WO2000020537A1

WO2000020537A1 - Gasoline additive for direct-injection gasoline engine

Info

Publication number: WO2000020537A1
Application number: PCT/JP1999/005446
Authority: WO
Inventors: Katsuhiko Haji; Masaki Nagao; Jun Akimoto; Masahiro Yoshida
Original assignee: Nippon Mitsubishi Oil Corporation
Priority date: 1998-10-06
Filing date: 1999-10-04
Publication date: 2000-04-13
Also published as: EP1122295A1; AU6001899A; EP1122295A4; US20010020345A1

Abstract

A gasoline additive comprising at least one nitrogenous compound selected among polyoxyalkyleneamine compounds (1A) and polybutenylamine compounds (1B). It gives a gasoline composition suitable for use in direct-injection gasoline engines. The compounds (1A) can be obtained by using an appropriate ketimine compound as a reaction initiator to polymerize an epoxy compound and hydrolyzing the resultant polyoxyalkylene glycol derivative.

Description

Description Gasoline additive for in-cylinder direct injection gasoline engine Technical field

TECHNICAL FIELD 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. Background art

From the perspective of resource saving and the suppression of global warming, it is required to reduce the use of fossil fuels worldwide, and improving fuel economy is the biggest issue for gasoline vehicles. On the other hand, in some urban areas, pollutants such as NOx do not meet environmental standards, and gasoline vehicles are required to further reduce pollutants. In order to simultaneously improve fuel efficiency and reduce environmental pollutants in exhaust gas in response to such demands, direct injection gasoline engines are considered to be the most promising.

Conventional gasoline engines form a uniform premixed gasoline and air by injecting gasoline into the intake port. On the other hand, 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. In addition, since 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.

However, direct injection gasoline engines inject gasoline into the combustion chamber, which may present new problems that differ from conventional gasoline engines. One of them is deposits that accumulate in the combustion chamber, especially in the cavity. There is a bird. In 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. . At this time, if 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.

In view of such circumstances, 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. . Disclosure of the invention

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.

That is, one of the gasoline additives according to the present invention comprises a nitrogen-containing compound represented by the following general formula (la).

(In the general formula (1a), R ¹ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ² , RR ^4, and R ⁵ each independently represent hydrogen, 1 to 16 carbon atoms. A hydrocarbon group or a group represented by the following general formula (2a), wherein a is 1

An integer of up to 200, 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, and d + e = 3. )

(In the general formula (2a), 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. Represents an alkylene group of 2 to 6, or an alkylene group having a total carbon number of 4 to 10 having an alkoxyalkyl group as a substituent,

R ^{1 ()} represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and f represents an integer of 0 to 50. )

Group A

A 1-0-C 0-

A 2 C-1

A 3 _〇一 CO-R ^{1 1-}

(R ¹¹ represents an alkylene group having 1 to 6 carbon atoms)

A 4 - 0- C O- 0 -R 12 -

(R ¹² represents an alkylene group having 1 to 6 carbon atoms)

A 5-CO-0-R ^{1 3-}

(R ¹³ represents an alkylene group having 1 to 6 carbon atoms)

Group B

B 1: hydrogen

B 2: hydrocarbon group having 1 to 30 carbon atoms

B 3: Alkinol group represented by the following general formula (3a)

One R ¹⁴ -〇 H (3 a)

(In the general formula (3a), R ¹⁴ represents an alkylene group having 1 to 6 carbon atoms.)

B 4: Nitrogen-containing group represented by the following general formula (4a)

(In the general formula (4a), R ¹⁵ represents an alkylene group having 2 to 6 carbon atoms, and 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.)

B 5: a group represented by the following general formula (5a)

(In the general formula (5a), 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; Represents an imino group or oxygen substituted with a hydroxyl group, and h is 1 when e = 1, 0 or 1 when e = 2 (however, when h = 0, the general formula (5) a) N (nitrogen) in the general formula (la) corresponds to N (nitrogen)

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).

(In the general formula (1 b), 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, and an R ^{2 G,} R ^27, the total number of carbon atoms of R ²⁸ and R ^{2 9} are 2, Q any of the following formulas (2 b) ~ (7 b ) 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, and m represents an integer of 1 to 100. )

(In the general formula (8 b), 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. BEST MODE FOR CARRYING OUT THE INVENTION

In the general formula representing the first nitrogen-containing compound of the present invention (la), 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 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 branched octadecyl group, straight or branched nonadecyl group, straight or branched icosyl group, straight or branched heicosyl group, straight or branched docosyl group, Straight chain Other Branched preparative glycosyl groups, and straight-chain or branched tetracosyl groups.

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 icosenyl groups, linear or branched hexicosenyl groups, linear or Branched docosenyl, straight or branched Application Benefits Koseniru group, straight or branched Te Torakoseniru group.

Preferred cycloalkyl groups as R ¹ include cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Similarly 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 substituted isomers), di-linear or branched provircyclopentyl group (all , Linear or branched propylethylmethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (all ), Ethylcyclohexyl group (including all substituted isomers), linear Or branched propylcyclohexyl group (including all substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers) ), Getylcyclohexyl group (including all substituted isomers), ethyldimethylcyclohexyl group (including all substituted isomers), linear or branched propyl methylcyclohexyl group (including all substituted isomers) Straight-chain or branched pyrethylcyclohexyl groups (including all substituted isomers), di-linear or branched propylcyclohexyl groups (including all substituted isomers), straight-chain Or branched propylethylmethylcyclohexyl group (including all substituted isomers), methylcycloheptyl group (including all substituted isomers) Dimethylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), linear or branched propylcycloheptyl group (including all substituted isomers), Ethylmethylcycloheptyl group (including all substituted isomers), trimethylcycloheptyl group (including all substituted isomers), getylcycloheptyl group (including all substituted isomers), and ethyl dimethylcyclo Butyl group (including all substituted isomers), linear or branched propylmethylcycloheptyl group (including all substituted isomers), linear or branched propylethylcycloheptyl group (including all substituted isomers) Isomers), di-linear or branched propylcycloheptyl groups (including all substituted isomers), linear or branched propyl Rutylmethylcycloheptyl group (all substitution isomers Including the body).

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 all substituted isomers), linear or branched hexylphenyl groups (including all substituted isomers), Linear or branched heptylphenyl group (including all substituted isomers), linear or branched octylphenyl group (including all substituted isomers), linear or branched nonylphenyl group (including all substituted isomers) ), Linear or branched decylphenyl group (including all substituted isomers), linear or branched decylphenyl group (including all substituted isomers), linear or branched Branched dodecylphenyl groups (including all substituted isomers) and the like are also included. Similarly preferred 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

Among them, when 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).

As used herein, 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. Alkenyl group, cycloalkyl group or alkylcycloalkyl group having 5 to 16 carbon atoms, aryl or alkylaryl group having 6 to 16 carbon atoms, arylalkyl group having 7 to 16 carbon atoms, etc. Included.

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. Include vinyl, propenyl, isopropyl, straight or branched butenyl, butenyl, straight or branched pentenyl, straight or branched hexenyl, Senyl, straight- or branched-heptenyl, straight- or branched-octenyl, straight- or branched-nonenyl, straight- or branched-decenyl, straight- or branched-n-decenyl, straight- or branched-chain Examples include a branched dodecenyl group, a linear or branched tridecenyl group, a linear or branched tetradecenyl group, a linear or branched pendecenyl group, a linear or branched hexadecenyl group, and the like.

Similarly, preferred cycloalkyl groups include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. Examples of the 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 propylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl Group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), straight-chain or branched propylcyclohexyl Group (including all substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers), trimethylcyclyl Hexyl group (including all substituted isomers), getylcyclohexyl group (including all substituted isomers), ethyl dimethylcyclohexyl group (including all substituted isomers), linear or branched propylmethyl Cyclohexyl group (including all substituted isomers), methylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (all , A linear or branched propylcycloheptyl group (including all substituted isomers), an ethylmethylcycloheptyl group (including all substituted isomers), Limethylcycloheptyl group (including all substituted isomers).

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

(Including all substituted isomers), ethyl dimethyl phenyl group (including all substituted isomers), tetramethyl phenyl group (including all substituted isomers) And so on. Preferred 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).

Among the above-mentioned 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.

However, when the polarity of the nitrogen-containing polar group is large, it is preferable that one to several hydrocarbon groups having 8 to 16 carbon atoms be contained in the whole molecule. 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. As used herein, 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. Group, an alkyl group having 5 to 10 carbon atoms or an alkylcycloalkyl group, an aryl or alkylaryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like. You.

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. Vinyl, propenyl, isopropyl, straight or branched butenyl, butenyl, straight or branched pentenyl, straight or branched hexenyl, straight or branched heptenyl Groups, linear or branched octenyl groups, linear or branched nonenyl groups, linear or branched decenyl groups, and the like.

Similarly, preferred cycloalkyl groups include cyclopentyl and Examples include a chlorohexyl group and a cycloheptyl group. Examples of the alkylcycloalkyl group 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 substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers) All substituted isomers), getyl cyclohexyl group (including all substituted isomers), ethyl dimethylcyclohexyl group (including all substituted isomers), linear or branched propylmethylcyclohexyl group (Including all substituted isomers), methylcycloheptyl group (including all substituted isomers), dimethylcyclohepty (Including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), linear or branched propylcycloheptyl group (including all substituted isomers), Examples include a methylmethylcycloheptyl group (including all substituted isomers) and a trimethylcycloheptyl group (including all substituted isomers).

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, η-propoxymethyl group, isopropoxymethyl group, η-butoxymethyl group, isobutoxymethyl group, sec-butoxy group. Methyl, tert-butoxymethyl, pentoxymethyl (including all isomers), hexoxymethyl (including all isomers), heptoxymethyl (including all isomers), octoxymethyl Groups (including all isomers), nonyloxymethyl groups (including all isomers), methoxethyl groups (including all isomers), ethoxyxyl groups (including all isomers), and propoxicetyl Group (including all isomers), butoxyshethyl group (including all isomers), Toxityl group (including all isomers), hexoxyshetyl group (including all isomers), heptoxicetyl group

(Including all isomers), octoxyshethyl group (including all isomers), methoxypropyl group (including all isomers), ethoxypropyl group (including all isomers), propoxy Propyl group (including all isomers), butoxypropyl group (including all isomers), pentoxypropyl group (including all isomers), hexoxypropyl group (including all isomers) ), Heptoxypropyl group (including all isomers), methoxybutyl group (including all isomers), ethoxybutyl group (including all isomers), propoxybutyl group (including all isomers) ) Butoxybutyl group (all isomers ), Pentoxybutyl group (including all isomers), hexoxybutyl group (including all isomers), methoxypentyl group (including all isomers), ethoxypentyl group (including all isomers) ), Propoxypentyl group (including all isomers), butoxypentyl group (including all isomers), pentoxypentyl group (including all isomers), methoxyhexyl group (all Ethoxyhexyl group (including all isomers), propoxyhexyl group (including all isomers), butoxyhexyl group (including all isomers), methoxyheptyl Group (including all isomers), ethoxyheptyl group (including all isomers), propoxyheptyl group (including all isomers) ), Main Tokishiokuchiru group (including all isomers), including E Tokishiokuchiru group (all isomers), including main Tokishinoniru group (all isomers) and the like. It is preferable that 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. Examples of the 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). 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene group (1- Butylethylene group, 2-butylethylene group), 1-ethyl-1-methylethylene group, 1-ethyl-2-methylene group, 1,1,2_trimethylethylene group, 1,2,2- Limethylethylene group, 1-Ethyl trimethylene group, 2-Ethyl trimethylene group, 3-Ethyl trimethylene group, 1, 1-Dimethyl trimethylene group, 1, 2 —Dimethyltrimethylene group, 1,3—dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3—dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene Group, 4-methyltetramethylene group, pentamethylene group, hexylene group (1-butylethylene group, 2-butylethylene group), 1-methyl-1-propylethylene group, 1-methyl-12-propylethylene group, 2-Methyl-2-propylethylene group, 1,1-Jetylethylene group, 1,2-Jetylethylene group, 2,2-Jetylethylene group, 1-Ethyl-1,2-dimethylethylene group, 1-ethylethyl group 2,2-dimethylethylene group, 2-ethyl-1,1,1-dimethylethylene group, 2-ethyl-1,1,2-dimethylethylene group, 1,1,2,2-tetra Lamethylethylene group, 1-Provirted rimethylene group, 2-Propyltrimethylene group, 3—Provirted rimethylene group, 1—Ethyl 1—Methyltrimethylene group, 1-Ethyl 1-2-Methyltrimethylene group, 1-Ethyl 13- Methyltrimethylene group, 2-ethyl-11-methyltrimethylene group, 2-ethyl-12-methyltrimethylene group, 2-ethyl-13-methyltrimethylene group, 3-ethyl-11-methyltrimethylene group, 3-ethyl 1,2-methyltrimethylene group, 3-ethyl-13-methyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3—trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group , 1,2,3—trimethyltrimethylene group, 1,3,3-trimethyltrimethylene group, 2,2,3—trimethyltrimethylene 2, 3, 3-trimethyltrimethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 3-ethyltetramethylene, 4-ethyltetramethylene, 11-dimethyltetramethylene, 1 2 -Dimethyltetramethylene group, 13-dimethyltetramethylene group, 14-dimethyltetramethylene group, 22-dimethyltetramethylene group, 23-dimethyltetramethylene group, 24-dimethyltetramethylene group, 33-dimethyltetramethylene group Methylene group, 34-dimethyltetramethylene group, 44-dimethyltetramethylene group, 1 methylpentamethylene group, 2-methylpentamethylene group, 3

—Methylpentamethylene group, 4-methylpentamethylene group, 5-methylpen And a tamethylene group and a hexamethylene 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. — (Methoxyl) Ethylene, 2— (Methoxyl) Ethylene, 1— (Ethoxymethyl) Ethylene, 2 _ (Ethoxymethyl) Ethylene, 1-Methoxymethyl — 2-Methylethylene, 1, 1 —Bis (methoxymethyl) ethylene group, 2,2-bis (methoxymethyl) ethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1—Bis (methoxethyl) ethylene group, 2,2-bis (Methoxyxetyl) Ethylene group, 1,2-bis (methoxyxethyl) Ethylene group, 1,1-bis (ethoxymethyl) Ethylene group, 2,2-bis (Ethoxymethyl) ethylene group, 1,2-bis (ethoxymethyl) ethylene group, 1-methyl-2-methoxymethylethylene group, 1-methoxymethyl-12-methylethylene group, 1-ethyl-2-methoxymethylethylene group , 1-methoxymethyl 2-ethyl ether group, 1-methyl-2-ethoxymethyl ethylene group,

1-ethoxymethyl 1-2-methylethylene group, 1-ethyl-12-ethoxymethylethylene group, 1-ethoxymethyl-12-ethylethylene group, 1-methyl—2-methoxyethoxyethylene group, 1—methoxethyl-2 Methylethylene group, 1-ethyl-1-2-methoxethyl ethylene group, 1-methoxyl

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. In the general formula (2a), 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. Further, 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. Accordingly, 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. 2 to 6, 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, and R ^{1 (1} is an alkyl group having 1 to 24 carbon atoms, and f is 0 It is preferably an integer of up to 30. Hereinafter, such a group (referring to a group represented by the general formula (2a)) is referred to as a “preferred substituent group (PF 1)” for convenience. 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, and R ¹⁰ is an alkyl group having 1 to 12 carbon atoms. And more preferably f is an integer of 0 to 20. Hereinafter, such a group (represented by the general formula (2)) For convenience) is referred to as “more preferred substituent group (PF 2).” In the nitrogen-containing compound of the present invention, 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)". in addition, 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. Z in the general formula (la) represents a group selected from the following group A.

Group A

A 1:-0-C 0-

A 2: ー C 0—

A 3:-0- C OR ^{1 1-}

(R ¹¹ represents an alkylene group having 1 to 6 carbon atoms)

A 4: - 0- C O- 0-R 12 -

(R ¹² represents an alkylene group having 1 to 6 carbon atoms)

A 5:-C O-0-R ^13-

(R ^{1 3} 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-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene group (1-butylethylene group, 2-butylethylene group), 1-ethyl-1-1-methylethylene group, 1-ethyl-2 —Methylethylene group, 1, 1, 1,

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,

3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3- Dimethyl trimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, pentamethylene group, hexylene group (1-butylethylene group, 2-butylethylene group) ), 1-Methyl-1-propylethylene group, 1-Methyl-2-propylethylene group, 2-Methyl-2-propylethylene group, 1,1-Jetethylethylene group, 1,2-Jetylethylene group, 2 1,2-Diethylethylene group, 1-Ethyl-1,2-dimethylethylene group, 1-Ethyl-2,2-dimethylethylene group, 2-Ethyl-1,1,1-dimethylethylene group, 2-Ethyl-1,2 —Dimethylethylene group, 1,1,2,2-Tetramethylethylene group, 1-port built-limethylene group, 2—Probuilt-methylene group, 3 —Probuilt-lime Tylene, 1-Ethyl-1-methyltrimethylene, 1-Ethyl-2-methyltrimethylene, 1-Ethyl-3-methyltrimethylene, 2-Ethyl-1-methyltrimethylene, 2-Ethyl-2-methyltrimethylene , 2-Ethyl-1-methyltrimethylene, 3-Ethyl-1-methyltrimethylene, 3-Ethyl-2-methyltrimethylene, 3-Ethyl-3-methyltrimethylene, 1,1,2—Trimethyltol Limethylene group, 1,1,3—trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1,2,3-trimethyltrimethylene group, 1,3,3-trimethyltrimethylene group, 2,2,3—trimethyltrimethylene group, 2,3,3—trimethyltrimethylene group, 1-ethyltetramethylene group, 2-ethylethyltramethi 1,3-dimethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 1,4-dimethyltetramethylene Group, 22-dimethyltetramethylene group, 23-dimethyltetramethylene group, 24 mono-dimethyltetramethylene group, 33-dimethyltetramethylene group, 34-dimethyltetramethylene group, 44-dimethyltetramethylene group, 1 Examples thereof include a methylpentamethylene group, a 2-methylpentamethylene group, a 3-methylpentamethylene group, a 4-methylpentamethylene group, a 5-methylpentamethylene group, and a hexamethylene group. Among them, 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. Further, as I ¹¹ , R ¹² and R ¹³ , 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. In the general formula (la) representing the nitrogen-containing compound of the present invention, a is an integer of 1 to 200, preferably 2 to 100.

In the general formula (la), b and c are each independently 0 or 1.

That is, when b is 0 and c is 0, it represents a compound represented by the following general formula (6a). When b is 0 and c is 1, a compound represented by the following general formula (7a) is represented. And when b is 1 and c is 0, it represents a compound represented by the following general formula (8a), and when b is 1 and c is 1, a compound represented by the following general formula (9a) Represents

(RR ² 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 in the general formula ^{(7 a), R 3,} R 4, R 5 and X, Z are, RR ² in the general formula ^{(la), R 3, R} 4, R 5 and X, Z and the same group 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). C in the general formula (la) is 0 or 1 as described above. Yes, but it is preferable that c = 0. In the general formula (la), d is 1-3, preferably 1-2, e is an integer of 0-2, preferably 1-2, and d + e is 3, most preferably d2 1 And e = 2. When d is 2 in the nitrogen-containing compound represented by the general formula (la), 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).)

In the general formula (la) representing the nitrogen-containing compound of the present invention, X represents a group selected from the following group B.

Group B

B 1: hydrogen

B 2: a hydrocarbon group having 1 to 30 carbon atoms

B 3: alcohol group represented by the following general formula (3a)

-R ¹⁴ -〇 H (3 a)

(In the general formula (3a), R "represents an alkylene group having 1 to 6 carbon atoms.)

(In the general formula (4a), R ¹⁵ represents an alkylene group having 2 to 6 carbon atoms, and 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)

)

(In the 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. Represents a substituted imino group or oxygen, h is 1 when e = 1, ◦ or 1 when e = 2 (however, when h = 0, the general formula (5a) 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.

As B 2, 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 is more preferable. A linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 9 carbon atoms is most preferable. In the general formula (3a) representing the alkanol group of B 3, 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. Among these 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. Groups (11-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene And the like. Still R ^14, 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. In the general formula (4 a) which represents the nitrogen-containing group of the B 4, 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.

Among them, 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). 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. But preferably 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. Alkenyl group, cycloalkyl group having 5 to 13 carbon atoms or alkyl group, alkyl group or alkyl aryl group having 6 to 18 carbon atoms, aryl alkyl group having 7 to 19 carbon atoms, etc. Included.

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. In particular, hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, and a carbon number? Most preferred are arylalkyl groups of 1 to 9 or groups represented by the general formula (3a).

G in the general formula (4a) is an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.

Further, 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.

RII ^ (12a)

R ¹⁶

(Formula (1 1 a) and (1 R ¹⁵ in 2 a), R ^{1 6} and g show in one general formula ^{(4 a) R 15, R} 16 and g the same group, the integer.) Therefore, 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.

(1) Combination of one kind of structural unit represented by general formula (1 2a)

(2) Two or more different structural units contained in the general formula (12a) are randomly combined, alternately combined, or block-coupled.

The nitrogen-containing group represented by the formula (4 a) which are classified into B 4, 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. In the group represented by the general formula (5 a) corresponding to the B 5, 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 . Among them, 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.

R ^{1 9,} R ² ° in the general formula (5 a), R ^{2 1} and R ^22, which it independently hydrogen, represents a hydrocarbon group or a hydroxyl group from 1 to 1 0 carbon atoms. 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. A linear or branched alkenyl group having 10 carbon atoms, a cycloalkyl group or an alkylcycloalkyl group having 5 to 10 carbon atoms, an aryl group or an alkylaryl group having 6 to 10 carbon atoms, and having 7 to 1 carbon atoms And an arylalkyl group of 0.

Among ^{^{these, 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.

In the general formula (5a), 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. 0 linear or branched alkenyl group, 5-10 carbon atoms or alkylcycloalkyl group, 6-10 carbon atoms or alkylaryl group, carbon number Examples thereof include a 7-10 arylalkyl group. Of these, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

Among these, 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. Or 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. H in the group represented by the general formula (5a) is h = 1 when e = 1 in the general formula (la), and ι = 0 until e = 2 in the general formula (la). Or] = 1. However, when e = 2 and h = 0, N (nitrogen) in the general formula (5a) is also N (nitrogen) in the general formula (1). That is, when e = 2 and h = 0, as represented by the general formula (13a), N (nitrogen) contained in the compound forms a heterocyclic ring represented by the general formula (5a) You are a member of

(Formula (1 3 RR in ^{^{a) \ R 3, R 4}} , R 5, R 6 and Z, the ^{^{R \ R 3, RR 5,}} R B and Z and the same group in the general formula (la) shown, a, b and c are a in the general formula (1 a), a b and c the same integer;] ^{^{^{9, R 20, R 2 1}}} , R 22 and Y have the general formula (5 a ) in representing the ^{^{R 1 9, R 20, R}} 2 1, R 22 and Y the same group.)

The group represented by the general formula is classified into Β 5 (5 a), 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, wherein 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. An amino group or an oxygen substituted with an alkyl group or a hydroxyl group, wherein h is e = 1, h = 1, and 6 = 2] 1 = 0 or h = l (where h = In the case of 0, it is more preferable that N (nitrogen) in the general formula (5a) is also N (nitrogen) in the general formula (la), and 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, and Y is an amino group, an amino group substituted with an alkyl group or hydroxyl group having 1 to 3 carbon atoms, or oxygen, and when h is e = 1, h = 1 When e = 2, h = 0 or h = 1 (However, when h2 °, N (nitrogen) in the general formula (5a) is also N (nitrogen) in the general formula (1a) Is most preferred.

In the general formula (1) representing the nitrogen-containing compound of the present invention, 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. As described above, the 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),

In 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. Group or an alkoxyalkylene group-substituted ethylene group having 2 to 8 carbon atoms, wherein 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,

a is an integer of 1-200, b and c are independently 0 or 1, d is an integer of 1-2, e is an integer of 1-2, and d + e = 3 and

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), and 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

A group represented by (3a), g is an integer of 1 to 4, and in the general formula (5a) corresponding to B5, R ¹⁸ is an alkylene group having 2 to 4 carbon atoms; ^{^{1 £), R 20, R}} 2 1 and R ^{2 2} it it independently hydrogen, an alkyl group or a hydroxyl group from 1 to 6 carbon, Y is a methylene group, an alkyl group or hydroxyl group of carbon number 1-6 A substituted methylene group, an imino group, an amino group substituted with an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, or oxygen; when e = 1, h = 1 and e = 2 If h = 0 or h = 1 (however, if h = 0, the general formula

(5a) and general formula (la) share the same N (nitrogen)). Further preferred 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);

In 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, and 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,

Formula corresponding to B 3 (3 a) In R ¹⁴ is Ri der alkylene group having 1 to 3 carbon atoms, the general formula corresponding to B4 (4 a) In the alkylene group of R ^{1 5} is 2 carbon number 3 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? An arylalkyl group represented by the general formula (3a) or a group represented by the general formula (3a), wherein g is an integer of 1 to 3, and in the general formula (5a) corresponding to B5, R ¹⁸ is a carbon atom R ¹⁹ , R ² R ²¹ and R ²² are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and Y is an amino group, 1 to 3 carbon atoms. An amino group or an oxygen substituted with an alkyl group or hydroxyl group, and h is 0 or 1 (however, when h = 0, the general formula (5a) is the same as the general formula (la) N (nitrogen) is shared). The nitrogen-containing compound represented by the general formula (la) can be produced by any method.

As an example, 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.

(A) Ketimination process

Starting from a compound having two or more amino groups in the molecule or a compound having at least one amino group and another active hydrogen group such as an alkanol group, an imino group, a carboxyl group, etc. 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. Dipropylene triamine, di (trimethylene) triamine, dimethylamino diamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentane 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), and 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. As the ketone, one represented by the following general formula (14a) is usually used.

_R ? ^ _ _C _ _R 24 (14a)

II

o

(In the above formula (14a), R ²³ and { ² } independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.)

Further, among the compounds represented by the above general formula (14a), ketones having a branched alkyl group and having large steric hindrance are preferable, and isobutylmethylketone, isobutylethylketone, and diisobutylketone are preferable. Etc. are preferably used. By reacting an alkanolamine with a ketone, a ketimine compound represented by the following general formula (15a) can be obtained.

R ²³

HO-RN = C ( ^15a )

V ⁴

(In the above formula (1 5 a), 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 When an amino acid is reacted with a ketone, a ketimine compound represented by the following general formula (16a) can be obtained.

(In the above formula (1 6 a), 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 In addition, when a diamine and a ketone are reacted, a ketimine compound represented by the following general formula (17a) can be obtained.

twenty three

R

H ₂ NR— N = C (17a)

twenty four

R

(In the above formula (17 a), 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 In addition, 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.

(18a)

(In the above formulas (18a) and (19a), R ¹⁵ and R ¹⁶ are

1 6

In (4a), R ¹⁵ and R ^iU represent the same group, and g, g, and g "represent one group.

2 3 2 4 represents the same integer as g in the general formula (4a), and R and R represent the general formula

twenty four

It represents the same group as R ²³ and (14a). ) When reacting a starting amine with a ketone of the general formula (14a) The molar ratio is preferably such that the amino group to be protected is reacted with an equimolar ketone.

Equimolar for alkanolamine, amino acid and diamine, polyamine

In the case of (the number of N atoms is 3 or more), it is preferable to react an equimolar or double molar ketone.

The reaction temperature in the ketimination step is optional, but is usually preferably 40 to 180 ° C, more preferably 80 to 150 ° C.

(B) Polymerization process

For example, using a base such as potassium hydroxide or sodium hydroxide as a catalyst, and using the ketimine compound obtained in the ketimination step (A) as a reaction initiator, 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.

R ² R ^J

R, 4

— C— C— R ^J (20a) R— T (21a) \ I

0

In the general formulas (20a) and (21a), I ¹ , RR ³ , R ^4, and R Ί ⁵ Ί 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. )

(24a)

(The above general formula (22 a), (23 a ) and (a in ^{24 a), R, RR 3} , R 4, R 5 and R ^6, a in the general formula (la), R \ R

1 1

R \ R \ R. And R. Same and are the same, R ^{1 1} and R ^{1 1} in Group A A 3

R ¹⁵ is the same as R "in the general formula (4a)

23 24

R ² is the same as RR in the general formula (14a), and i is an integer such that d + i = 2. )

(A in the above formula (25 a), 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)

R R 23

R

R- 0— C— C- ■ R— N— R then N2 C. (26a)

16

R ⁴ R, R ²⁴

(A in the above formula (26 a), d, R \ R \ RR 4 and R ⁵ are the same as ^{a, d, R \ R 3} , R 4 and R ⁵ in the general formula (la), g, R ¹⁵ and R ¹⁶ are the same as g, R ¹⁵ and R ¹⁶ in the general formula (4a) There, R ^{² 3,} R ² ⁴ is identical to R ^{² 3,} R ² ⁴ in the general formula (1 4 a), i is an integer such that d + i = 2. 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 glycidyl ether, linear or branched benzyl glycidyl ether, linear or branched hexyl glycidyl ether, linear or branched heptyl glycidyl ether, linear or branched Octyl glycidyl ether, straight or branched nonyl glycidyl ether, straight or branched decyl glycidyl ether, straight or branched decyl glycidyl ether, straight or branched dodecyl glycidyl ether, Chain or branched tridecylglycidyl ether, linear or branched tetradecylglycidyl ether, linear or branched pendecylglycidyl ether, linear or branched hexadecylglycidyl ether Tereyl, straight or branched heptane decylglycidyl ether, straight or branched hexyl Decyl glycidyl ether, linear or branched octadecyl glycidyl ether, vinyl glycidyl ether, linear or branched probenyl glycidyl ether, linear or branched butenyl glycidyl ether, straight Chain or branched pentenyl glycidyl ether, straight or branched hexenyl glycidyl ether, straight or branched heptenyl glycidyl ether, straight or branched octenyl glycidyl ether, straight or branched Branched nonenilda Lysidyl ether, linear or branched decenyl glycidyl ether, linear or branched undecenyl glycidyl ether, linear or branched dodecyl glycidyl ether, linear or branched tridece Nylglycidyl ether, linear or branched tetradecenyl glycidyl ether, linear or branched pendecenyl glycidyl ether, linear or branched hexadeceyl glycidyl ether, linear or branched Branched heptane decenyl glycidyl ether, straight or branched hexadecenyl dalicidyl ether, straight or branched octenyl decenyl glycidyl ether, phenyl glycidyl ether, trin Glycidyl ether, xylyl glycidyl ether, linear or branched propyl phenyl glycidyl ether, linear or Branched butyl phenyl glycidyl ether, straight or branched pentyl phenyl glycidyl ether, straight or branched hexyl phenyl glycidyl ether, straight or branched heptyl phenyl glycidyl ether, straight or branched Octylphenylglycidylether, linear or branched nonylphenylglycidylether, linear or branched decylphenylglycidylether, linear or branched pentadecylphenylglycidylether, linear or To branched dodecylphenyl glycidyl ether, linear or branched tridecylphenyl glycidyl ether, linear or branched dodecylphenyl glycidyl ether, 1,2-epoxy-3-methoxy-5-oxa Kisan, 1,2—epoxy-1,4,7—dioxaoctane, 4,5—epoxy—2,7—dioxaoctane, 1,2—epoxy-5-methyl-1,4,7-dioxaoctane, 1,2—epoxy-1 6—methyl-4,7—dioxaoctane, 1,2—epoxy-1 5- (2-oxapropyl) 1-4,7-dioxaoctane, 1,2-epoxy-1,3,5-bis (2-oxapropyl) _4,7-dioxaoctane, 1,2-epoxy-1,3,6-bis (2-year-old oxapropyl) 1,4,7-dioxaoctane, 1,2—epoxy-6—methoxy-4,8—dioxanonane, 1,2—epoxy-1,4,7,10—trioxanedecane, 1,2-Epoxy-5-methyl-4,7,10-trioxanedecane, 1,2-Epoxy-18-methyl-1,4,7,10- Lioxanedecane, 4,5-epoxy-19-methyl-1,2,7,10-trioxanedecane, 1,2-epoxy-6,9-dimethyl-1-4,7,10- Lioxanedecane, 1,2-epoxy-1,6,9-bis (2-oxapropyl) -14,7,10-Trioxanedecane, 1,2-epoxy-4,7,1 0,1 3—Tetraoxate Tradecane, 4,5—Epoxy 2,7,10,13—Te Traoxate Tradecane, 7,8—Epoxy 1,2,5,10,13—Tetraoxate Tradecane, 7 , 8-Epoxy-1,3,12-Dimethyl-1,2,5,10,13-Tetraoxate Tradecane, 1,2-Epoxy-6,9,12 2-Trimethyl-1,4,7,10,1 3-tetraxatetradecane and the like. When the ketimine compound is reacted with the epoxy compound of the general formula (20a), the molar ratio can be arbitrarily selected. Usually, 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.

(C) Hydrolysis step

By heating the polyoxyalkylene glycol derivative having a ketimine compound at the terminal obtained in the above step in the presence of excess water, 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.

Further, by adding 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.

Also, morpholine, N-/?-Hydroxyl morpholine, N- (2-hydroxypropyl) morpholine, piperidine, 1- (2-hydroxyl) Tyl) piperidine, 2-dimethylaminoethanol, 2-dimethylamino-1-propanol, 1-dimethylamino-2-propanol, 4-dimethylamino-1-butanol, 2-dimethylamino2- Methyl 1-propanol, 2-methylaminopropyl, 3-methylaminopropanol, 1-ethylamino-2-propanol, 2-diisopropylaminopropyl, 2-dimethylaminoethyl, 3-dimethylaminoethyl, 3-dimethylamine Minopropylamine, 2-ethylaminopropylamine, 3-ethylaminopropylamine, 2-diisopropylaminoethylamine, 1-aminopyridine, 1- (2-aminoethyl) piperidine , 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, pi When azine, 1-methylbiperazine, 11- (2-aminoethyl) piperazine, etc. are used, there is no need to perform the (A) ketiminization step and (C) hydrolysis step, B) The polymerization step can be performed, and the nitrogen-containing compound of the present invention represented by the general formula (la) can be obtained. Alternatively, 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.

(D) Polymerization process

For example, using a base such as potassium hydroxide or sodium hydroxide or an alkoxide thereof as a catalyst, an oxygen-containing compound represented by the general formula (27a) as a reaction initiator, and a compound represented by the general formula (20a) 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 To obtain a polyoxyalkylene glycol derivative represented by the formula:

R- ~ OH ( ^27a )

Formula (27 a) and a in the (2 8 a), 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.

(E) Chloroformate process

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).

(F) Carbamate process

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.

'X in general formula (30a) is the case where e = 2 in general formula (la) Indicates the X and the same group, R ^{1 2} represents the same group as R ^{1 2} in Group A A 4, j is 0 or 1.

The amine compound represented by the general formula (30a) includes ethylenediamine, propylenediamine (1,2-diaminopropane), trimethylenediamine (1,1-diaminopropane) and dimethylaminopropylamine. , Diethylenetriamine, dipropylenetriamine, di (trimethylene) triamine, dimethylaminopropylenediamine, triethylenetetramine, tripropylenetetramine, tetraethylenetetramine , Tetrapropylene pentanemin, pentaneethylenehexamine, pentahexanepropyleneamine, piperidine, 1-aminobiperidine, 4-aminoaminobiperidine, 1-1 (2-aminoethyl ) Peridine, morpholine, 4-amino morpholine, 4- (2-amino Ethyl) morpholin, 4- (3-aminopropyl) morpholin, piperazine, 1-amino-4- 4-methylbiperazine, 1-1 (2-aminopropyl) piperazine, 1- (3-aminopropyl) Nopropyl) piperazine, monomethanolamine, monoethanolamine, mono-n-propanolamine, monoisopropanolamine, mono (linear or branched) bushylamine (position of hydroxyl group) Is optional), mono (linear or branched) pentanoluamine (position of hydroxyl group is arbitrary), mono (linear or branched) hexanolamine (position of hydroxyl group is arbitrary), 2- (2-aminoethyl) ethanol (see formula a), D-glucamine (see formula b)

H N— CH CH NH- CH CH OH (a)

OH H OH OH NH ₂ — CH factory C—C to CC—H ₂ OH

H OH H H

Dimethanoamine, jetanoamine, g-n-propanolamine, diisopropanolamine, di (linear or branched) butanoamine (the position of the hydroxyl group is arbitrary) , Di (linear or branched) pennanolamine (position of hydroxyl group is arbitrary), di (linear or branched) hexanolamine (Hydroxyl position is optional), monohydroxypyrrolidine, monohydroxypyrroline (hydroxyl position is optional), monohydroxypyrrole

(Position of hydroxyl group is arbitrary), Monohydroxypyrazolidine (Position of hydroxyl group is arbitrary), Monohydroxypyrazoline (Position of hydroxyl group is arbitrary), Monohydroxypyrazole (Position of hydroxyl group is arbitrary) Yes), monohydroxymidazolidine (position of hydroxyl group is arbitrary), monohydroxymidazoline (position of hydroxyl group is arbitrary), monohydroxymidazol (position of hydroxyl group is arbitrary), monohydroxyl Phloxane (position of hydroxyl group is arbitrary), Monohydroxypiperidine (position of hydroxyl group is arbitrary), Monohydroxypiperazine (position of hydroxyl group is arbitrary), Monohydroxypiperidine (position of hydroxyl group) Is optional), monohydroxyindolin (position of hydroxyl group is optional) In it is), mono human Dorokishii down Doll

(Position of hydroxyl group is arbitrary), Monohydroxyisoindole (Position of hydroxyl group is arbitrary), Monohydroxypurine (Position of hydroxyl group is arbitrary), Monohydroxycarbazole (Position of hydroxyl group is arbitrary) Yes), monohydroxy-carboline (position of hydroxyl group is arbitrary), monohydroxyphenoxazine (position of hydroxyl group is arbitrary), monohydroxyperimidine (position of hydroxyl group is arbitrary), dihydroxypyrrolidine , Dihydroxypyrroline (the position of the hydroxyl group is arbitrary), dihydroxypyrrole

(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, methyldi (linear or branched) butylamine, ethyldi (linear or branched) butyl Amines, tris (straight or branched) pennolsamine, methyldi (straight or branched) pennolsamine, ethildi (straight or branched) pennosamines, etc. . 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. Other than butene and isopten, such as ethylene and propylene, may be contained. In addition, 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.

Specific examples of the polybutenylamine-based compound of the present invention include a compound represented by the aforementioned general formula (lb). In the 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.

R ²⁶ in the general formula (lb), ² R ^{2 8} and R ^{2 9,} it it independently hydrogen atom or a methyl group or Echiru group, the total number of carbon atoms of R ²⁶ to R ^{2 9} are Shitamawaru 2 There is no difference, there are always two. In other words, the repeating unit in the general formula (lb) has a structure derived from 1-butene, 2-butene or isobutene. However, 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.

However, from the viewpoint of more excellent detergency, the above repeating unit is 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. In addition, in order to suppress the generation of deposits in the combustion chamber due to the deterioration of the valve stick due to the high thermal decomposition property, it is necessary that m is 100 or less. It is preferably at most 40, more preferably at most 40. In the general formula (lb), 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 in the} general formula (lb). And 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). As used herein, 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. And a cycloalkyl group or alkylcycloalkyl group having 5 to 10 carbon atoms, an aryl group or alkylaryl group having 6 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms.

Specific examples of the 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. Examples of the alkenyl group having 2 to 10 carbon atoms 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. Specific examples of the 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 propylcyclohexyl group (including all substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers) ), Trimethylcyclohexyl group (including all substituted isomers), getylcyclohexyl group (including all substituted isomers), ethyl dimethylcyclohexyl group (including all substituted isomers) , Linear or branched propylmethylcyclohexyl group (including all substituted isomers), methylcycloheptyl group (all Dimethylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), linear or branched propylcycloheptyl group (including all substituted isomers) A methylmethylcycloheptyl group (including all substituted isomers), a trimethylcycloheptyl group (including all substituted isomers), and the like. 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. Enyl group (including all substituted isomers), linear or branched propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers), trimethyl Phenyl group (including all substituted isomers), linear or branched butylphenyl group (including all substituted isomers), linear or branched propylmethylphenyl group (including all substituted isomers) , Getyl phenyl group (including all substituted isomers), ethyl dimethyl phenyl group (including all substituted isomers), tetramethyl phenyl group (including all substituted isomers) And the like. Specific examples of the 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). , A phenyl group, a methyl phenyl group (including all substituted isomers), and a dimethyl: π-netyl group (including all substituted isomers). Examples of the 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. And 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. Among these, 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). In the general formula (8 b), 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. Furthermore: ³² is an alkylene group having 1 to 3 carbon atoms, specifically methylene group, ethylene group, propylene group (1-methylethylene group, 21-methylethylene group) or Limethylene groups are most preferred. 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. No. Among them, 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.} Among them, 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. When 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). However, 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. In order to improve the cleanliness of the combustion chamber of a direct injection gasoline engine, especially in the cavity, the lower limit of the content is 0.001% by mass, preferably 0.03% by mass. Preferably it is 0.005% by weight, even more preferably 0.01% by weight, most preferably 0.015% by weight. In addition, 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. As 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.

One typical blending example of lead-free gasoline that can be used as a fuel oil for a direct injection gasoline engine by blending the nitrogen-containing compound of the present invention is shown below.

(1) Modified gasoline: 0 to 70% by volume

(2) Light fraction of modified gasoline (boiling point range: 25 to 120 ° C):

0 to 35% by volume

(3) Heavy fraction of modified gasoline (boiling point range: about 110 ° C to 200 ° C) 0 to 45% by volume

(4) Decomposed gasoline: 0 to 50% by volume

(5) Light fraction of cracked gasoline (boiling point range: about 259 ° C)

0 to 45% by volume

(6) Cracked gasoline heavy distillate (boiling range: about 900 ° C)

0-40% by volume

(7) Alkylate: 0 to 40% by volume

(8) Propylene dimerization, followed by hydrogenation of the paraffin fraction: 0 to 30% by volume

(9) Isomerized gasoline: 0 to 30% by volume

(10) MTBE: 0 to 15% by volume

(11) Light naphtha: 0 to 20% by volume

(12) Butane: 0 to 10% by volume In order to reduce the benzene content in the gasoline composition, 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. As another measure, there is a method in which reformed gasoline is preliminarily treated by one of the following exemplified methods, and reformed gasoline having a reduced benzene concentration is used as a gasoline base material.

(1) Distill the reformed gasoline to remove the benzene fraction.

(2) Extract benzene in the reformed gasoline using a solvent such as sulfolane.

(3) Convert benzene in reformed gasoline to other compounds.

(A) Hydrogenates benzene and converts it to cyclohexane, methylcyclopentane, etc.

(B) Reacts with benzene and an aromatic hydrocarbon compound having 9 or more carbon atoms to convert to toluene, xylene, ethylbenzene and the like.

(C) Alkylize benzene with lower olefins (ethylene, propylene, etc.) or lower alcohols (methanol, ethanol, etc.).

(4) Desulfurized heavy naphtha obtained by distilling and removing hydrocarbon compounds having 6 carbon atoms is used as the raw material for the catalytic reformer.

(5) Change the operating conditions of the catalytic reformer. Other 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.

One or more of these additives can be added, and the total added amount is preferably 0.1% by mass or less based on the total amount of the gasoline composition. 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.

₁₀ % by volume distillation temperature (Τ10) 35 to 55 ° C

₃₀ % by volume distillation temperature (Τ30) 55 to 75 ° C

₅₀ % by volume distillation temperature (Τ50) 75 to ₁₀₀ ° C

₇₀ % by volume distillation temperature (Τ70) 100 to 130. C

₉₀ % by volume distillation temperature (Τ90) 110 to 160. C

Distillation end point 130 to 210 ° C

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. On the other hand, 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.

If the temperature is lower than 75 ° C, there is a possibility that high-temperature operability may be impaired. on the other hand, 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. On the other hand, 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. On the other hand, T _9. 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. On the other hand, 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. In addition, 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. The term "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 . on the other hand, 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.

Here, 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

Offline component (V (O)): 0 to: L 5% by volume

Aromatic (V (Ar)): 0 to 35% 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.

Also, 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.

Further, 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.

The above V (P), V (〇) 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.

(1) V (B z): 0 to 1% by volume

(2) V (T o 1): 0 to 30% by volume

(3) V ( _C8A ): 0 to 20% by volume

(4) V ( _C9A ): 0 to 5% by volume

(5) V (C10 _{+ A} ): 0 to 3% by volume

(6) V (PA) = 0

Or

V (MA) / V (PA) 1 or more when V (P A) ≠ 0

_{(7) V (C 4)} 0~ 1 0 volume%

_{(8) V (C 5)} 1 0~ 3 5 volume%

_{(9) V (C 6)} 1 0~ 3 0 volume%

(10) V (C7 _{+ p} ): 10 to 50% by volume

(11) V (C ₉₊ ) 0 to 10% by volume The above 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. By adjusting the benzene content to 0 to 1% by volume, the benzene concentration in the exhaust gas can be kept low.

The above 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.

The above 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.

The above 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. In the present invention, 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”.

The above 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. Examples of the hydrocarbon compound having 4 carbon atoms include n-butane, 2-methylbutane (isobutane), 1-butene, 2-butene, and 2-methylpropene.

The above 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. By setting the content of the aliphatic hydrocarbon compound having 5 carbon atoms to 10% by volume or more, a gasoline composition excellent in normal-temperature operability can be obtained. Further, by setting the content to 35% by volume or less, a gasoline composition excellent in high-temperature operability can be obtained. Then, from the viewpoint of preventing coking gasoline in the injectors evening, 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. Similarly, 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. It 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. By setting the content of the aliphatic hydrocarbon compound having 6 carbon atoms to 10% by volume or more, a gasoline composition excellent in normal-temperature operability can be obtained. Further, by setting the content to 30% by volume or less, a gasoline composition excellent in high-temperature operability can be obtained. Then, the content of Lee Njeku terms of gasoline in anti-coking in the evening, 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.

Examples of the saturated aliphatic hydrocarbon compound having 6 carbon atoms 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.

The above 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. By setting the content of the saturated aliphatic hydrocarbon compound having 7 or more carbon atoms to 10% by volume or more, a gasoline composition excellent in normal-temperature operability can be obtained, and this is reduced to 50% by volume or less. By doing so, a gasoline composition having better high-temperature operability can be obtained. Examples of the saturated aliphatic hydrocarbon compound having 7 or more carbon atoms include n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, and 2,4-dimethyl ぺ. Pentane, 3,3-dimethylpentane, 3-ethylpentane, and 2,2,3-trimethylbutane.

The above 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. .

Note that V (C ₄ ), V (C ₅ ), V (C _5p ), V (C _5o ), V

(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. In other words, 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, and the carrier gas flow rate is 0. 5-1.5 ml / min, split ratio 1: 50-; L: 250, inlet temperature 150-250 ° C, initial column temperature—10-10 ° C, final column temperature 150 These values are measured under the conditions of ~ 250 ° C and detector temperature of 150 ~ 250 ° C.

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.

Here, the oxygen-containing compound refers to alcohols having 2 to 4 carbon atoms, ethers having 4 to 8 carbon atoms, and the like. Examples of 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. There are, for example, 1ME (TAME) and Yuichi Shari Amylethyl ether, among which MTBE and TAME are preferable, and MTBE is most preferable. In addition, 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. Here, 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. Here, 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). Further, the gasoline composition of the present invention desirably has a kerosene mixing amount of 0 to 4% by volume. Here, 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. In other words, a methyl silicon cavity column is used for the column, hemi- or nitrogen is used for the carrier gas, and a hydrogen ionization detector (FID) is used for the detector. 0.5 to 1.5 ml / min, split ratio 1:50 to 1: 250, inlet temperature 150 to 250. Initial column temperature-measured at 10 to 10 ° C, final column temperature at 150 to 250 ° C, detector temperature at 150 to 250 ° C. Hereinafter, examples of the present invention will be described, but these examples do not limit the present invention.

First, a synthesis example of the nitrogen-containing compound included in the general formula (la) is shown below. Synthesis example 1

In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet, 6.1 g (0.1 mol) of monoethylamine, 10 g (0.1 mol) of methyl isobutyl ketone and toluene After 100 ml was charged and the inside of the reaction vessel was replaced with nitrogen, the reaction vessel was heated at 120 ° C. for 5 hours to cause a dehydration and ketimine reaction. After the ketimination reaction, 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.

(31a)

Synthesis example 2

In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet, monoethanolamine 6.1 (0.1 mol), diisobutyl ketone 14.2 g (0.1 mol) and toluene 10 After 0 ml was charged and the inside of the reaction vessel was replaced with nitrogen, the reaction vessel was heated at 120 ° C. for 5 hours to cause a dehydration and ketimination reaction. After the ketimine-forming reaction, the reaction mixture was cooled to room temperature, 5.6 g of hydrogen hydroxide was added as an additional catalyst, and the mixture was purged with nitrogen gas, heated to 120 ° C, and heated to 1,2-butylene oxide. After adding 3 g (3.0 mol) and reacting 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, 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. As a result of ¹³ C-NMR analysis, this nitrogen-containing compound was a polymer having an average structure represented by the formula (32a). This is hereinafter referred to as Compound 2.

H— (-OCHCH ₂ OCH ₂ CH ₂ NH ₂ (32a)

CH ₂

CH ₃ synthesis example 3

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. After the 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). 7 mol) and 130.4 g (0.7 mol) of 2-ethylhexylglycidyl ether were added and reacted for 5 hours. Then, 9.3 g (0.1 mol) of 2-chlorobutane was added and reacted for 2 hours. Then, the reaction product solution was purified 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, after removing excess water, toluene and ketone, 8.8 g (0.2 mol) of ethylene oxide was added to obtain 160 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 190, and exhibited a pale yellow color. As a result of ¹³ C-NMR analysis, 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.

Synthesis example 4

In a pressure-resistant reactor equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet, 10.3 g (0.1 mol) of diethylenetriamine, 28.4 g (0.2 mol) of diisobutyl ketone and 1 mol of toluene After charging the reaction vessel with nitrogen and replacing the inside of the reaction vessel with nitrogen, the reaction vessel was heated at 120 ° C. for 5 hours to cause dehydration and ketimine reaction. After the ketimination reaction, 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. As a result of ¹³ C-NMR analysis, 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.

Synthesis example 5

In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet, 6.1 mol (0.1 mol) of monoethanolamine, 14.2 g (0.1 mol) of diisobutyl ketone and 100 ml of toluene were placed. After charging and replacing the inside of the reaction vessel with nitrogen, the reaction vessel was heated at 120 ° C. for 5 hours to cause dehydration and ketiminization reaction. After the ketimination reaction, cool to room temperature, add 5.6 g of potassium hydroxide as an addition catalyst, replace with nitrogen gas, heat to 120 ° C, and heat 1,2-butylene oxide 180. After adding 3 g (2.5 mol) and reacting for 5 hours, further adding 24.0 g (0.1 mol) of 1,2-epoxyhexadecane and reacting for 2 hours, the reaction product solution was acidified. And the mixture was filtered to remove the added catalyst. Further, 5 g of water was added, and a hydrolysis reaction was performed at 90 ° C for 3 hours. After removing excess water, toluene and ketone, ethylene By adding 4.4 g (0.1 mol) of the oxide, 190 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 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.

Synthesis Example 6

4.45 g (0.06 mol) of tert-butanol and 3.37 g (0.06 mol) of hydrating water were placed in a 1-liter autoclave. After replacing the inside with nitrogen gas, it is heated to 90 ° C. Then, 100 ml of toluene, 67.1 g (0.36 mol) of 2-ethylhexylglycidyl ether and 62.7 g (1.08 mol) of propylene oxide were added thereto. In addition, the reaction was carried out at a reaction temperature of 120 ° C. for 5 hours. After completion of the reaction, the reaction product solution was neutralized with hydrochloric acid, and then extracted with toluene and the solvent toluene was distilled off to obtain 120 g of a polyoxyalkylene compound.

Next, 8.0 g (0.081) of liquid phosgene was added to a mixed solution of 89.4 g (0.04 mol equivalent: calculated from the weight average molecular weight) of this polyoxyalkylene compound and 100 ml of toluene. ) Was added at 0 ° C, and the reaction was carried out at room temperature for 12 hours while cooling the reflux tube with dry ice. After completion of the reaction, excess phosgene was removed, and toluene as a solvent was distilled off to obtain 88 g of a chlorine-containing compound.

Then, after cooling a mixed solution of 100 ml of toluene and 24.0 g (0.4 mol) of ethylenediamine to 5 ° C, 85.0 g of the above chlorine-containing compound (equivalent to 0.037 mol) : Calculated from the weight average molecular weight), and the mixture was reacted for 3 hours while maintaining the system at 5 ° C, and then reacted at room temperature for 2 hours. After the reaction, The corresponding ethylenediamine, the generated hydrochloride, and the solvent, toluene, were removed and purified to obtain 82 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2300, and had a dark orange color. As a result of ¹³ C-NMR analysis, 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.

Synthesis Example 7

4.45 g (0.06 mol) of tert-butanol and 3.37 g (0.06 mol) of hydrating water were placed in a 1-liter autoclave, After replacing the inside of the system with nitrogen gas, heat to 90 ° C. Thereafter, 100 ml of toluene, 64.9 g (0.90 mol) of 1,2-butylene oxide and 52.2 g (0.990 mol) of propylene oxide were added thereto, and the reaction temperature was 12.5 g. The reaction was performed at 0 ° C for 5 hours. After completion of the reaction, the reaction product solution was neutralized with hydrochloric acid, and then extracted with toluene and the solvent toluene was distilled off to obtain 108 g of a polyoxyalkylene compound.

Next, 8.0 g (0.081 mol) of liquid phosgene was added to a mixed solution of 81.0 g (0.04 mol equivalent: calculated from the weight average molecular weight) of this polyoxyalkylene compound and 10 Oml of toluene. The reaction mixture was added at 0 ° C. and reacted at room temperature for 12 hours while cooling the reflux tube with dry ice. After the completion of the reaction, excess phosgene was removed, and toluene as a solvent was distilled off to obtain a chlorine-containing compound (76 g).

Then, a mixed solution of 100 ml of toluene, 100 ml of pyridine and 59.6 g (0.4 mol) of triethanolamine was added. (After cooling to 73.1 g of the compound (equivalent to 0.035 mol: calculated from the weight average molecular weight) was dropped, reacted for 3 hours while maintaining the system at 5 ° C, and then reacted for 2 hours at room temperature. After the completion of the reaction, unreacted triethanolamine, generated hydrochloride, and toluene as a solvent were removed, and purification was performed to obtain 68 g of a desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2200, and had a dark orange color. As a result of ¹³ C-NMR analysis, 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.

Synthesis Example 8

3.37 g (0.06 mol) of potassium hydroxide is placed in a 1-liter autoclave, and the system is purged with nitrogen gas and heated to 90 ° C. Thereafter, 100 ml of toluene and 129.8 g (1.80 mol) of 1,2-butylene oxide were added thereto, and the mixture was reacted at a reaction temperature of 120 ° C. for 5 hours. After the completion of the reaction, the reaction product solution was neutralized with hydrochloric acid, and then extracted with toluene and distilled off the solvent, toluene, to obtain 115 g of a polyoxyalkylene compound.

Next, 8.0 g (0.01 mol) of liquid phosgene was added to a mixed solution of 87.3 g (0.04 mol equivalent: calculated from the weight average molecular weight) of this polyoxyalkylene compound and 100 ml of toluene at 0 ° C. The reaction was carried out at room temperature for 12 hours while cooling the reflux tube with dry ice. After completion of the reaction, excess phosgene was removed, and toluene as a solvent was distilled off to obtain 80 g of a chlorine-containing compound.

Then 100 ml of toluene, 100 ml of pyridine and 34.8 of morpholine g (0.4 mol) of the mixed solution was cooled to 5 C, and 78.5 g of the above chlorine-containing compound (equivalent to 0.035 mol: calculated from the weight-average molecular weight) was added dropwise. The reaction was carried out for 3 hours while maintaining the temperature, and then the reaction was carried out at room temperature for 2 hours. After completion of the reaction, unreacted morpholine, generated hydrochloride and toluene as a solvent were removed, and purification was carried out to obtain 73 g of a desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2300, and had a dark orange color. As a result of ¹³ C-NMR analysis, this nitrogen-containing compound was a polymer having an average structure represented by the formula (38a). Hereinafter this is referred to as Compound 8.

In addition, the following three compounds were prepared as nitrogen-containing compounds included in the general formula (lb).

Compound 9 (number average molecular weight 1050) CH “NH,

Compound 10 (number average molecular weight 1 050)

Compound 1 1 (number average molecular weight 1 050)

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.

Base gasoline properties

Reid vapor pressure: 0.6 5kgf / cm2

Specific gravity: 0.7 2 7

Boiling range: 30 to 190 ° C

Octane number: 98.1 Using this base gasoline and the above-mentioned compounds 1 to 11, gasoline compositions having the compounding amounts shown in Table 1 were prepared. The following engine evaluation tests were performed on each of these gasoline compositions and base gasoline containing no compound 1 to 11 at all.

[Engine evaluation test]

Use a passenger car equipped with a 1.8-liter direct-injection gasoline engine with cylinder displacement, repeat 10.15 modes for 400 hours, and then exhaust according to 10.15 modes Was collected, and the emission of THC (Total Hydrocarbon) was measured. Furthermore, the vehicle was driven at a constant speed of 40 km / h, and the amount of smoke was measured by sampling five times the amount of smoke every night with a Bosch type smoke meter. After that, the engine was disassembled and the amount of deposit in the combustion chamber was measured.

Table 1 shows the results.

table 1

As is clear from the results of the engine evaluation test in Table 1, 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.

It is possible to suppress an increase in the amount of THC and the amount of smoke.

Claims

The scope of the claims

1. In-cylinder direct injection gasoline engine consisting of at least one nitrogen-containing compound selected from the group consisting of a compound (1A) represented by the following general formula (la) and a polybutenylamine compound: For gasoline additives.

Compound (1A)

(In the general formula (la), R ¹ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ each independently represent hydrogen and 1 to 16 carbon atoms. Or a group represented by the following general formula (2a), wherein a is 1

Ten

R represents hydrogen or a hydrocarbon group having 130 carbon atoms, and f represents an integer of 0 to 50. )

Α group

A 1 one 0— C 0—

A 2-C 0-A 3-O-CO- ^{1 1-} R ¹¹ represents an alkylene group having 1 to 6 carbon atoms)

A 4 -0-CO-0- R 12 - (R 12 represents an alkylene group having 1 to 6 carbon atoms)

A 5 -CO-0- ¹³ -

(R ¹³ represents an alkylene group having 1 to 6 carbon atoms)

Group B

B 1 hydrogen

B 2 Hydrocarbon group having 1 to 30 carbon atoms

B 3 Alkinol group represented by the following general formula (3a)

^{- R 14 - 0 H (3} a)

(R ¹⁴ represents an alkylene group having 1 to 6 carbon atoms.)

B 4 Nitrogen-containing group represented by the following general formula (4a)

1 6

(R "represents an alkylene group having 2 to 6 carbon atoms, R ^1D represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a group represented by the above general formula (3a), and R ¹⁷ represents hydrogen, carbon Represents a hydrocarbon group of numbers 1 to 30 or a group represented by the above general formula (3a), and g represents an integer of 1 to 5.)

B 5 Group represented by the following general formula (5a)

And R ²² independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, Y represents a methylene group, a carbon group having 1 to 10 carbon atoms. A methylene group, an imino group, a hydrocarbon group having 1 to 10 carbon atoms, an imino group substituted by a hydroxyl group, or oxygen, wherein h is e = 1 In the case of, it is 1 and in the case of e = 2, it is 0 or 1 (however, in the case of h = 0, N (nitrogen) in the general formula (5a) becomes N (nitrogen) in the general formula (la) Nitrogen))

2. The gasoline additive according to claim 1, wherein the compound (1A) is represented by the following general formula (la).

(In the general formula (la), R ¹ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group or an alkyl aryl group having 6 to 18 carbon atoms,

R ² , R ³ , R ⁴ and R ⁵ represent hydrogen, an alkyl group having 1 to 8 carbon atoms or a group represented by the following general formula (2a), and a is an integer of 1 to 200;

R ⁶ represents an alkylene group having 1 to 6 carbon atoms, b represents 0 or 1, Z represents a group selected from the following group A, c represents 0 or 1, X represents the following group B And d represents an integer of 1-2, e is an integer of 1-2, and d + e = 3. )

In the general formula (2a), R and R independently represent hydrogen, an alkyl group having 16 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms,

R represents an alkylene group having 2 to 6 carbon atoms or an ethylene group substituted with an alkoxyalkyl group having 2 to 8 carbon atoms, R ^1Q represents an alkyl group having ¹²⁴ carbon atoms, and f represents an integer of 0 to 30 . ) Group A

A 1 1 1 C 1

A 2 C-1

A 3 -O-CO-R ¹¹ -A 4-0-CO-0-R ¹² -A 5-CO-0-R ^13-

(R ¹ R ¹² and R ¹³ each represent an alkylene group having 1 to 4 carbon atoms)

Group B

B 1: hydrogen

B 2: an alkyl group having 1 to 12 carbon atoms or an aryl group or an arylalkyl group having 6 to 12 carbon atoms

B 3: alcohol group represented by the following general formula (3a)

_R ¹⁴ —〇H (3a) (R ¹⁴ represents an alkylene group having 1 to 4 carbon atoms.)

1 6

(R ¹⁵ represents an alkylene group having 2 to 4 carbon atoms, and represents hydrogen, an alkyl group having 1 to 3 carbon atoms or a group represented by the above general formula (3a), and R ¹⁷ represents hydrogen. An alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an arylalkyl hydrocarbon group, or a group represented by the above general formula (3a). , G indicates an integer of 1 to 4.)

Β 5: Group represented by the following general formula (5a)

(R ¹⁸ represents an alkylene group having 2 to 4 carbon atoms, R ¹⁹ , R ² °, R ²¹ and R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and Y represents a methylene group. A methylene group or an imino group substituted with an alkyl group or a hydroxyl group having 1 to 6 carbon atoms, an imino group or an oxygen group substituted with an alkyl group or a hydroxyl group having 1 to 6 carbon atoms. When e = 1, h = 1; when e = 2, h = 0 or h = 1 (however, when h2 0, N (nitrogen) in the general formula (5a)) Corresponds to N (nitrogen) in the general formula (la).)

3. The gasoline additive according to claim 1, wherein the compound (1A) is represented by the following general formula (la).

(In the general formula (la), R ¹ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkylaryl group having 1 to 15 carbon atoms, and R ² , RR ⁴ and R ⁵ represent hydrogen. Represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following general formula (2a), a is an integer of 2 to 100, and R ⁶ represents an alkylene group having 3 to 6 carbon atoms. , B is 0 or 1, Z is a group selected from the following group A, c is 0 or 1, X is a group selected from the following group B, d is 1, e Is an integer of 2.

(In the general formula (2a), R ⁷ and R ^{8 each} independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms, R ⁹ represents an alkylene group having 2 to 4 carbon atoms, Ten

R ^ ^u represents an alkyl group having 1 12 carbon atoms, and f represents an integer of 0 to 20. )

Group A

A 1 1 1 C 1

A 2 C-1

A 4 one ^{0 - CO - 0 - R 12} - (R 1 2 represents an alkylene group having 1-4 carbon atoms)

Group B

B 1 hydrogen

B 3 Alkinol group represented by the following general formula (3a)

1

— R /, one 0H (3a)

14

(R represents an alkylene group having 1 to 3 carbon atoms.)

1 6

(R ¹⁵ represents an alkylene group having 2 to 3 carbon atoms, R represents hydrogen, a methyl group, an ethyl group or a group represented by the above general formula (3a), and R ¹⁷ represents hydrogen, 1 carbon atoms. Represents an alkyl group of 6 to 6, a phenyl group, an arylalkyl group having 7 to 9 carbon atoms or a group represented by the above general formula (3a), and g represents an integer of 1 to 3.)

B 5 Group represented by the following general formula (5a)

20 2 1

RR and R ² are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms Or a hydroxyl group, Y represents an imino group, an imino group substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or oxygen, and h

HHCII HCHII is 0 or 1 (however, when h = 0, N CHCIIC CCII (nitrogen) in the general formula (5a) corresponds to N (nitrogen) in the general formula (la).

You. ) One 33

4. The gasoline additive according to claim 1, wherein the polybutenylamine-based compound is a compound (1B) represented by the following general formula (lb).

Compound _ (1 B)

(lb)

In (the general formula (lb), R ^{2 5} is n- heptyl group, a sec- butyl group or tert- heptyl ^{^{group, R 26, R 27, R}} 28 and R ^{2 9} are water atom, a methyl group Or an ethyl group, and the total number of carbon atoms of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ is 2, and Q represents a group represented by any of the following formulas (2b) to (7b) ,: ³ ° 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:

And a group represented by (8b), and m represents an integer of 1 to 100. )

HC ₂ H ₅ C ₂ H ₅ H

-C— C— (4b) C— C- (5b)

I I I I

H H H H

(In the general formula (8 b), R ³² is indicates alkylene group having 1 to carbon atoms 4, R ^{3 3} represents hydrogen or an alkyl group having a carbon number of 1 to 4, R ³⁴ were hydrogen or carbon A hydrocarbon group of the numbers 1 to 10, and n represents an integer of 1 to 5.)

5. The gasoline additive according to claim 4, wherein the compound (1B) is represented by the following general formula (lb).

In (the general formula (lb),: R ²⁵ represents a tert- heptyl group, an R ^{2 6} and R ^{2 8} represents a hydrogen atom, or R ^{2 7} and R ^{2 9} represents a methyl group, there have the R ²⁶ and R ²⁸ represent a methyl group, R ²⁷ and R ²⁹ represent a hydrogen atom, Q represents a group represented by the following formula (2b) or (6b), R ³ and R ³¹ represent Separately, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group or an alkylcycloalkyl group having 5 to 10 carbon atoms, and a 6 to 10 carbon atoms An aryl or alkylaryl group, an arylalkyl group having 7 to 10 carbon atoms, an alkanol group having 1 to 8 carbon atoms, or a group represented by the following general formula (8b). And m represent an integer of 5 to 50.)

H CH ₃ H CH ^ H

I I I I

-C— C (2b) — C—C—— C— (6b) H CH ₃ H CH ₃ H

(In the general formula (8 b), the R ³² may indicates alkylene group having 1 to 3 carbon atoms, R ^{3 3} represents hydrogen or an alkyl group carbon atoms. 1 to 3, R ³⁴ were hydrogen or carbon Represents an alkyl group of numbers 1 to 3, and n represents an integer of 1 to 3.)

6. The gasoline additive according to claim 4, wherein the compound (1B) is represented by the following general formula 1b).

In (the general formula (lb), R ²⁵ represents a tert- butyl group, an R ^{2 6} and R ^{2 8} represents a hydrogen atom, or R ^{2 7} and R ^{2 9} represents a methyl group, there have the R ^{2 6} and R ²⁸ represent a methyl group; R ²⁷ and R ²⁹ represent a hydrogen atom; Q represents a group represented by the following formula (6b); R ³ ° and R ³¹ each independently represent water; Elemental atom, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, cycloalkyl group or alkylcycloalkyl group having 5 to 10 carbon atoms, aryl having 6 to 10 carbon atoms An alkyl group or an alkylaryl group, an arylalkyl group having 1 to 10 carbon atoms, an alkanol group having 1 to 4 carbon atoms, or a group represented by the following general formula (8b); Shows an integer of 10 to 40.)

(In the general formula (8 b), R ³² is indicates alkylene group having 1 to 3 carbon atoms, R ³³ and R ³⁴ represents hydrogen, n represents represents 1 integer.)

7. The gasoline additive according to claim 4, wherein the compound (IB) has a number average molecular weight of 200 to 60 ° 0.

8. The gasoline additive according to claim 4, wherein the compound (1B) has a number average molecular weight of 400 or more and 3000 or less.

9. The gasoline additive according to claim 4, wherein the compound (1B) has a number average molecular weight of 700 or more and 2400 or less.

10. A cylinder obtained by mixing at least one nitrogen-containing compound selected from the group consisting of the compound (1A) represented by the following general formula (la) and a polyptenylamine compound into a base gasoline. Gasoline composition for internal direct injection gasoline engine.

Compound (1A)

(In the general formula (1a), R represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ each independently represent hydrogen and 1 to 16 carbon atoms. Or a group represented by the following general formula (2a), wherein a is 1

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 1 X represents a group selected from the following group B, d is an integer of 1 to 3, e is an integer of 0 to 2, and d + e = 3. )

(In the general formula (2a), R ⁷ and R ⁸ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms. R ⁹ represents an alkylene group having 2 to 6 carbon atoms, or an alkylene group having a total carbon number of 4 to 10 having an alkoxyalkyl group as a substituent,

Ten

Group A

A 1 one 0— C 0—

A 2 C-1

A 3-0- C OR ^{1 1-}

(R ¹¹ represents an alkylene group having 1 to 6 carbon atoms)

A 4 one ^{0 - CO - 0 - R 1} 2 - (R 1 2 represents an alkylene group having 1 to 6 carbon atoms)

A 5 — CO-0-R ^{1 3-}

(R ¹³ represents an alkylene group having 1 to 6 carbon atoms)

Group B

B 1 hydrogen

B 2 Hydrocarbon group having 1 to 30 carbon atoms

B 3 Alkanol group represented by the following general formula (3a)

1

-R-0 H (3 a)

14

(R represents an alkylene group having 1 to 6 carbon atoms.)

B 4 Nitrogen-containing group represented by the following general formula (4a)

(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)

(5a)

19 20 21

(R ¹⁸ represents an alkylene group having ²⁶ carbon atoms, and R ", R '\ R

twenty two

And R "each independently represent hydrogen, a hydrocarbon group having 1 to 10 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 hydroxyl group, H represents an amino group, an amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, or oxygen, and h is 1 when e = 1, and 0 or 0 when e = 2. 1 (However, when h = 0, N (nitrogen) in the general formula (5a) corresponds to N (nitrogen) in the general formula (la).)

11. The gasoline composition according to claim 10, wherein the compound (1A) is added in an amount ranging from 0.001 to: 0% by mass based on the total composition.

12. The gasoline composition according to claim 10, wherein the polyptenylamine compound is added in an amount in the range of 0.001 to 10% by mass based on the total composition.