, among various gasoline substrates, the modified gasoline contains a relatively large amount of benzene.
  • (B) Reacts with benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms to convert to toluene, xylene, ethylbenzene and the like.
  • Desulfurized heavy naphtha obtained by distilling and removing hydrocarbon compounds having 6 carbon atoms is used as the raw material for the catalytic reformer.
  • gasoline additives which can be used in combination with the nitrogen-containing compound as the gasoline additive of the present invention include, for example, detergents and dispersants such as succinic acid imid and polyalkylamine; antioxidants such as phenolic and amine-based Metal deactivator such as Schiff-type compound and thioamide-type compound; Surface ignition inhibitor such as organic phosphorus compound; Anti-freezing agent such as polyhydric alcohol and ether thereof; Alkali metal salt of organic acid Or flame retardants such as alkaline earth metal salts and higher alcohol sulfates; antistatic agents such as anionic surfactants, cationic surfactants, and amphoteric surfactants; coloring agents such as azo dyes; alkenyl Succinic acid S Rust inhibitors such as tellurium; discriminants such as chirizanine and coumarin; odorants such as natural essential oil synthetic flavors.
  • detergents and dispersants such as succinic acid imid and polyalkylamine
  • antioxidants such as phenolic and amine-based
  • the gasoline composition consisting of the gasoline additive of the present invention, other gasoline additives as required, and base gasoline has a distillation property measured by JISK2254 “Petroleum products—distillation test method”. However, it is desirable to satisfy the following conditions.
  • the lower limit of T i 0 is preferably 35 ° C., more preferably 40 ° C. If the temperature is lower than 35 ° C, there is a possibility that gasoline coking may occur in the engine work.
  • the upper limit of the T 10 is 5 5 ° C, preferably 5 0 ° C, it is desirable more rather preferably is 4 8 ° C. If the temperature exceeds 55 ° C, there is a possibility that the low-temperature startability may be defective.
  • the lower limit of T 30 is 5 5 ° C, preferably rather is arbitrarily desired to be 6 0 ° C. If the temperature is lower than 55 ° C, high-temperature operability may be impaired or gasoline coking may occur in the injector. On the other hand, if it exceeds the upper limit value of T 30 is 7 5 ° C, preferably at 7 0 ° (, and particularly preferably in the range of 6 8 ° C. 7 5 ° C results in failure to low temperature operability there is a possibility.
  • the lower limit of T 50 is 7 5 ° C, it is desirable that preferably 8 0 ° C.
  • the upper limit of the T 50 is 1 0 0 ° C, preferably 9 5 ° C, properly is 9 3 ° C der Rukoto is desirable more preferred. If the temperature exceeds 100 ° C, there is a possibility that the low-temperature and normal-temperature operability may be degraded.
  • the lower limit of T 70 is desirably 1 0 0 ° C.
  • the upper limit of the T 70 is 1 3 0 ° C, preferably 1 2 5 ° C, good Ri preferably 1 2 3 ° C, it is desirable and most preferably 1 2 0 ° C. If the temperature exceeds 130 ° C, low-temperature and room-temperature operability may be impaired.
  • the lower limit of T 90 is 1 1 0 ° C, it is desirable that preferably 1 2 0 ° C.
  • the upper limit is set at low and normal temperatures, and also because it can reduce the dilution of engine oil with gasoline, increase exhaust gas emissions, prevent engine oil deterioration and prevent sludge formation. , 160 ° C, preferably 150 ° C, more preferably 140 ° C.
  • the lower limit of the distillation end point is desirably 130 ° C.
  • the upper limit of the distillation end point is 210 ° C., preferably 200. More preferably, the temperature is 195 ° C, and most preferably, it is 190 ° C. If the end point exceeds 21 ° C, normal room operability may be impaired.
  • the gasoline composition containing the gasoline additive of the present invention avoids caulking in the injector and suppresses the amount of evaporative emission. It is preferably at most 65 kPa, more preferably at most 60 kPa, most preferably at most 55 kPa.
  • vapor pressure as used herein means the vapor pressure (lead vapor pressure (RVP)) measured by the JISK 225 “Crude oil and fuel oil vapor pressure test method (lead method)”.
  • the gasoline composition containing the gasoline additive of the present invention preferably has a density (15 ° C.) in the range of 0.73 to 0.77 g / cm 3.
  • the lower limit of density is 0. 7 3 g / cm 3, preferably 0. 7 3 5 g / cm 3 , if less than 0. 7 3 g / c m3 is likely to fuel economy may deteriorate .
  • the upper limit of the density is 0. 77 g / cm 3, preferably 0. 7 6 g / cm3, if it exceeds 0. 77 g / cm 3 is likely to cause camphor first time of acceleration of the deterioration and plug is there.
  • the density mentioned here means the density measured by JISK 2249 “Density test method for crude oil and petroleum products and density / mass / volume conversion table”.
  • the gasoline composition of the present invention does not substantially contain an alkyl lead compound such as tetraethyl lead. Even when a trace amount of lead compound is contained, its content is below the lower limit of the applicable category of JIS K2255 “Test method for lead content in gasoline”.
  • the gasoline composition of the present invention desirably has a research octane number (R 0 N) of 89 or more, preferably 90 or more, more preferably 90.5 or more, and most preferably 91 or more. Further, in order to enhance anti-knock property during high-speed running, it is desirable that the Mo-One Octane Number (MON) is 80 or more, preferably 80.5 or more, and most preferably 81 or more.
  • R 0 N research octane number
  • MON Mo-One Octane Number
  • the octane number of the research method and the octane number of the molybdenum mean the octane number of the research method and the octane number of the molybdenum measured by JIS K 2280 "Octane number and cemeter number test method", respectively.
  • the gasoline composition of the present invention desirably has the following composition. Saturation (V (P)): 50-: 100% by volume
  • V (P) is to prevent gasoline coking in the injector, reduce plug smoldering, reduce the ability of the exhaust gas to produce ozone, reduce the benzene concentration in the exhaust gas, From the viewpoint of not generating soot, the content is desirably 50 to: 100% by volume, preferably 60 to: L00% by volume, and more preferably 70 to 100% by volume.
  • V (0) indicates the view of preventing gasoline caulking during the injection. From the viewpoint, it is desirable that the content is 0 to 15% by volume, preferably 0 to 10% by volume, more preferably 0 to 7% by volume, and most preferably 0 to 5% by volume.
  • V (A r) is 0 to 35 from the viewpoint of reducing the smoldering of the plug, suppressing the ozone generation ability of the exhaust gas, reducing the benzene concentration in the exhaust gas, and preventing soot generation.
  • % By volume preferably 0 to 30% by volume, more preferably 0 to 25% by volume, and most preferably 0 to 20% by volume.
  • V (P), V ( ⁇ ) and V (A r) are all values measured by the fluorescent indicator adsorption method of JIS K 2536 “Petroleum products-hydrocarbon type test method”. It is desirable that the gasoline composition of the present invention also satisfies the following conditions.
  • V (T o 1) 0 to 30% by volume
  • V (C 5) 1 0 ⁇ 3 5 volume%
  • V (C 9+ ) 0 to 10% by volume
  • V (B z) indicates the benzene content based on the total amount of the gasoline composition, and its value is 0 to 1% by volume, preferably 0 to 0% by volume. .5% by volume No.
  • V (T o 1) and V (C 8A ) indicate the toluene content and the content of the aromatic hydrocarbon compound having 8 carbon atoms, respectively, based on the total amount of the gasoline composition. 0 to 30% by volume, preferably 0 to 20% by volume, and V ( C8A ) should be 0 to 20% by volume, preferably 0 to 15% by volume.
  • the aromatic hydrocarbon compounds having 8 carbon atoms include ethylbenzene, xylene (including all substituted isomers), and the like.
  • V (C 9A ) indicates the content of aromatic hydrocarbon compounds having 9 carbon atoms based on the total amount of the gasoline composition, and the value is 0 to 5% by volume in order to suppress the ozone generation ability of the exhaust gas. It is desirable that the content be suppressed to preferably 0 to 3% by volume.
  • C9 aromatic hydrocarbons include n-propylbenzene, isopropylbenzene (cumene), ethylmethylbenzene (including all substituted isomers), and trimethylbenzene (including all substituted isomers). Etc. are included.
  • the above V (C10 + A ) indicates the content of aromatic hydrocarbon compounds having 10 or more carbon atoms based on the total amount of the gasoline composition, and the amount is 0 to reduce the ozone generation ability of the exhaust gas. It is desirable that the content be suppressed to 3% by volume, preferably 0 to 1% by volume, and more preferably 0% by volume.
  • the aromatic hydrocarbon compounds having 10 or more carbon atoms include getylbenzene (including all substituted isomers), dimethylethylbenzene (including all substituted isomers), tetramethylbenzene (including all substituted isomers). ), N-butylmethylbenzene (including all substituted isomers) and the like.
  • V (MA) and V (PA) were monoalkyl-substituted aromatic hydrocarbon compound content (% by volume) based on the total gasoline composition, and were substituted with two or more alkyl groups. The content (volume%) of the aromatic hydrocarbon compound is shown.
  • V (PA) when V (PA) is 0 or V (PA) is not 0, the content of the former and the content of the latter are compared. It is desirable that the content ratio, V (MA) / V (PA), be maintained at 1 or more, preferably 1.5 or more, more preferably 2 or more.
  • V (B z), V (T o 1), V (C 8 A ), V (C gA ), V (C 10 + A ), V (MA) and V (PA) This is a value obtained by quantification by the gas chromatograph method of JISK 2536 “Petroleum products-Test methods for hydrocarbon types”.
  • V (C 4 ) indicates the content of a hydrocarbon compound having 4 carbon atoms based on the total amount of the gasoline composition.
  • V (C 4 ) is desirably 0 to 10% by volume, preferably 0 to 5% by volume, and more preferably 0 to 3% by volume, from the viewpoint that the amount of evaporation can be kept lower.
  • the hydrocarbon compound having 4 carbon atoms include n-butane, 2-methylbutane (isobutane), 1-butene, 2-butene, and 2-methylpropene.
  • V (C 5 ) indicates the content of an aliphatic hydrocarbon compound having 5 carbon atoms based on the total amount of gasoline, and the lower limit is 10% by volume, preferably 15% by volume, and the upper limit. It is desirable that the value be in the range of 35% by volume, preferably 30% by volume.
  • the content of the unsaturated hydrocarbon compound in the aliphatic hydrocarbon compound having 5 carbon atoms (V (C 50)) (volume%) is 0 there are a content of saturated hydrocarbon compounds in a certain stomach fat aliphatic hydrocarbon compounds having 5 carbon atoms (V (C 5p)) ratio (volume%) and V (C 5.), i.e., V (C 5p) / V ( C 5.) is 1 or more, preferably 1.5 or more, more preferably 2 or more, and more preferably most preferably 3 or more.
  • the saturated aliphatic hydrocarbon compounds having 5 carbon atoms include n-pentane, 2-methylbutane (isopentane), 2,2-dimethylpropane (neopentane) and the like.
  • unsaturated aliphatic hydrocarbon compounds include: 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene and the like are included.
  • V (C 6 ) above is a C6 fat based on the total amount of the gasoline composition.
  • the content of the group hydrocarbon compound indicates the content of the group hydrocarbon compound, and the lower limit is desirably in a range of 10% by volume, preferably 15% by volume, and the upper limit is desirably in a range of 30% by volume, preferably 25% by volume.
  • V (C 6.) unsaturated hydrocarbonated compound having 6 aliphatic hydrocarbon compound in the carbon (V (C 6.)) ( Volume%) Is 0, or the ratio of the content (V (C 6p )) (volume%) of saturated hydrocarbon compounds in aliphatic hydrocarbon compounds having 6 carbon atoms to V (C 6 ), ie , V (C 6p ) / V (C 6 ) is more preferably 2 or more, preferably 3 or more, more preferably 5 or more, and most preferably 10 or more.
  • saturated aliphatic hydrocarbon compound having 6 carbon atoms examples include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • the hydrocarbon compounds include 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-1-2 Examples include pentene, 3-methyl-1-pentene, 4-methyl-2-pentene, 2,3-dimethyl-11-butene, 3,3-dimethyl-11-butene, and 2,3-dimethyl-1-butene.
  • V (C 7 + p ) indicates the content of the saturated aliphatic hydrocarbon compound having 7 or more carbon atoms based on the total amount of the gasoline composition, and the lower limit thereof is 10% by volume, preferably 20% by volume. It is desirable that the upper limit value is in the range of 50% by volume, preferably 45% by volume.
  • saturated aliphatic hydrocarbon compound having 7 or more carbon atoms examples include n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, and 2,4-dimethyl ⁇ . Pentane, 3,3-dimethylpentane, 3-ethylpentane, and 2,2,3-trimethylbutane.
  • V (C 9+ ) indicates the content of hydrocarbon compounds having 9 or more carbon atoms based on the total amount of the gasoline composition, and from the viewpoint of low-temperature and normal-temperature operability, the dilution of gasoline with engine oil is also considered. It is desirable that this value be 0 to 10% by volume, preferably 0 to 5% by volume, and more preferably 0% by volume, because it can reduce the amount of exhaust gas, prevent deterioration of engine oil and generation of sludge. .
  • (C 6 ), V (C 6p ), V (C 6. ), V (C 7 + p ) and V (C 9+ ) are values quantified by the following gas chromatography method.
  • the column uses a methyl silicon cavitation ram
  • the carrier gas is hemi- or nitrogen
  • the detector is a hydrogen ionization detector (FID)
  • the column length is 25 to 50 m
  • the carrier gas flow rate is 0. 5-1.5 ml / min, split ratio 1: 50-;
  • the gasoline composition of the present invention can contain an oxygen-containing compound, and its content is 0 to 2.7% by mass, preferably 0 to 2.0% by mass of the total gasoline composition in terms of oxygen element. % Is desirable. If the content exceeds 2.7% by mass, the fuel efficiency of the gasoline composition may deteriorate and NOx in the exhaust gas may increase.
  • the oxygen-containing compound refers to alcohols having 2 to 4 carbon atoms, ethers having 4 to 8 carbon atoms, and the like.
  • the oxygen-containing compounds that can be added to the gasoline composition according to the present invention include ethyl, methyl ethyl butyl ether (MTBE), ethyl ethyl butyl ether, and ethyl amyl methyl ether.
  • MTBE methyl ethyl butyl ether
  • ethyl ethyl butyl ether ethyl amyl methyl ether.
  • 1ME TAME
  • Yuichi Shari Amylethyl ether MTBE and TAME are preferable, and MTBE is most preferable.
  • methanol may increase the aldehyde concentration in the exhaust gas, It is not preferable because it is corrosive.
  • the gasoline composition of the present invention has a sulfur content of 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 20 mass ppm or less, and most preferably 1 mass ppm or less, based on the total amount of the gasoline composition. Desirably, it is 0 mass ppm or less. If the sulfur content exceeds 50 ppm, it may adversely affect the performance of the exhaust gas treatment catalyst, increase the concentration of NOx, CO, and HC in the exhaust gas, and increase the amount of benzene emission there is a possibility.
  • the sulfur content means the sulfur content measured by JIS K 2541, “Crude oil and petroleum products-Test method for sulfur content”.
  • the gasoline composition of the present invention contains 2 Omg / 100 ml of unwashed real gum measured by JISK2261 “Petroleum products—Automobile gasoline and aviation fuel oil—Real gum test method—Injection evaporation method”. It is desirable that the content of the washed real gum is 3 mg / 100 ml or less, preferably 1 mg / 100 ml or less. If the unwashed real gum and the washed real gum exceed the above values, there is a concern that deposits will be formed in the fuel introduction system and that the suction valve will stick.
  • the total calorific value of the above gasoline composition measured by JISK 2279 "Crude oil and petroleum products-Calorimetric test method and estimation method by calculation” is 40 000 J / g or more, preferably 45 000 J / g or more Is desirable o
  • the gasoline composition of the present invention may have an oxidation stability of at least 480 minutes, preferably at least 1440 minutes, as measured by JISK 2287 “Testing method for gasoline oxidation stability (induction period method)”. desirable. If the oxidation stability is less than 480 minutes, gums may form during storage.
  • the gasoline composition of the present invention desirably has a copper plate corrosion (50 ° C., 3 h) of 1, preferably 1 a. If the copper plate corrosion exceeds 1, the fuel system conduit may corrode.
  • copper plate corrosion is measured in accordance with JISK2513 “Copper plate corrosion test method for petroleum products” (test temperature 50 ° C, test time 3 hours).
  • the gasoline composition of the present invention desirably has a kerosene mixing amount of 0 to 4% by volume.
  • the amount of kerosene mixed refers to the hydrocarbon content (volume%) of 13 to 14 carbon atoms based on the total amount of the gasoline composition, and this amount is obtained by quantifying by the gas chromatography method shown below. It is something that can be done.
  • a methyl silicon cavity column is used for the column
  • hemi- or nitrogen is used for the carrier gas
  • a hydrogen ionization detector (FID) is used for the detector.
  • FID hydrogen ionization detector
  • the reaction mixture was cooled to room temperature, 5.6 g of potassium hydroxide was added as an addition catalyst, and the atmosphere was replaced with nitrogen gas.Then, the mixture was heated to 120 ° C, and 87.0 g of propylene oxide (1.5 mol ) And 1,2-butylene oxide (108.2 g, 1.5 mol) were added, and the mixture was reacted for 5 hours.
  • the reaction product solution was neutralized with an acid and filtered to remove the additional catalyst. Further, 5 g of water was added, and a hydrolysis reaction was performed at 90 ° C for 3 hours. Subsequently, by removing excess water, toluene and ketone, 180 g of the desired nitrogen-containing compound was obtained.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2000, and had a pale yellow color. As a result of 13 C—NMR analysis, this nitrogen-containing compound has the formula It was a random copolymer having an average structure represented by (31a). The two are hereinafter referred to as Compound 1.
  • reaction product solution was neutralized with an acid and filtered to remove the additional catalyst. Further, 5 g of water was added, and a hydrolysis reaction was performed at 90 ° C. for 3 hours. Subsequently, excess water, toluene and ketone were removed to obtain 205 g of the desired nitrogen-containing compound.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 220, and exhibited a pale yellow color.
  • this nitrogen-containing compound was a polymer having an average structure represented by the formula (32a). This is hereinafter referred to as Compound 2.
  • a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet Monoethylamine 6.1 (0.1 mol), methyl isobutyl ketone (10 g, 0.1 mol) and toluene (100 ml) were charged, and the atmosphere in the reaction vessel was replaced with nitrogen.
  • the mixture was heated at ° C for 5 hours to cause dehydration and ketimination reaction.
  • the reaction mixture was cooled to room temperature, 5.6 g of potassium hydroxide was added as an addition catalyst, and the mixture was purged with nitrogen gas, heated to 120 ° C, and heated to 40.6 g of propylene oxide (0.4 g).
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 190, and exhibited a pale yellow color.
  • the nitrogen-containing compound was a random copolymer having an average structure represented by the formula (33a). Hereinafter this is referred to as Compound 3.
  • the mixture is cooled to room temperature, After adding 5.6 g of potassium fluoride and purging with nitrogen gas, the mixture was heated to 120 ° C, and 40.6 g (0.7 mol) of propylene oxide and 130.2 g of tert-butylglycidyl ether (10.3 g) were added. ) was added and the mixture was reacted for 5 hours. After that, the reaction product solution was neutralized with an acid and filtered to remove the additional catalyst. Further, 5 g of water was added, and a hydrolysis reaction was performed at 90 ° C. for 3 hours. Subsequently, by removing excess water, toluene and ketone, 165 g of the target nitrogen-containing compound was obtained.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 1800, and exhibited a pale yellow color.
  • this nitrogen-containing compound was a random copolymer having an average structure represented by the formula (34a). Hereinafter, this is referred to as Compound 4.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 210 and was yellow. As a result of 13 C_NMR analysis, this nitrogen-containing compound was a polymer having an average structure represented by the formula (35a). Hereinafter this is referred to as Compound 5.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2300, and had a dark orange color.
  • this nitrogen-containing compound was a random copolymer having an average structure represented by the formula (36a). Hereinafter this is referred to as Compound 6.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2200, and had a dark orange color.
  • this nitrogen-containing compound was a random copolymer having an average structure represented by the formula (37a). Hereinafter this is referred to as Compound 7.
  • This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2300, and had a dark orange color.
  • this nitrogen-containing compound was a polymer having an average structure represented by the formula (38a). Hereinafter this is referred to as Compound 8.
  • Examples 1 to: I 1 and Comparative Example 1 A base gasoline (gasoline for an internal combustion engine) having the following properties was prepared by mixing 60 parts by volume of catalytic reforming gasoline, 30 parts by volume of catalytic cracking gasoline, and 10 parts by volume of alkylate.
  • Boiling range 30 to 190 ° C
  • the gasoline compositions of Examples 1 to 11 according to the present invention were all deposited in the combustion chamber in the direct injection gasoline engine. Can be reduced. In particular, the rate of reduction of the amount of deposit in the cavity where fuel directly hits during stratified combustion is large, and this is considered to be due to control disturbance caused by adsorption of fuel to the deposit.

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Abstract

Un additif pour essence comprend au moins un composé azoté sélectionné entre des composés polyoxyalkylèneamine (1A) et des composés polybutenylamine (1B). Cette composition d'essence est adaptée pour être utilisée dans des moteurs à essence à injection directe. Les composés (1A) peuvent être obtenus au moyen d'un composé kétimine approprié qui sert d'initiateur de réaction pour polymériser un composé époxy et hydrolyser le dérivé polyoxyalkylèneglycol résultant.
PCT/JP1999/005446 1998-10-06 1999-10-04 Additif pour essence destinee a un moteur a essence a injection directe WO2000020537A1 (fr)

Priority Applications (3)

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EP99970110A EP1122295A4 (fr) 1998-10-06 1999-10-04 Additif pour essence destinee a un moteur a essence a injection directe
AU60018/99A AU6001899A (en) 1998-10-06 1999-10-04 Gasoline additive for direct-injection gasoline engine
US09/826,282 US20010020345A1 (en) 1998-10-06 2001-04-04 Gasoline additive for direct injection gasoline engine

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JP10284068A JP2000109861A (ja) 1998-10-06 1998-10-06 ガソリン添加剤
JP10/284068 1998-10-06
JP10342308A JP2000144157A (ja) 1998-11-17 1998-11-17 筒内直接噴射式ガソリンエンジン用ガソリン組成物
JP10/342308 1998-11-17

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US6616776B1 (en) 2002-11-06 2003-09-09 Chevron Oronite Company Llc Method for removing engine deposits in a reciprocating internal combustion engine
WO2003078553A2 (fr) 2002-03-12 2003-09-25 The Lubrizol Corporation Procede de fonctionnement d'un moteur a essence a injection directe au moyen d'une composition de carburant
US6652667B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Method for removing engine deposits in a gasoline internal combustion engine
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JP2003183679A (ja) * 2001-12-21 2003-07-03 Nippon Oil Corp 燃料油添加剤および燃料油組成物
US6651604B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Delivery device for removing interior engine deposits in a reciprocating internal combustion engine
WO2003070861A2 (fr) * 2002-02-19 2003-08-28 The Lubrizol Corporation Procede de fonctionnement d'un moteur a combustion interne a l'aide d'une composition de combustible
NZ535013A (en) 2002-03-14 2005-03-24 Shell Int Research Use of hydrocarbyl primary monoamines as gasoline additives
JP4881222B2 (ja) 2007-05-17 2012-02-22 シェブロンジャパン株式会社 ガソリンエンジンの内面部品の洗浄方法
CN101932679A (zh) * 2008-01-02 2010-12-29 国际壳牌研究有限公司 液体燃料组合物
US8465560B1 (en) 2009-02-05 2013-06-18 Butamax Advanced Biofuels Llc Gasoline deposit control additive composition
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WO2001082401A1 (fr) * 2000-04-24 2001-11-01 Idemitsu Kosan Co., Ltd. Composition de carburant
WO2001088066A1 (fr) * 2000-05-19 2001-11-22 Nippon Mitsubishi Oil Corporation Additif pour carburant diesel et composition de carburant diesel
JP4537642B2 (ja) * 2000-05-19 2010-09-01 新日本石油株式会社 燃料油添加剤及び燃料油組成物
EP1236789A3 (fr) * 2001-02-28 2004-01-28 Chevron Oronite Company LLC Procédé permettant d'empêcher la formation de dépots dans un moteur à essence à injection directe
US6475251B1 (en) 2001-02-28 2002-11-05 Chevron Oronite Company Llc Method for controlling engine deposits in a direct injection spark ignition gasoline engine
US6652667B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Method for removing engine deposits in a gasoline internal combustion engine
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WO2003078553A2 (fr) 2002-03-12 2003-09-25 The Lubrizol Corporation Procede de fonctionnement d'un moteur a essence a injection directe au moyen d'une composition de carburant
US6616776B1 (en) 2002-11-06 2003-09-09 Chevron Oronite Company Llc Method for removing engine deposits in a reciprocating internal combustion engine
WO2004050806A3 (fr) * 2002-12-02 2004-07-29 Basf Ag Utilisation d'amines et/ou de produits d'addition de mannich dans des compositions de carburant et de lubrifiant utilisees dans des moteurs a allumage commande et injection directe
AU2003294756B2 (en) * 2002-12-02 2009-09-10 Basf Aktiengesellschaft Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct injection spark ignition engines
US8449630B2 (en) 2002-12-02 2013-05-28 Basf Se Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct injection spark ignition engines
US9309475B2 (en) 2002-12-02 2016-04-12 Basf Se Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct injection spark ignition engines
US9938479B2 (en) 2002-12-02 2018-04-10 Basf Se Use of amines and/or Mannich adducts in fuel and lubricant compositions for direct-injection spark ignition engines
US10604655B2 (en) 2014-08-29 2020-03-31 Iowa State University Research Foundation, Inc. Asphalt products and materials and methods of producing them

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EP1122295A1 (fr) 2001-08-08
AU6001899A (en) 2000-04-26
EP1122295A4 (fr) 2002-02-06
US20010020345A1 (en) 2001-09-13

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