WO1999013027A1

WO1999013027A1 - Fuel oil additive and fuel oil composition containing the same

Info

Publication number: WO1999013027A1
Application number: PCT/JP1998/004100
Authority: WO
Inventors: Katsuhiko Haji; Masaki Nagao; Tohru Yoshii; Tatsuo Omata
Original assignee: Nippon Mitsubishi Oil Corporation
Priority date: 1997-09-11
Filing date: 1998-09-11
Publication date: 1999-03-18
Also published as: AU9002498A

Abstract

A fuel oil additive comprising a nitrogen-containing compound of general formula (1), having an excellent effect of cleaning the intake system and combustion chamber of a gasoline engine and free from lowering of the performance of the engine and sludging even when the engine is cold.

Description

Specification

Fuel oil additive and fuel oil composition containing the additive

〔Technical field〕

The present invention relates to a fuel oil additive having excellent solubility in fuel oil, particularly excellent cleanliness in an intake system and a combustion chamber of a gasoline engine, and a fuel oil composition containing the additive. It is.

(Prior art)

Deposits such as sludge and deposits in the fuel system and combustion chamber of an internal combustion engine cause inconveniences such as reduced engine function and increased concentrations of carbon monoxide and unburned hydrocarbons in exhaust gas. Happens. For this reason, fuel oils such as gasoline are used in gasoline detergents such as polyetheramines and polyamines, mainly for the purpose of removing deposits such as carburetors, electronically controlled injection devices, and intake valves, and preventing adhesion. Is often added.

Among such fuel additives, the polyester gasoline detergents disclosed in U.S. Pat. Nos. 4,247,301 and 4,160,648 are the It has demonstrated excellent performance in removing deposits and preventing adhesion of intake valves.

[Problem of the Invention]

In recent years, there has been much interest in improving the fuel efficiency of cars and eliminating the negative effects on human bodies and the environment caused by vehicle exhaust gas. Against this background, compared to conventional gasoline detergents such as polyetheramines and polyamines as representatives, the gasoline engine is more effective in cleaning the intake system and combustion chamber of gasoline engines, There is a long-awaited need to develop a fuel oil additive that does not reduce its effect even under severe conditions such as when the engine is cold.

The present invention has been made in view of such circumstances, and its object is to provide a novel gas containing a special nitrogen-containing compound which has performance exceeding that of conventional gasoline detergents and does not itself form sludge. An object of the present invention is to provide a novel fuel oil additive and a fuel oil composition containing the fuel oil additive.

[Detailed Description of the Invention]

The fuel oil additive according to the present invention is a nitrogen-containing compound represented by the following general formula (1). Become. Further, the fuel oil composition according to the present invention can be used for gasoline for an internal combustion engine,

It contains the nitrogen-containing compound represented by (1).

[In the general formula (1), H ¹ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ represent hydrogen, 1 to 10 carbon atoms, respectively. And a group represented by the following general formula (2) (provided that R ² , R

At least one of R ⁴ and R ⁵ is a group represented by the general formula (2)), R ⁶ represents an alkylene group having 1 to 6 carbon atoms, and Z represents the following general formula (3) to ( 5) represents a group represented by one of the following, X represents a group selected from the following group A, a is an integer of 1 to 100, b is 0 to: an integer of L00, and a + b = 1 to 200, c is 0 or 1, d is an integer of 1 to 3, e is an integer of 0 to 2, and d + e = 3 ₍ where Z is In the case of formula (4) or (5), when e = l, X is not A3, and when e = 2, one of X is A3 and the other is A2 or A3. There is no.]

[In the general formula (2), 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 having 2 to 10 carbon atoms. 6 represents an alkylene group, or represents an alkylene group having 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, R ^lfl represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and f represents Indicates an integer from 0 to 50. ] 11

■ O-C-R (3)

II

o

12

■ O-C-O-R (4)

II

o

^{^{- OR 13 - COR 14 - (}} 5)

II

o

[In the general formula (3) to (5), shows the ^{^{R! 1, R 12, R}} 13 and R ^M It it individually an alkylene group having 1 to 6 carbon atoms. ]

Group A

A 1: hydrogen

A2: Hydrocarbon group having 1 to 30 carbon atoms

A ^ _: Alkinol group represented by the following general formula (6)

― R ¹ — 0H (6)

[In the general formula (6), R ¹⁵ represents an alkylene group having 1 to 6 carbon atoms. ]

A: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), ¹⁶ represents an alkylene group having 2 to 6 carbon atoms, R ¹⁷ represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a group represented by the general formula (6); R ¹⁸ represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or a group represented by the above general formula (6), and g represents an integer of 1 to 5. ] A group represented by the following general formula (8)

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 6 carbon atoms, and R ^2fl , R ²¹ , R ²² and each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, Y represents a methylene group, a hydrocarbon group having 1 to 10 carbon atoms, a methylene group substituted with a hydroxyl group, an imino group, an imino group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, or oxygen; h is 1 when e = 1, 0 or 1 when e = 2 (however, when h = 0, N (nitrogen) in the general formula (8) is represented by the general formula (1) The fuel oil additive of the present invention comprising a nitrogen-containing compound represented by the general formula (1) is a conventional gasoline based on a polyetheramine-based / polyamine-based gasoline. Compared to detergents, they have a better ability to keep the intake system and combustion chamber of gasoline engines clean. Exhibit excellent cleaning effect in severe conditions such as when cold the engine, is not a tooth or even to itself sludging. The above formula (1), R ¹ is hydrogen or C1-30 Wherein R ¹ is hydrogen, or a linear or branched alkyl group having 1 to 24 carbon atoms, or a linear or branched alkenyl group having 2 to 24 carbon atoms. A cycloalkyl group or an alkylcycloalkyl group having 5 to 13 carbon atoms, an aryl group or an alkylaryl group having 6 to 18 carbon atoms, or an arylalkyl group having 1 to 19 carbon atoms. .

Preferred alkyl groups for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, linear or branched pentyl, Chain or branched hexyl, straight or branched heptyl, straight or branched octyl, straight or branched nonyl, straight or branched decyl, straight or branched decyl , Straight or branched dodecyl, straight or branched tridecyl, straight or branched tetradecyl, straight or branched pendecyl, straight or branched hexadecyl, straight or branched hep Evening Decil Group, straight or branched octadecyl group, straight or branched nonadecyl group, straight or branched icosyl group, straight or branched helicosyl group, straight or branched docosyl group, straight or branched tricosyl group , Including straight-chain or branched tetracosyl groups

Preferred alkenyl groups for R ¹ include vinyl, propenyl, isopropenyl, straight-chain or branched butenyl, puenyl, straight-chain or branched pentenyl, straight-chain or branched pentenyl. Branched hexenyl, straight or branched heptenyl, straight or branched octenyl, straight or branched nonenyl, straight or branched decenyl, straight or branched undecenyl, straight or branched Dodecenyl group, straight or branched tridecenyl group, straight or branched tetradecenyl group, straight or branched pentadecenyl group, straight or branched hexadecenyl group, straight or branched hepdecenyl group Linear or branched ocenyl decenyl group such as oleyl group, linear or branched nonadecenyl group, linear or branched icosenyl group, linear or branched helicosenyl group, linear or branched Branched docosenyl, straight or branched tricosenyl group, straight or branched Tetorako Seniru group and the like.

Preferred cycloalkyl groups as R ¹ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, and similarly preferred alkylcycloalkyl groups include a methylcyclopentyl group, a 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), getylcyclopentyl group (including all substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers), linear or A branched propylmethylcyclopentyl group (all substituted isomers Linear or branched propylethylcyclopentyl group (including all substituted isomers), di-linear or branched propylcyclopentyl group (including all substituted isomers), linear or branched propyl Tylmethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (all ), 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) Isomers), ethyldimethylcyclohexyl groups (including all substituted isomers), linear or branched propylmethylcyclohexyl groups (including all substituted isomers), linear or branched Branched propylethycyclohexyl (including all substituted isomers), di-straight or branched propylcyclohexyl (including all substituted isomers), straight or branched propylethylmethylcyclohexyl (all ), Methylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers) (Including all isomers), ethylcycloheptyl group (including all substituted isomers), linear or branched propylcycloheptyl group (including all substituted isomers), ethylmethylcycloheptyl group (all Trimethylcycloheptyl group (including all substituted isomers), getylcycloheptyl group (including all substituted isomers), ethyldimethylcycloheptyl group (including all substituted isomers) ), Linear or branched propylmethylcycloheptyl group (including all substituted isomers), linear or branched propylethylcycloheptyl group (including all substituted isomers), Chain or branched propylcycloheptyl group (including all substituted isomers), linear or branched propylethylmethylcycloheptyl group (including And all substitution isomers).

Preferred aryl groups for R ¹ include a phenyl group and a naphthyl group, and similarly preferred alkylaryl groups include a tolyl group (including all substituted isomers) and a xylyl group (including all substituted isomers). ), Ethenyl phenyl group (including all substituted isomers), linear or branched propyl phenyl group (including all substituted isomers), ethyl methyl phenyl 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) Includes), getyl phenyl group (including all substituted isomers), ethyl dimethyl phenyl group (including all substituted isomers), tetramethyl phenyl Benzyl group (including all substituted isomers), linear or branched pentyl phenyl group (all Linear or branched hexylphenyl group (including all substituted isomers), linear or branched heptylphenyl group (including all substituted isomers), linear Or a branched octylphenyl group (including all substituted isomers), a linear or branched nonylphenyl group (including all substituted isomers), a linear or branched decylphenyl group (including all substituted isomers), A straight-chain or branched undecylphenyl group (including all substituted isomers), a straight-chain or branched dodecylphenyl group (including all substituted isomers) and the like are also included. Benzyl group, methylbenzyl group (including all substituted isomers), dimethylbenzyl group (including all substituted isomers), phenethyl group, methylphenene This includes tyl groups (including all substituted isomers), dimethylphenethyl groups (including all substituted isomers), and the like.

Among them, 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 aryl group. The case is even more preferable. In particular, when it is a linear or branched alkyl group having 1 to 6 carbon atoms, when it is a phenyl group, or when it has carbon atoms? Most preferably, there are up to 15 linear or branched alkylaryl groups. R ² , R ³ R ⁴ and R ⁵ in the general formula (1) each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or a group represented by the general formula (2) (however, At least one of R ² , RR ⁴ and R ⁵ is a group represented by the general formula (2)). 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, cycloalkyl group or alkylcycloalkyl group having 5 to 10 carbon atoms, aryl or alkylaryl group having 6 to 10 carbon atoms, carbon number? Up to 10 arylalkyl groups.

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-chain or branched heptyl, straight-chain or branched octyl, straight-chain or branched nonyl, straight-chain Or a branched decyl group, and similarly preferred alkenyl groups include a vinyl group, a propenyl group, an isopropyl group, a straight-chain or branched butenyl group, a butenyl group, a straight-chain or branched Examples include a branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched octenyl group, a linear or branched nonenyl group, a linear or branched decenyl group, and the like. ―

Similarly, preferred cycloalkyl groups include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the alkylcycloalkyl group include a methylcyclopentyl group (including all substituted isomers) and dimethyl Cyclopentyl group (including 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), getylcyclopentyl group (including all substituted isomers), ethylmethylcyclopentyl group (including all substituted isomers) Body, including linear or branched propylmethylcyclopentene Le 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), ethyl cyclohexyl group (including all substituted isomers), linear or branched propylcyclyl hexyl group (including all substituted isomers), and ethyl cyclocyclohexyl group

(Including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), getylcyclohexyl group (including all substituted isomers), ethyldimethylcyclohexyl group (all , A straight-chain or branched pyrmethylcyclohexyl group (including all substituted isomers), a methylcycloheptyl group (including all substituted isomers), a 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) and 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), a xylyl group (including all substituted isomers), an ethylphenyl group (including all substituted isomers), linear or branched. Propylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers), straight chain or branched Butylphenyl group (including all substituted isomers), linear or branched propylmethylphenyl group (including all substituted isomers), getylphenyl group (including all substituted isomers), ethyldimethyl Examples include a phenyl group (including all substituted isomers) and a tetramethylphenyl group (including all substituted isomers). 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). Dimethylphenethyl group (including all substituted isomers) and the like.

Among the above-mentioned hydrocarbon groups having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is particularly preferable. Groups are most preferred. Any one of R ² , R ³ , R ⁴ and R ^{5 in} the general formula (1) is a group represented by the general formula (2), and in the general formula (2), R ⁷ and R ⁸ individually represents hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 10 carbon atoms. 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 ² to R ⁵ , and 2 to 10 carbon atoms. Linear or branched alkenyl group, cycloalkyl group or alkylcycloalkyl group having 5 to 10 carbon atoms, aryl or alkylaryl group having 6 to 10 carbon atoms and 7 to 10 carbon atoms And all arylalkyl groups.

The alkoxyalkyl group having 2 to 10 carbon atoms includes, for example, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group. , Sec—butoxymethyl Group, tert-butoxymethyl group, pentoxymethyl group (including all isomers), hexoxymethyl group (including all isomers), heptoxymethyl group (including all isomers), octoxymethyl Group (including all isomers), nonyloxymethyl group (including all isomers), methoxethyl group (including all isomers), ethoxyxyl group (including all isomers), and propoxicetyl group (including all isomers) All but isomers), butoxystyl group (including all isomers), pentoxyl group (including all isomers), hexoxyl group (including all isomers), heptoxethyl group (all Octoxityl group (including all isomers), methoxypropyl group (including all isomers) ), Ethoxypropyl group (including all isomers), propoxypropyl group (including all isomers), butoxypropyl group (including all isomers), pentoxypropyl mouth 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 (including all isomers), pentoxybutyl group (including all isomers), hexoxybutyl group (including all isomers) ), Methoxypentyl group (including all isomers), ethoxypentyl group (including all isomers), propoxy Methyl group (including all isomers), butoxypentyl group (including all isomers), pentoxypentyl group (including all isomers), methoxyhexyl group (including all isomers) , 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), methoxyoctyl group (including all isomers), ethoxyoctyl group (including all isomers) ), Methoxynonyl group (including all isomers) and the like.

R ⁷ and R ⁸ in the general formula (2) are preferably or individually hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms, particularly hydrogen or carbon atom. Even more preferably, it is an alkyl group of 1-3. R ⁹ in the general formula (2) represents an alkylene group having 2 to 6 carbon atoms or an alkylene group having 4 to 10 total carbon atoms having an alkoxyalkyl group as a substituent. Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group), a trimethylene group, and a propylene group (1-ethylethylene group, 2- 1,2-diethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene group Butylethylene group, 2-butylethylene group), ethyl-1-methylethylene group, 1-ethyl-12-methylethylene group, 1,1,2-trimethylethylene group, 1,2,2-trimethylethylene Group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 3-ethylethylmethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group Len, 1,3-dimethyltrimethylene, 2,3-dimethyltrimethylene, 3,3-dimethyltrimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 3-methyltetramethylene, 4-methyl Tetramethylene group, pentamethylene group, hexylene group (1-butylethylene group, 2-butylethylene group), 1-methyl-1-propylethylene group,

1-methyl-1-propylethylene group, 2-methyl-1-propylethylene group, 1,1-getylethylene group, 1,2-getylethylene group, 2,2-getylethylene group, 1-ethylethyl group 1,2-dimethylethylene group, 1-ethyl-1,2,2-dimethylethylene group, 2-ethyl-1,1,1-dimethylethylene group, 2-ethyl-1,1,2-dimethylethylene group, 1,1,2, 2-tetramethylethylene group, 1-provided rimethylene group, 2-provyl trimethylene group, 3-provided rimethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-12-methyltrimethylene group, 1— Ethyl-3—methyltrimethylene group, 2-ethyl-1-methylene trimethylene group, 2-ethyl-2-methyltrimethylene group, 2-ethyl-3-methyl-trimethylene group, 3-ethyl-1-methylene group Belt Rimechiren group, 3-Echiru one 2 - Mechiruto Rimechiren group, 3 - Echiru one 3- Mechiruto Rimechiren group, 1, 1, 2 - DOO Rimechiruto Rimechiren group, 1, 1, 3-preparative Rimechiruto Rimechiren 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-ethylethyltramethylene group, 3-ethylethyltramethylene Group, 4-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2,2 —Dimethyltetramethylene, 2,3-dimethyltetramethylene, 2,4-dimethyltetramethylene, 3,3-dimethyltetramethylene, 3,4-dimethyltetramethylene, 4,4-dimethyltetramethylene, 1-methylpentyne Methylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 4-methylpentamethylene group, 5-methyl Le pentamethylene group, etc. Kisamechiren group and the like to.

Examples of the alkylene group having a total number of carbon atoms of 4 to 10 containing an alkoxyalkyl group as R ⁹ as a substituent include, for example, 1- (methoxymethyl) ethylene group, 2- (methoxymethyl) ethylene group, (Methoxyl) Ethylene group, 2- (Methoxyl) Ethylene group, 1- (Ethoxymethyl) Ethylene group, 2- (Ethoxymethyl) Ethylene group, 1-Methoxymethyl1-2-Methylethylene group, 1,1-bis ( (Methoxymethyl) ethylene group, 2,2-bis (methoxymethyl) ethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxyethyl) ethylene group, 2,2-bis (Methoxyxetil) Ethylene group, 1,2-bis (methoxyl) Ethylene group, 1,1-bis (ethoxymethyl) ethylene group, 2,2-bis (E Toximethyl) ethylene group, 1,2-bis (ethoxymethyl) ethylene group, 1-methyl-12-methoxymethylethylene group, 1-methoxymethyl-2-methylethylene group, 1-ethyl-2-methoxymethylethylene group, 1-methoxymethyl-1-ethylethylene group, 1-methyl-2-ethoxymethylethylene group, 1-ethoxymethyl-1-methylethylene group, 1-ethyl-2-ethoxymethylethylene group, 1-ethoxymethylethylene group 2-Ethylethylene group, 1-Methyl-1-2-Methoxylethylene group, 1-Methoxyl-2-methylethylene group, 1-Methyl1-2-Methoxylethyl group, 1-Methoxyl-2-ethylethylene group And alkoxyalkyl group-substituted ethylene having 2 to 8 carbon atoms. Are preferred.

R ⁹ in the general formula (2) is particularly preferably an alkylene group having 2 to 4 carbon atoms, or an ethylene group substituted with an alkoxyalkyl group having 2 to 6 carbon atoms.

In the general formula (2), R ^lfl represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, but ^_R ^{1 ()} 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 alkylcycloalkyl group having 5 to 13 carbon atoms, carbon number 6 to 18 It is preferably any one of an aryl group or an alkylaryl group, and an arylalkyl group having 7 to 19 carbon atoms. Further, R ¹¹¹ 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 (2) may be any integer in the range of 0 to 50, but is preferably an integer of 0 to 30, and more preferably 0 to 20. Accordingly, in the group represented by the general formula (2), 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 group having 2 to 6 carbon atoms or an ethylene group substituted with an alkoxyalkyl 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 3 °. (Hereinafter, this group is referred to as “preferred substituent (2a)” for convenience), and R ⁷ and R ⁸ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms; It is more preferred that ⁹ is an alkylene group having 2 to 4 carbon atoms, R ¹¹¹ is an alkyl group having 1 to 12 carbon atoms, and that f is an integer of 0 to 20 (hereinafter, this group is referred to as For convenience, referred to as “more preferred substituent (2b)”) _c The nitrogen-containing compound of the present invention has the general formula (1) But R ^2, one even without less of R \ R ⁴ and R ⁵ but it is important that the group represented by the general formula (2) in one of R ^2, R \ R ⁴ and R ⁵ or Two are groups represented by the general formula (2), and the remaining three or two are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. preferable. Furthermore, one of R ² , RR ⁴ and R ⁵ is the above “preferred substituent (2a)” or “more preferred substituent (2b)”, and the other three are each independently hydrogen. Alternatively, an alkyl group having 1 to 3 carbon atoms is more preferable. R ⁶ in the general formula (1) represents an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group (1-methylethylene group, 2-methylethylene group). 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-methylethylene group, 1-ethyl1-2-methylethylene group, 1,1, 2-trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 3-ethylethylmethylene Group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1-methyl Tetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, pentamethylene group, hexylene group (one butylethylene group, 2-butylethylene group), one methyl _ 1-propylethylene group, 1-methyl-2-propylpyrethylene group, 2-methyl-2-propylethylene group, 1,1-gethyrethylene group, 1,2-getylethylene group, 2,2-getylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 2-ethyl-1,1-dimethylethylene group, 2-ethyl-1,2-diene Tylethylene group, 1,1,2,2-tetramethylethylene group, 1-propyl trimethylene group, 2-provyl trimethylene group, 3-propyl trimethylene group, 1-ethyl-1-methyltrimethylene group 1-ethyl-12-methyltrimethylene group, 1-ethyl3-methyltrimethylene group, 2-ethyl-methylene group 1, 2-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 2-ethyl-3-methyltrimethylene Group, 3-ethyl-1-methyltrimethylene group, 3-ethyl-12-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 group, 2,3,3-trimethyltrimethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 3-ethyltetramethylene group, 4-ethyltetramethylene group, 1,1-dimethyltetramethylene group Methylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 2,3-dimethyltetramethylene group 2,4-dimethyltetramethylene group, 3,3-dimethyltetramethylene group, 3,4-dimethyltetramethylene group, 4,4-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene Group, 3-methylpentamethylene group, 4-methylpentamethylene group, 5-methylpentamethylene group, hexamethylene group and the like. Among them, R ⁶ is preferably an alkylene group having 1 to 4 carbon atoms, specifically, methylene, ethylene, propylene (1-methylethylene, 2-methylethylene), trimethylene, and butylene. Groups (1-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetra A methylene group is preferred. Further, as R ⁶ , an alkylene group having 1 to 3 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group (a monomethylethylene group, a 2-methylethylene group) or a trimethylene group is most preferred. In the general formula (1) representing the nitrogen-containing compound of the present invention, a represents an integer of 1 to 100, preferably 2 to 50, b represents an integer of 0 to 100, preferably 0 to 50, and a + b is in the range of 1 to 200, preferably 2 to: L00.

That is, in the nitrogen-containing compound of the present invention, the group represented by the following general formula (9) has 1 to 100, preferably 2 to 100, structural units represented by the following general formula (10). It contains 50, more preferably 2 to 30, and 0 to 100, preferably 0 to 50, more preferably 0 to 30, structural units represented by the following general formula (11). And a total of 1 to 200, preferably 2 to 100, structural units represented by the general formula (10) and structural units represented by the general formula (11).

— O R (11)

[Formula (9) R ² in ^{~ (1 1), R 3} , R 4, R 5 and R ⁶ are defined in ^{^{^{R 2, R 3, R 4}}} , R 5 and R ⁶ in the general formula (1) And a and b are the same as the definitions of a and b in the general formula (1). ]

In the group represented by the general formula (9), the order and the number of bonds between the structural unit represented by the general formula (10) and the structural unit represented by the general formula (11) are arbitrary. The typical connection modes are as follows.

(1) Combination of one kind of structural unit represented by general formula (10) (when b = 0)

(2) Two or more different structural units included in the general formula (10) are randomly combined, alternately combined or block-connected (when b = 0).

③ Randomly, alternately or block-bonded one structural unit represented by the general formula (10) and one structural unit represented by the general formula (11) (b ≠ 0 )

も When two or more different structural units contained in general formula (10) and one type of structural unit represented by general formula (11) are random-bonded, alternate-bonded, or block-bonded (b ≠ 0 in the case of) 1A structure in which one structural unit represented by the general formula (10) and two or more different structural units included in the general formula (11) are random-bonded, alternate-bonded, or block-bonded (b ≠ 0 Case)

もの Randomly, alternately or 'lock_linked' two or more different structural units of general formula (10) and two or more different structural units of general formula (11) (In the case of b ≠ 0) When the nitrogen-containing compound according to the present invention is represented by the chemical formula, the structural unit represented by the general formula (10) is bonded to R ¹ in the general formula (1), and the general formula (11) )), The nitrogen-containing compound of the present invention is displayed in a form in which it is bonded to Z. This display is for convenience, and the structural unit of general formula (10) and the structural unit of general formula (11) are As described above, the bonding order of the structural units is not limited to the bonding order shown in the general formula (1). Z in the general formula (1) is represented by any of the following general formulas (3) to (5).

_0- _C -R ^n- ( ³ )

II

0

^{_0-C-0-R 12} - (4)

II

o

^{^{- OR 13 - COR 14 - (}} 5)

II

o In formulas (3) to (5), II ¹¹ , R ¹² , R ¹³ and R ^{14 each} independently represent an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include, 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-methylethylene group, 1-ethyl-2-methylethylene group,

1,1,2-trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethylethylmethylene group, 3-ethylethylmethylene group,

1,1-dimethyltrimethylene 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-propyl ethylene group, 1-methyl-1--2-ethylene group, 2-methyl-

2-propylethylene group, 1,1-getylethylene group, 1,2-ethylethylene group, 2,2-getylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl1-2, 2-dimethylethylene group, 2-ethyl-1,1,1-dimethylethylene group, 2-ethyl-1,1,2-dimethylethylene group, 1,1,2,2-tetramethylethylene group, 1-propytrimethylene group, 2-Provirtimethylene group, 3-Provirthimethylene group, 1-Ethyl-1-methyltrimethylene group, 1-Ethyl-1-methyltrimethylene group, 1-Ethyl-3-methyltrimethylene group, 2-Ethyl-1-methyltrimethylene group, 2 —Ethyl-1-2-methyltrimethylene group, 2-ethyl-3—methyltrimethylene group, 3-ethyl-1-methyltrimethylene group, 3-ethyl-12-methyltrimethylene Group, 3-ethyl-1-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 group, 2,3,3-trimethyltrimethylene group, 1-ethyltetramethylene group, 2- Ethyl-tetramethylene, 3-ethyltetramethylene, 4-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 1, 4-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, 2.4-dimethyltetramethylene group, 3,3-dimethyltetramethylene group Methylene group, 3,4-dimethyltetramethylene group, 4,4-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 4-methylpentamethylene group , 5-methylpentamethylene group, hexamethylene group and the like.

Among these, alkylene groups having a carbon number of 1 to 4 are preferred, and specific examples thereof include a methine group, an ethylene group,

3-pyrene 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, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 3-methyltrimethylene group, a tetramethylene group, and the like. Then, R ", R ^12, if an alkylene group of R ¹³ and R ¹⁴ forces separately carbon number 1 to 3 include a methylene group, an ethylene group, a propylene group (1 one methylethylene, 2 —Methylethylene group) or a trimethylene group, and in the general formula (1), c represents 0 or 1. When c is 0, the nitrogen-containing compound of the present invention is represented by the following general formula (1) When c is 1, it is represented by the following general formulas (13) to (15).

R 丄 0— R • N- X (12)

R ⁴

R "

R ¹における R ² , R ³ , R ⁴ , RR ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X in the general formulas (12) to (15) are the same as R ¹ in the general formula (1) ^{2 As} defined for R ² , R ³ , R ⁴ , RR ⁶ , R ", R ¹² , R ¹³ , R ¹⁴ and X, a, b, d and e also represent a, b in the general formula (1) In the general formula (1), d is an integer of 1 to 3, preferably 1 to 2, e is an integer of 0 to 2, preferably 1 to 2, And d + e is 3, most preferably d = 1 and e = 2.

When d is 2 in the nitrogen-containing compound represented by the general formula (1), the compound has two groups represented by the following general formula (16) in one molecule. The groups may have the same structure or different structures.

RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ and Z in the general formula ( ¹⁶ ) are I ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (1). And Z have the same definitions as above, and a, b and c have the same definitions as a, b and c in the general formula (1). In the general formula (1) representing the nitrogen-containing compound of the present invention, X represents a group selected from the following group A. Group A

A hydrogen

A2: Hydrocarbon group having 1 to 30 carbon atoms

A: Alkinol group represented by the following general formula (6)

― R— OH (6)

[In the general formula (6), R ¹⁵ represents a carbon number.] 6 represents an alkylene group. ]

A: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), R ¹⁶ represents an alkylene group having 2 to 6 carbon atoms, R ¹⁷ represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a group represented by the general formula (6), R ¹⁸ represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or a group represented by the above general formula (6), and g represents an integer of 1 to 5. ]

A 5: a group represented by the following general formula (8)

twenty one

2 ⁰ R

R "R ²³

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 6 carbon atoms, and R ²⁰ , R ²¹ , R ²² and R ²³ 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, an imino group, an imino group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, or oxygen. Where h is 1 when e = 1, 0 or 1 when e = 2 (however, when h = 0, N (nitrogen) in the general formula (8) is represented by the general formula ( 1) Corresponds to N (nitrogen) in] Preferred as the hydrocarbon group having 1 to 30 carbon atoms corresponding to the above A 2 include a linear or branched alkyl group having 1 to 24 carbon atoms described above for R ¹ , A linear or branched alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group or an alkylcycloalkyl group having 5 to 13 carbon atoms, an aryl or alkylaryl group having 6 to 18 carbon atoms, carbon number And a straight-chain or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 7 to 19 carbon atoms. An arylalkyl group is more preferred, and hydrogen, 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 preferred. In the general formula (6) showing the alkanol group of A 3 above, R ¹⁵ represents an alkylene group having 1 to 6 carbon atoms. Examples of such an alkylene group include the groups described above as R ^6. No. Among them, R ¹⁵ is preferably an alkylene group having 1 to 4 carbon atoms, specifically, 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, A tetramethylene group is preferred. R ¹⁵ is most preferably an alkylene group having 1 to 3 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group (a monomethylethylene group, a 2-methylethylene group) or a trimethylene group. . In the general formula (7) representing the nitrogen-containing group represented by A4, R ¹⁶ represents an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group include an ethylene group and 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-methyl Trimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene group

(1-butylethylene group, 2-butylethylene group), 1-ethyl-1 -methyl Tylene group, 1-ethyl-12-methylethylene group, 1,1,2-trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethylethylmethylene group, 3 —Ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,

3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1-l-tetramethylene 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-propyl ethylene group, 1,

1-Jethyl ethylene group, 1,2-Jethyl ethylene group, 2,2-Jethylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 2-ethylethyl group 1, 1-dimethylethylene group, 2-ethyl-1,

2-dimethylethylene group, 1,1,2,2-tetramethylethylene group, 1-provided trimethylene group, 2-provided trimethylene group, 3-provided trimethylene group, 1-ethyl-11-methyltrimethylene group, 1 —Ethyl-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-1-methyltrimethylene, 3-ethyl-12-methyltrimethylene, 3-ethyl-3-methyltrimethylene, 1,1,2-trimethyltrimethylene, 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-ethyltetramethylene group, 3-ethyltetramethylene group , 4-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,

3-dimethyltetramethylene, 1,4-dimethyltetramethylene, 2,2-dimethyltetramethylene, 2,3-dimethyltetramethylene, 2,4-dimethyltetramethylene, 3,3-dimethyltetramethylene, 3, 4-dimethyltetramethylene group, 4,4-dimethyltetramethylene group, 1-methylpentyne It includes a len group, a 2-methylpentamethylene group, a 3-methylpentamethylene group, a 4-methylpentamethylene group, a 5-methylpentamethylene group, a hexamethylene group, and the like.

Among them, R ¹⁶ 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, a 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, A tetramethylene group and the like are preferable, and an alkylene group having 2 to 3 carbon atoms, specifically, an ethylene group, a propylene group (a monomethylethylene group, a 2-methylethylene group), and a trimethylene group are more preferable.

R ¹⁷ in the general formula (7) represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a group represented by the general formula (6). 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. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

R ¹⁸ in the general formula (7) represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, or a group represented by the general formula (6). Preferred as the hydrocarbon group having 1 to 30 carbon atoms here are linear or branched alkyl groups having 1 to 24 carbon atoms described above for R ¹ , and linear groups having 2 to 24 carbon atoms. Alkenyl, cycloalkyl or alkylcycloalkyl having 5 to 13 carbons, aryl or alkylaryl having 6 to 18 carbons, arylalkyl having 7 to 19 carbons, etc. Included.

R ¹⁸ represents 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 group represented by the general formula (6). And most preferably hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, an arylalkyl group having 7 to 9 carbon atoms, or a group represented by the general formula (6). preferable. G in the general formula (7) is an integer of 1 to 5, preferably 1 to 4, and more preferably 1 to 3.

The group represented by the following general formula (17), which is included in the nitrogen-containing group of the general formula (7), has 1 to 5 structural units represented by the following general formula (18), It preferably has 1 to 4, more preferably 1 to 3.

-R ¹⁶ -N— ( ¹⁸ )

R ¹⁷

R ¹⁶ and R ¹⁷ in the general formulas (17) and (18) are the same as the definitions of R ¹⁶ and R ^{17 in} the general formula (7), and g is the same as the definition of g in the general formula (7). The same.

Therefore, the group represented by the general formula (17) represents a group obtained by bonding the structural units represented by the general formula (18) as follows.

(1) Combination of one kind of structural unit represented by general formula (18).

(2) A structure in which two or more different structural units included in the general formula (18) are random-bonded, alternate-bonded, or block-bonded.

A preferred group as the nitrogen-containing group of general formula (7) corresponding to A is that R ¹⁶ is an alkylene group having 2 to 4 carbon atoms, R ¹⁷ is hydrogen, an alkyl group having 1 to 3 carbon atoms or a general formula (6) R ¹⁸ is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group or an alkyl aryl group having 6 to 12 carbon atoms, Is a group represented by the general formula (6), and g is 1 to 4. R ¹⁶ is an ethylene group, a propylene group (a monomethylethylene group, a 2-methylethylene group) or a trimethylene group And R ¹⁷ is hydrogen, methyl, ethyl or a general formula

Wherein R ¹⁸ is hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, an alkyl aryl group having 7 to 9 carbon atoms, or a general formula

Most preferably, it is a group represented by (6), and g is 1 to 3. In the group represented by the general formula (8) corresponding to the A 5, R ¹⁹ represents an alkylene group having 2-6 carbon atoms. The alkylene groups referred to herein include groups described for R ¹⁶ above. Among them, H ¹⁹ is preferably an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group (1-butylene group, a 2-methylethylene group), a trimethylene group, a 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, tetra A methylene group or the like is preferable, and 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 is more preferable.

R ^2Q , R ²¹ , R ²² and R ²³ in the general formula (8) each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the linear or branched alkyl group having 1 to 10 carbon atoms described above for R ² , RR ⁴ and R ⁵ , and 2 carbon atoms. Linear or branched alkenyl group having up to 10 carbon atoms, cycloalkyl group or alkylcycloalkyl group having 5 to 10 carbon atoms, aryl or alkylaryl group having 6 to 10 carbon atoms, carbon atom having 7 to 10 carbon atoms And 10 arylalkyl groups.

Among these, it is preferred that R ^2Q , R ²¹ , R ²² and R ²³ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by a hydroxyl group, and each of them is independently hydrogen or carbon. More preferably, it is an alkyl group or a hydroxyl group having a number of 1 to 3. In the general formula (8), Y is a methylene group, a hydrocarbon group having 1 to 10 carbon atoms, a methylene group substituted with a hydroxyl group, an imino group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group. Shows a substituted imino group or oxygen. Here, 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 ² , R ³ , R ⁴ and R ⁵ , A linear or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group or an alkylcycloalkyl group having 5 to 10 carbon atoms, an aryl or alkylaryl group having 6 to 10 carbon atoms, carbon And an arylalkyl group having 7 to 10 carbon atoms. Preferred are alkyl groups having 1 to 6 carbon atoms, and more preferred are alkyl groups having 1 to 3 carbon atoms. Among these, 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, an imino group substituted with an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, or oxygen. Most preferred is a methylene group, a methylene group substituted with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, an imido, a imino 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 (8) is h = l when e = l in the general formula (1), and h = 0 or h = when e = 2 in the general formula (1). It is 1. However, when 6 = 2 = 0, N (nitrogen) in the general formula (8) is the general formula

This corresponds to N (nitrogen) in (1). That is, when e = 2 and h = 0, as represented by the general formula (19), N (nitrogen) contained in the compound is represented by the general formula

It is a member of the heterocyclic ring represented by (8).

R ² , RRR ⁵ and R ⁶ in the general formula (19) are the same as the definitions of RR ² , RRR ⁵ and R ^{6 in} the general formula (1), and a, b and c are the same as those in the general formula (1) R ^2G , R ²¹ , R ²² , R ²³ and Y are the same as the definitions of R ² °, R ²¹ , R ²² , R ²³ and Y in the general formula (8). Same as righteousness.

As the group represented by the general formula (8), R ¹⁹ is an alkylene group having 2 to 4 carbon atoms, and R ² °, R ²¹ , R ²² and R ²³ each independently represent hydrogen, An alkyl group or a hydroxyl group having 1 to 6 carbon atoms, wherein Y is a methylene group, a methylene group substituted with an alkyl group or a hydroxyl group having 1 to 6 carbon atoms, an imino group, an alkyl group or a hydroxyl group having 1 to 6 carbon atoms Is an imino group or oxygen substituted with, when h is e 2 1, h = l, and when e = 2, h = 0 or h = 1 (however, when h = 0, N (nitrogen) in the general formula (5) is also preferably N (nitrogen) in the general formula (1), and R ¹⁹ is an ethylene group, a propylene group (1-methylethylene group, 2 —A methylethylene group or a trimethylene group, R ^2D , R ²¹ , R ²² and R ²³ are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and Y is a methylene group, 1 carbon atom A methyl bromide substituted with an alkyl group or a hydroxyl group, an imino group, an imino group substituted with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, or oxygen, and when h is e = 1, h = 1 and e = 2 when h = 0 or h = l (However, when h = 0, N (nitrogen) in the general formula (8) becomes N (nitrogen) in the general formula (1) In the general formula (1) representing the nitrogen-containing compound of the present invention, Z is a group represented by the general formula (3). X can be selected arbitrarily from the above A1 to A5, and among these, X is preferably A1, A3, A4 and A5. In this case, it is more preferable that X is A 3, A 4 or A 5. When e = 2, that is, when two X are selected, the two are the same but different. However, there is no problem.

However, when Z is a group represented by the general formula (4) or (5), when e = l, X is not A3, and when e = 2, one of X is A3 and the other is not A2 or A3. As described above, the substituents of the general formula (1), which collectively represent the nitrogen-containing compound of the present invention, have been individually described. Preferred examples of the nitrogen-containing compound of the present invention include: The case where Z in 1) is a group represented by the general formula (3) and the case where Z is a group represented by the general formula (4) or (5) are separately described as follows. is there.

(a) When Z is a group represented by the general formula (3)

R ¹ is hydrogen in the general formula (1), or a linear or branched alkyl group having 1 to 12 carbon atoms, or an Ariru group or Arukirua aryl group of carbon number. 6 to 18, R ^2, One or two of R ³ , R ⁴ and R ⁵ are groups represented by the general formula (2), and the other 3 to 2 are each independently hydrogen or an alkyl having 1 to 6 carbons. Group

In the general formula (2), 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. A group or an alkoxyalkyl group-substituted ethylene group having 2 to 8 carbon atoms, R ^lfl is an alkyl group having 1 to 24 carbon atoms, and f is an integer of 0 to 30. an R ¹¹ it it Al Killen group having 1 to 4 carbon atoms of R ⁶ and general formula (3),

a is 1 to 100, b is 0 to: L is an integer of 00, and a + b = l to 200, c is 0 or 1, d is an integer of 1 to 2, and e is An integer from 1 to 2 and d + e = 3;

X is A 1, A 3, A 4 or A 5, R ¹⁵ in the general formula (6) corresponding to is an alkylene group having 1 to 4 carbon atoms, and R ¹⁶ in the general formula (7) corresponding to An alkylene group having 2 to 4 carbon atoms, R ¹⁷ is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a group represented by the general formula (6); and R ¹⁸ is hydrogen, an alkyl group having 1 to 12 carbon atoms. A linear or branched alkyl group, an aryl group having 6 to 12 carbon atoms or an aryl alkyl group, or a group represented by the general formula (6), wherein g is an integer of 1 to 4 and corresponds to AA In the general formula (8), R ¹⁹ is an alkylene group having 2 to 4 carbon atoms, and R ² °, R ²¹ , R ²² and R ²³ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group. Wherein Y is a methylene group, an alkyl group having 1 to 6 carbon atoms or a methylene group substituted with a hydroxyl group, an imino group, or an alkyl group having 1 to 6 carbon atoms. Or an imino group or oxygen replaced by a hydroxyl group, h = 1 when e = 1, h = 0 or h = 1 when e = 2 (where h = 0 In this case, general formula (8) and general formula (1) share the same N (nitrogen)). More preferably,

R ¹ in the general formula (1) is hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkylaryl group having 7 to 15 carbon atoms, and R ² , R \ R ⁴ and R ⁵ Is a group represented by the general formula (2), and the remaining three are each independently a hydrogen or an alkyl group having 1 to 3 carbon atoms; In the general formula (2), 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 ^{1 ()} is a carbon atom. An alkyl group of the numbers 1 to 12, and: is an integer of 0 to 20,

R ^{6 in the} general formula (1) is an alkylene group having 1 to 4 carbon atoms, R ^{11 in the} general formula (3) is an alkylene group having 1 to 3 carbon atoms,

a is 2 to 50, b is an integer of 0 to 50, and a + b = 2 to: L is 00, c is 0 or 1, d is 1, e is 2, X Is A 1 ヽ A3, A 4 or A 5, R ¹⁵ is an alkylene group having 1 to 3 carbon atoms in the general formula (6) corresponding to, and R ¹⁶ in the general formula (7) corresponding to A An alkylene group having 2 to 3 carbon atoms, R ¹⁷ is hydrogen, a methyl group, an ethyl group or a group represented by the general formula (6), and R ¹⁸ is hydrogen, a linear group having 1 to 6 carbon atoms. Or a branched alkyl group, a phenyl group, an arylalkyl group having 7 to 9 carbon atoms or a group represented by the general formula (6), wherein g is an integer of 1 to 3, and In 8), R ¹⁹ is an alkylene group having 2 to 3 carbon atoms, R ^2l) , R ²¹ , R ²² and R ²³ are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and Y Is a methylene group, carbon 1-3 § alkyl group or a hydroxyl substituted methylene group, an imino group, a nitrogen-fluorinated compounds as are Imino group or an oxygen substituted with § alkyl group or hydroxyl group having 1 to 3 carbon atoms.

(b) When Z is a group represented by the general formula (4) or (5)

R ¹ in the general formula (1) is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group or an alkyl aryl group having 6 to 18 carbon atoms; One or ^{two of} R ² , R ³ , R ⁴ and R ⁵ are a group represented by the general formula (2), and the other 3 to 2 are each independently hydrogen or a group having 1 to 6 carbon atoms. An alkyl group,

In the general formula (2), 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. A group or an alkoxyalkyl group-substituted ethylene group having 2 to 8 carbon atoms, wherein R ^{1 ()} is an alkyl group having 1 to 24 carbon atoms, and f is an integer of 0 to 30; R ⁶ in) is an alkylene group having 2 to 4 carbon atoms, the general formula (4) R ¹² or R ¹³ and R ^{14 in} the general formula (5) are each independently an alkylene group having 1 to 4 carbon atoms;

a is 1 to: L00, b is an integer of 0 to: L00, and a + b = l to 200, c is 0 or 1, d is an integer of 1 to 2, e is an integer from 1 to 2 and d + e = 3,

X is selected from group A (except when e = 1, X is A3, except when e-2, one of X is A3 and the other is A2 or A3 ), A 2 It is a linear or branched alkyl group having 1 to 12 carbon atoms or an aryl group or aryl alkyl group having 6 to 12 carbon atoms, and is represented by the general formula (6) In the formula, R ¹⁵ is an alkylene group having 1 to 4 carbon atoms, and in the general formula ( ⁷ ) corresponding to ±, R ¹⁶ is an alkylene group having 2 to 4 carbon atoms, R ¹⁷ is hydrogen, and has 1 to 3 carbon atoms. An alkyl group or a group represented by the general formula (6), wherein R ¹⁸ is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group or an aryl alkyl group having 6 to 12 carbon atoms. Or a group represented by the general formula (6), g is an integer of 1 to 4, and in the corresponding general formula (8), R ¹⁹ is an alkylene group having 2 to 4 carbon atoms. R ^2D , R ²¹ , R ²² and are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and Y is a methylene group, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group. Methylene group, imino group, imino group substituted with an alkyl group having 1 to 6 carbon atoms or hydroxyl group or oxygen, h = 1 when e = 1, h when e = 2 = 0 or h = 1 (however, when h = 0, the general formula (8) and the general formula (1) share the same N (nitrogen)).

More preferably,

In the general formula (1), R ¹ is hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkylaryl group having 7 to 15 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ One group is a group represented by the general formula (2), and the remaining three are each independently a hydrogen or an alkyl group having 1 to 3 carbon atoms;

In the general formula (2), 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 ^{1 ()} has 1 carbon atom. An alkyl group of from 12 to 12, and f is an integer of 0 to 20, R ⁶ of the general formula (1) is an alkylene group having 2 to 4 carbon atoms, and R ¹² of the general formula (4) or R ¹³ and R ^{14 of the} general formula (5); ~ 3 alkylene groups,

a is 2 to 50, b is an integer of 0 to 50, and a + b = 2 to 100, c is 0 or 1, d is 1, e is 2, and X is A Selected from the group (except when one of X is A3 and the other is A2 or A3), and 82 is a linear or branched alkyl group having 1 to 12 carbon atoms or carbon Is an aryl group or arylalkyl group having the number of 6 to 12, R ¹⁵ is an alkylene group having 1 to 3 carbon atoms in the general formula (6) corresponding to and a general formula (? ), R ¹⁶ is an alkylene group having 2 to 3 carbon atoms, R ¹⁷ is hydrogen, a methyl group, an ethyl group or a group represented by the general formula (6), and R ¹⁸ is hydrogen, 1 to 6 carbon atoms. A linear or branched alkyl group, phenyl group, arylalkyl group having 7 to 9 carbon atoms or a group represented by the general formula (6), g is an integer of 1 to 3, and A 5 General formula ( In 8), R ¹⁹ is an alkylene group having 2 to 3 carbon atoms, R ^2fl , R ²¹ , R ²² and R ²³ are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, and Y is A nitrogen-containing compound such as an imino group, an imino group substituted with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group, or oxygen. The nitrogen-containing compound according to the present invention can be produced by any method.

For example, the nitrogen-containing compound of the present invention represented by the general formula (1) 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. Is heated and dehydrated to obtain a ketimine compound.

Compounds having two or more amino groups in the molecule include ethylenediamine, Diamines such as lopylenediamine (1,2-diaminopropane) and trimethylenediamine (1,3-diaminopropane), diethylenetriamine, dipropylenetriamine, di (trimethylene) triamine, dimethylaminopropylenediamine, triethylenetetramine , Tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, penethyleneethylenehexamine, and penamine: polyamines such as 7 ° ropylenehexamine (having three or more N atoms).

Examples of the compound having an amino group and an alkanol group in the molecule include monoethanolamine, monoethanolamine, mono-n-propanolamine, monoisopropanolamine, mono (linear or branched) phenolamine ( The position of the hydroxyl group is arbitrary), mono (linear or branched) pennoolamine (position of the hydroxyl group is arbitrary), mono (linear or branched) hexanolamine (position of the hydroxyl group is arbitrary) And alkanolamines such as 2- (2-aminoethylamino) ethanol and the like.

Examples of the compound having an amino group and an imino group in the molecule include the above polyamine and 4-aminomethylbiperidine.

Examples of the compound having an amino group and a carboxyl group in a molecule include amino acids such as alanine, alanine, and N- (2-aminoethyl) glycine. Further, as the ketone, one represented by the following general formula (20) is usually used.

R—C—R ²⁵ (20)

II '

0 In the above general formula (20), R ²⁴ and R ²⁵ each 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 (20), ketones having a branched alkyl group and having large steric hindrance are preferable, and isobutylmethylketone, isobutylethylketone, diisobutylketone and the like are preferably used. .

By reacting an alkanolamine with a ketone, a ketimine compound represented by the following general formula (21) can be obtained. _R 24

HO— R ⁶ -N = C ⁽²¹⁾

, R ²⁵

In the general formula (2 1), R ⁶ is the formula (1) in indicates the same group as R ^6, R ²⁴ and R ²⁵ represent the same group as R ²⁴ and R ²⁵ in the general formula (20). By reacting an amino acid with a ketone, a ketimine compound represented by the following general formula (22) can be obtained.

R ²⁴

HO-CR ¹ — N = C ^ ( ²² )

II, _R 25

0 ^κ

In the general formula (22), R is formula (3) in indicates the same group as R ^11, R ²⁴ and R ²⁵ represent the same group as R ²⁴ and R ²⁵ in the general formula (20). Further, when a diamine and a ketone are reacted, a ketimine compound represented by the following general formula (23) can be obtained.

_R 24

H ₂ N— R ¹⁶ — N = C ' ⁽²³ )

In R ²⁵ the formula (23), R ¹⁶ represents the same group as R ¹⁶ in the general formula (7), the R ²⁴ and R ²⁵ are the general formula (20) in R ²⁴ and R ²⁵ the same groups Show. When a polyamine (having 3 or more N atoms) is reacted with a ketone, a ketimine compound represented by the general formula (24) or (25) can be obtained. ( ²⁴ )

In the general formula (24) and (25), R ¹⁶ and R ¹⁷ represents a general formula (7) to put that R ¹⁶ and R ¹⁷ the same groups, g, g 'and g "of the general formula (7) And R ²⁴ and: ²⁵ represent the same groups as R ²⁴ and R ²⁵ in the general formula (20), wherein the starting amine and the ketone of the general formula (20) are the same. When reacting, it is preferable that the protected amino group and the ketone are equimolar.

When using alkanolamine, amino acid or diamine as a starting material, it is preferable to react an equimolar ketone, and when using a polyamine (3 or more N atoms), it is preferable to react an equimolar or 2 times mole of ketone. .

The reaction temperature in the ketimination step is optional, but is usually in the range of 40 to 180 ° C, more preferably in the range of 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 above-mentioned ketimination step as a reaction initiator,

① Polymerize the epoxy compound represented by the general formula (26) alone,

② Polymerizing a mixture of an epoxy compound represented by the general formula (26) and an oxysilane compound represented by the general formula (27),

(3) After obtaining a homopolymer of the epoxy compound of the general formula (26), the oxysilane compound of the general formula (27) is further polymerized.

後 After obtaining a homopolymer of the oxysilane compound of the general formula (27), the epoxy compound of the general formula (26) is further polymerized;

The reaction of the polymerization product (in the form of metal alkoxide) obtained by the above method is stopped with a halogen compound represented by the general formula (28), and then the salt is removed to obtain the compound represented by the general formula (28). 29) to obtain a polyoxyalkylene glycol derivative having a ketimine compound at the terminal represented by (33) (when b ≠ 0, the polyoxyalkylene glycol derivative having a ketimine compound at the terminal is a random copolymer And the case of a block copolymer are included).

R ⁶ = 0 (27) R—Q (28) In the general formulas (26) to (28), II ¹ , RR \ R: ⁵ and R ⁶ are R ¹ R ² in the general formula (1) , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same groups, and Q represents chlorine, bromine or iodine.

In general formula (27), two hydrogen atoms bonded to any two adjacent carbon atoms in the alkylene group R ⁶ are replaced by one oxygen atom to form an alkoxy group. Shown below are the oxysilane compounds.

R on O- (29)

(33)

In the above general formulas (29) to (33), RR ² , R \ R ⁴ , R ⁵ and R ⁶ are the same as RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (1). And a, b, and d represent the same integers as a, b, and d in the general formula (1), and g, and g, 'represent g and g in the general formula (7). And j represents an integer such that d + j = 2, R ¹¹ represents the same group as R ¹¹ in formula (3), and R ¹⁶ and R ¹⁷ represent indicates the same group as R ¹⁶ and R ¹⁷ in formula (7), R ²⁴ and R ²⁵ show the same group as R ²⁴ and R ²⁵ in the general formula (20).

Preferred examples of the epoxy compound represented by the general formula (26) include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, and isobutyl glycidyl ether. , Sec-butyl glycidyl ether, tert-butyl glycidyl ether, linear or branched pentyl 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 on the branch Straight or branched tridecyl glycidyl ether, straight or branched tetradecyl glycidyl ether, straight or branched pendecyl glycidyl ether, straight or branched hexadecyl glycidyl ether, straight or branched Is a branched heptane decyl glycidyl ether, a linear or branched hexadecyl glycidyl ether, a linear or branched octadecyl glycidyl ether, a vinyl glycidyl ether, a linear or branched probenyl Glycidyl ether, linear or branched butenyl glycidyl ether, linear or branched pentenyl glycidyl ether, linear or branched hexenyl glycidyl ether, linear or branched Heptenyl glycidyl ether, linear or branched octenyl glycidyl ether, linear or branched nonenyl glycidyl ether, linear or branched decenyl glycidyl ether, linear or branched benzyl ester Nylglycidyl ether, straight or branched dodecenyl glycidyl ether, straight or branched tridecenyl dalidyl ether, straight or branched tetradecenyl glycidyl ether chain. Pencenyl decenyl glycidyl ether, linear or branched hexadecenyl glycidyl ether, linear or branched heptanyl decenyl glycidyl ether, linear or branched hexadecenyl glycidyl ether Ter, linear or branched octenyl glycidyl ether, phenyl glycidyl ether, triglycidyl ether Xylylglycidyl ether, linear or branched propylphenylglycidyl ether, linear or branched butylphenylglycidyl ether, linear or branched pentylphenylglycidyl ether, direct Chain or branched hexyl phenyl glycidyl ether, straight or branched heptyl phenyl glycidyl ether, straight or branched octyl phenyl glycidyl ether, straight or branched nonyl phenyl Glycidyl ether, linear or branched decylphenyl glycidyl ether, linear or branched pentadecylphenyl glycidyl ether, linear or branched dodecylphenyl glycidyl ether, linear or branched tridecylphenyl glycidyl ether Mono-ter, straight-chain or branched dodecylphenylglycidyl lutee , 1, 2-Epoxy-1-3-methoxy-1-oxahexane, 1, 2-Epoxy-1, 7-dioxaoctane, 4, 5-Epoxy-1, 7-Dioxaoctane, 1, 2-Epoxy-1-5 —Methyl-1,4,7-dioxaoctane, 1,2—Epoxy-1-6-methyl-4,7—dioxaoctane, 1,2-epoxy-1-5 -— (2-oxaprovir) -4,7-dioxaoctane, 1,2-epoxy-1 3,5-bis (2-oxapropyl) 1-4,7-dioxaoctane, 1,2-epoxy 3,6-bis (2-oxapropyl) 1-4,7-dioxaoctane, 1,2-epoxy-1-6-methoxy 1,4,8-dioxanonane, 1,2-epoxy-1,4,7,10-trioxanedecane, 1,2-epoxy-5-methyl-4,7,10-trioxanedecane, 1, 2-epoxy-1-methyl-4,7,10-trioki Undekan, 4, 5 - epoxy one 9-methyl-2, 7, 1 0-reserve Sandecan, 1,2-epoxy-1,6,9-dimethyl-1,4,7,10-trioxanedecane, 1,2-epoxy-1,6,9-bis (2-oxapropyl) -1,4,7,10-trioxane Decane, 1,2-epoxy-1,4,7,10,13-tetraoxatetradecane, 4,5-epoxy-1,2,7,10,13-tetraoxatetradecane, 7,8-epoxy-1,2,5,10 , 13-tetraoxytetra.decane, 7,8-epoxy-1,3,12-dimethyl-1,2,5,10,13-tetraoxatetradecane, 1,2-epoxy-1,6,9,12-trimethyl-4,7, 10, 13-tetraoxatetradecane and the like. Preferred examples of the oxysilane compound represented by the general formula (27) include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide (1,2-butylene oxide), 2-butene oxide, Examples thereof include 1-pentenoxide, trimethylethylene oxide, 1-hexenoxide, and tetramethylethylene oxide. The molar ratio when reacting the ketimine compound with the epoxy compound of the general formula (26), and the molar ratio when reacting the ketimine compound with a mixture of the epoxy compound of the general formula (26) and the oxysilane compound of the general formula (27) Can be chosen arbitrarily. However, it is usually preferable to react 5 to 100 moles of the epoxy compound or a mixture of the epoxy compound and the oxysilane compound with respect to 1 mole of the ketimine compound.

The reaction temperature in the polymerization step can be arbitrarily selected, but is usually in the range of 60 to 180 ° C, preferably in the range of 80 to 150 ° C.

(C) hydrolysis step

The nitrogen-containing compound of the present invention can be obtained by heat-treating the polyoxyalkylene glycol derivative having a ketimine compound at the terminal obtained in the above-mentioned polymerization step in the presence of excess water.

The reaction temperature in the hydrolysis step can also be arbitrarily selected. But usually 40 ~ It is selected in the range of 150 ° C, preferably in the range of 50 to 100 ° C.

By adding an oxysilane compound of the general formula (27) to the terminal amino group obtained by hydrolyzing a polyoxyalkylene glycol derivative having a ketimine compound at the terminal, a nitrogen-containing compound having an alkanolamine type terminal can be obtained. the _c can be obtained, morpholine, N-5-arsenide de Loki Chez methylmorpholine, N-(2-arsenide] ^ mouth. Kishipuropiru) morpholine, piperidine, 1- (2-arsenate Dorokishechiru) Piperi Jin, 2- Dimethylaminoethanol, 2-dimethylamino-1-propanol, 1-dimethylamino-12-propanol, 4-dimethylamino-11-butanol, 2-dimethylamino-12-methyl-1-propanol, 2-getylaminoethanol , 3-Jetylamino-1-propanol, 1-Jethylamino-2-propanol, 2-diisopro L-aminoamine, 2-dimethylaminoethylamine, 3-dimethylaminopropylamine, 2-getylaminoethylamine, 3-dimethylaminopropylamine, 2-diisopropylaminoethylamine, 1-aminobiperidine, 1 1 (2-aminoethyl) biperidine, 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, biperazine, 1-methylbiperazine, 1- (2-aminoethyl) pi When perazine or the like is used, the nitrogen-containing compound of the present invention represented by the general formula (1) can be obtained by directly polymerizing without the necessity of the above-mentioned ketimination step and hydrolysis step. I can go. Alternatively, as another method, the nitrogen-containing compound of the present invention represented by the general formula (1) may be prepared by the following (Β ′) polymerization step, (C) chromate format step, and (D) ester carbonate method. It can be synthesized through a conversion step.

(Β,) Polymerization process

Except for using the oxygen-containing compound represented by the general formula (34) in place of the ketimine compound as the reaction initiator, the polymerization is carried out by any of the methods (1) to (4) in the same manner as in the above (前記) polymerization step. The obtained polymerization product (in the form of a metal alkoxide) is neutralized with an acid such as hydrochloric acid to obtain a polyoxyalkylene glycol derivative represented by the general formula (35) (b ≠ In the case of 0, poly with a ketimine compound at the end Both the case where the oxyalkylene glycol derivative is a random copolymer and the case where it is a block copolymer are included).

R—OH (34)

/ R ^3,

R— 0-(— C— C—Hi H (35)

R ⁴ R ⁵ ; In the general formulas (34) and (35), RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ are RR ² , R ³ , R ⁴ , R ⁵ and R ⁵ in the general formula (1). It represents the same group as R ^6, and a and b are the same integers as a and b in the general formula (1).

The molar ratio when reacting the oxygen-containing compound of the general formula (34) with the epoxy compound of the general formula (26), the oxygen-containing compound of the general formula (34), the epoxy compound of the general formula (26) and The molar ratio when reacting with the mixture of the oxysilane compound of the formula (27) can be arbitrarily selected. However, it is usually preferable to react 5 to 100 moles of the epoxy compound or a mixture of the epoxy compound and the oxysilane compound with respect to 1 mole of the oxygen-containing compound.

(C) Black mouth forming process

The polyoxyalkylene glycol derivative of the general formula (35) obtained in the above polymerization step or the metal alkoxide compound before neutralization thereof is reformed with an excess amount of phosgene, for example, at room temperature, to obtain a compound of the general formula (36) To obtain a chlorine-containing compound represented by the formula:

R— 0- C1 (36)

I ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (36) represent the same groups as RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (1) A and b also represent the same integer as a and b in the general formula (1).

(D) Carbonic acid ester-forming step-1-1-With the chlorine-containing compound of the general formula (36) obtained in the above-mentioned chromate forming step and the alkanoic acid represented by the general formulas (37) to (39) The nitrogen-containing compound of the present invention can be obtained by reacting with luamine.

26

R '

/

HO— R ¹² -N (37)

\ „ ₂₇

R

twenty one

2 ⁰ R

In the general formula (37) ~ (39), R 12 represents the same group as R ¹² in the general formula (4), R ²⁶ and R "represents it it hydrocarbon group having 1 to 30 carbon atoms, R ¹⁶ , R ¹⁷ , R ¹⁸ and g represent the same groups as ⁶ , R ¹⁷ and R ^{18 in the} general formula (7), g is the same integer as g in the general formula (7), and R ²⁸ is Represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ¹⁹ , R ² °, R ²¹ , R ²² , R ²³ and Y represent R ¹⁹ , R ² ° in the general formula (8). , R ²¹ , R ²² , R ²³ and the same group as Y, and h is also the same integer as h in the general formula (8) .Alkinolamine represented by the general formulas (37) to (39) Examples of particularly preferred compounds include N, N-dimethylmethanolamine, N, N-methylethylmethanolamine, and N, N-methyl (linear or branched) propylmethanolamine. Min, N, N_Methyl (straight or branched) Butylmethanolamine, N, N-Dimethylmethanolamine, N, N_ethyl (straight or branched) Propylmethanolamine, N, N —Ethyl (straight or branched) butyl methanolamine, N, N di (straight or branched) propyl methanolamine, N, N— (straight or branched) propyl (straight or branched) Butyl methanolamine, N, N-di- (straight or branched) Butyl methanolamine, N, N-dimethylethanolamine, N, N-methylethylethanolamine, N, N-methyl (Linear or branched) Propylethanolamine, N, N-methyl (linear or branched) Butylethanolamine, N, N-Jetyletanoylamine, N, N-ethyl (linear or branched) Pyrethanolamine, N N- Echiru (straight or branched) butyl ethanol Amin, N, N- di (straight or branched) propyl ethanol § Min, N, N-

(Linear or branched) propyl (linear or branched) butylethanolamine, N, N-di (linear or branched) butylethanolamine, N, N-dimethylpropano-lamine (all isomers) , N, N-methylethylpropanolamine (including all isomers), N, N-methylpropylpropanolamine (including all isomers), N, N-methyl Butylpropanolamine (including all isomers), N, N-Getylpropanolamine (including all isomers), N, N-ethylpropylpropanolamine (including all isomers) N, N-Ethylbutylpropanolamine (including all isomers), N, N-Dipropylpropanolamine (including all isomers), N, N-Propylbutylpropanolamine N, N-Dibutylpropanolamine (including all isomers), N, N-Dimethylbutanolamine (including all isomers), N, N-methylethylbutanolamine (including all isomers) Isomer), N, N-methylpropylbutanolamine (including all isomers), N: N-methylbutylbutanolamine (including all isomers), N, N-methylbutanol L-lamine (including all isomers), N, N-ethylpropyl butylamine, N, N-ethylethylbutylamine

(Including all isomers), N, N-dipropylbutaneolamine (including all isomers), N, N-provirptylbutaneolamine (including all isomers) )), N, N-dibutylbutanolamine (including all isomers),

N, N-dimethylpentanolamine (including all isomers), N, N-methylethylpentanolamine (including all isomers), N, N-methylpropylpentanolamine (including all isomers) , N, N-Methylbutyltyl phenolamine (including all isomers), N, N-Jetylpentanolamine

(Including all isomers), N, N-ethylpropyl pentanolamine (including all isomers), N, N-ethylbutylpentanolanolamine (including all isomers), N, N— Dipropylpentanolamine (including all isomers), N, N-propylbutylpentanolamine (including all isomers), N, N—dibutylpentanolamine (including all isomers), N— — Hydroxyethylmorpholine, N- (2-hydroxypropyl) morpholine, 1- (2-hydroxyxethyl) piperidine and the like. The molar ratio of the reaction of the chlorine-containing compound of the general formula (36) and the alkanolamine of the general formulas (37) to (39) in the carbonic acid esterification step can be arbitrarily selected. The alkanolamine is preferably reacted at least 1 mol or more, more preferably 1 to 10 mol, with respect to 1 mol of the chlorine-containing compound.

The reaction temperature in the carbonic acid esterification step is also optional, but is usually preferably from 120 to 150 ° C, more preferably from 110 to 80 ° C. Instead of using the alkanolamines represented by the general formulas (37) to (39), an alkanolamine having an amino group in addition to a hydroxyl group represented by the general formula (40) or (41) is used. When used, the amino group of the alkanolamine is protected with a ketone represented by the general formula (45), and then reacted with a chlorine compound represented by the general formula (36). By releasing the protection, the nitrogen-containing compound of the present invention can be obtained. 12

HO— R— NH ₂ (40)

,-:-One-

In the general formula (40) ~ (42), R ¹² represents in the general formula (1) and R ¹² the same groups, R ¹⁶ and R ¹⁷ are the same as R ¹⁶ and R ¹⁷ in the general formula (7) G represents the same integer as g in the general formula (7), R ²⁹ represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and R ^3fl and R ³¹ each independently represent a carbon number. 1 to 10, preferably 1 to 5 linear or branched alkyl groups. Particularly preferred examples of the alkanolamine having a hydroxyl group and an amino group represented by the general formula (40) or (41) include monomethanolamine, monoethanolamine, mono-n-propanolamine, Monoisopropanolamine, mono (linear or branched) buenoylamine (position of hydroxyl group is arbitrary), mono (linear or branched) pentanoylamine (position of hydroxyl group is arbitrary), mono (direct Hexanolamine (the position of the hydroxyl group is arbitrary), 2- (2-aminoethylamino) ethanol and the like.

Further, as the compound represented by the general formula (42), a ketone having a branched alkyl group and having a large steric hindrance is preferable, and isobutylmethylketone, isobutylethylketone, diisobutylketone and the like are preferably used. . When the alkanolamine of the general formula (40) is reacted with a ketone, the ketimine compound represented by the general formula (43) is reacted with the alkanolamine of the general formula (41) and ketone to obtain a general compound. The ketimine compound represented by the formula (44) can be obtained in various ways. HO)

In formulas (43) to (44), R ¹² represents the same group as R ¹² in formula (4), and R ¹⁶ and R ¹⁷ are the same as R ¹⁶ and R ¹⁷ in formula (7) G also represents the same integer as g in the general formula (7), and R ²⁹ represents the general formula (4

1) represents the same group as R ²⁸ in R), and R ^3D and R ³¹ represent the group represented by the general formula (42)

Shows the same group as R and R ^31. The molar ratio when reacting the alkanolamine with the ketone of the general formula (42) can be arbitrarily selected, but usually, at least 1 mol of ketone is reacted with 1 mol of alkanolamine. The reaction is more preferably performed in an amount of 1 to 10 mol, and most preferably in an equimolar amount.

The reaction temperature at the time of ketimine formation is optional, but is usually selected in the range of 40 to 180 ° C, preferably in the range of 80 to 150 ° C. The molar ratio in the case of reacting the alkano-lamine of the general formula (43) or (44) in which the amino group is protected by ketimination with the chlorine-containing compound of the general formula (36) can be arbitrarily selected. Preferably, at least 1 mol of alkanolamine is reacted with 1 mol of the chlorine-containing compound, more preferably 1 to 10 mol. The reaction temperature at this time is also arbitrary, but is usually in the range of 120 to 150 ° C, preferably in the range of 110 to 80 ° C. The nitrogen-containing compound of the present invention represented by the general formula (1) is obtained by subjecting the thus obtained polyoxyalkylene glycol derivative having a ketimine terminal to a heat treatment in the presence of excess water. be able to. The reaction temperature in this hydrolysis step is also optional, but is usually in the range of 40 to 150 ° C, preferably 50 to 10 ° C. in the range o ° c.

Further, by adding an oxysilane compound of the general formula (27) to the terminal amino group of the product obtained by the above hydrolysis reaction, a nitrogen-containing compound having an alkanolamine type terminal can be obtained. As an alternative to the method for producing the nitrogen-containing compound of the present invention, instead of employing the above (C) chloroformation step and (D) carbonic acid esterification step, (Β ′) By employing the following (II) ester group introduction step and (F) transesterification reaction step, it is possible to synthesize the nitrogen-containing compound of the present invention represented by the general formula (45). -0-R ¹⁴ Doo N- X (45)

In the general formula (45), RR ² , R ³ , R \ R ⁵ , Ra, b, d and X are the same as the definitions of a, b, d and X in the general formula (1). ¹³ and R "are the same as defined for R ¹³ and R ¹⁴ in the general formula (5).

(E) Ester group introduction step

The polyoxyalkylene glycol derivative of the general formula (35) obtained in the polymerization step (Β ') or the metal alkoxide compound before neutralization thereof is converted into a monohalocarboxylic acid represented by the following general formula (46). By reacting with an acid ester, an ester compound represented by the general formula (47) is obtained.

QR ¹³ -C-0- ² (46)

II

0

In the general formulas (4 6) to (4 7), R ² , R ³ , RKR \ Ra and b represent I ¹ , R ² , R ³ , R ⁴ , R \ R ⁶ in the general formula (1). it is as defined for a and b, R ¹³ are the same as defined in R ¹³ in the general formula (5). R32 represents a hydrocarbon group having 1 to ³⁰ carbon atoms, and Q represents chlorine, bromine or iodine. In the general formula (46) representing a monohalocarboxylic acid ester, R32 represents a hydrocarbon group having 1 to ³⁰ carbon atoms, and the hydrocarbon group is a linear or branched hydrocarbon group having 1 to 24 carbon atoms. Alkyl group, linear or branched alkenyl group having 2 to 24 carbon atoms, cycloalkyl group or alkylcycloalkyl group having 5 to 13 carbon atoms, aryl group or alkyl having 6 to 18 carbon atoms Aryl group, carbon number? It is preferably any one of the arylalkyl groups from 1 to 19.

Preferred alkyl groups as R ^32, a methyl group, Echiru group, n- propyl group, an isopropyl group, n- heptyl group, an isobutyl group, sec- butyl group, tert- butyl group, straight 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 decyl , Linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pendecyl group, linear or branched hexadecyl group, linear or branched hepta group Even decyl, straight or branched octadecyl, straight or branched nonadecyl, straight or branched icosyl, straight or branched helicosyl, straight or branched docosyl, straight or branched A branched tricosyl group, a linear or branched tetracosyl group, etc.

Preferred alkenyl groups as R ³² include vinyl group, propenyl group, isopropenyl group, linear or branched butenyl group, phenyl group, linear or branched pentenyl group, linear or branched Hexenyl, linear or branched heptenyl, linear or branched octenyl, linear or branched nonenyl, linear or branched decenyl, linear or branched pendecenyl, linear or branched Branched dodecenyl, straight or branched tridecenyl, straight or branched tetradecenyl, straight or branched pentadecenyl, straight or branched hexadecenyl, straight or branched heptenyl decenyl, oleyl Linear or branched octadecenyl groups, such as linear or branched nonadecenyl groups A straight-chain or branched icosenyl group, a straight-chain or branched hexocenyl group, a straight-chain or branched docenyl group, a straight-chain or branched tricosenyl group, a straight-chain or branched tetracosenyl group, and the like. .

Preferred cycloalkyl groups as R ³² include cyclopentyl group, cyclohexyl group, cycloheptyl group and the like, and similarly preferred alkyl chloroalkyl groups include methylcyclopentyl group, dimethylcyclopentyl group (all substituted isomers include ), Ethyl cyclopentyl group (including all substituted isomers), linear or branched propyl cyclopentyl group (including all substituted isomers), ethyl methyl cyclopentyl group (including all substituted isomers) ), Trimethylcyclopentyl (including all substituted isomers), getylcyclopentyl (including all substituted isomers), ethyldimethylcyclopentyl (including all substituted isomers), linear or branched Branched propylmethylcyclopentyl group (all substituted isomers ), Linear or branched propylethylcyclopentyl group (including all substituted isomers), di-linear or branched propylcyclopentyl group (including all substituted isomers), linear or branched propyl Ethylmethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including To all substituted isomers), linear or branched propylcyclohexyl group (including all substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers), and trimethylcyclo to Xyl group (including all substituted isomers), getylcyclohexyl group (including all substituted isomers), ethyldimethyl K-hexyl group (including all substituted isomers), linear or branched propylmethylcyclohexyl group (including all substituted isomers), linear or branched propylethyl cyclohexyl group (including all substituted isomers) , Di-linear or branched propyl cyclohexyl group (including all substituted isomers), linear 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 Vilcycloheptyl group (including all substituted isomers) Tylcycloheptyl group (including all substituted isomers), trimethylcycloheptyl group (including all substituted isomers), getylcycloheptyl group (including all substituted isomers), ethyldimethylcycloheptyl Group (including all substituted isomers), linear or branched propylmethylcycloheptyl group (including all substituted isomers), linear or branched propylethylcycloheptyl group (including all substituted isomers) Di-linear or branched propylcycloheptyl groups (including all substituted isomers), linear or branched propylethylmethylcycloheptyl groups (including all substituted isomers) And cycloalkyl groups or alkylcycloalkyl groups.

The Ariru groups preferred as R ^32, phenyl group, a naphthyl group ani Gerare, the same preferred alkyl § aryl group (including all isomers) tolyl, xylyl (all isomers ), Ethylphenyl 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), tet Main Chirufueniru (inclusive of all isomers) group, (including all isomers) straight or branched Penchirufue two group, Kishirufu to straight or branched! : Nyl group (including all substituted isomers), linear or branched heptylphenyl group (including all substituted isomers), linear or branched octylphenyl group (including all substituted isomers) Straight-chain or branched nonylphenyl (including all substituted isomers), straight-chain or branched decylphenyl (including all substituted isomers), straight-chain or branched decylphenyl (including all substituted isomers) Including isomers), straight-chain or branched dodecylphenyl groups (including all substituted isomers), etc. Similarly preferred aryl alkyl groups include benzyl group, methylbenzyl group (including all substituted isomers) ), Dimethyl pendyl group (including all substituted isomers), phenethyl group, methylphenethyl group (including all substituted isomers), dimethyl Methyl group (all of the replacement Including isomers).

Among them, R ³² is more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl aryl group. In particular, when it is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, when it is a phenyl group, or when it is a direct sales or branched alkylaryl group having 7 to 9 carbon atoms, Even more preferred is a straight-chain or branched alkyl group having 1 to 3 carbon atoms. In the general formula (46), Q represents chlorine, bromine or iodine, and particularly preferably chlorine or bromine. The molar ratio when the polyoxyalkylene glycol derivative represented by the general formula (35) is reacted with the monohalocarboxylic acid ester represented by the general formula (46) can be arbitrarily selected. It is preferable to react the monohalocarboxylic acid ester in an amount of 1 mol or more, more preferably 1 to 8 mol, per mol.

The reaction temperature in the ester group introduction step can be arbitrarily selected, but is usually preferably selected in the range of 120 to 150 ° C, more preferably in the range of 110 to 80 ° C.

(F) Transesterification step

By performing an ester exchange reaction between the ester compound of the general formula (47) obtained in the above ester group introduction step and the alkanolamines represented by the aforementioned general formulas (37) to (39), Alternatively, the ester compound of the general formula (47) is transesterified with an alkanolamine in which the amino group represented by the general formulas (43) to (44) is protected with a ketone, and then the protection of the amino group is released. By doing so, the nitrogen-containing compound of the present invention represented by the general formula (45) can be obtained.

The molar ratio when the ester compound of the general formula (47) is reacted with the alkanolamine of the general formulas (37) to (39), (43) and (44) can be arbitrarily selected. Alkanolamine is reduced per mole of the ester compound. The reaction is preferably at least 1 mol, more preferably 1 to 20 mol.

The reaction temperature in the transesterification reaction step can be arbitrarily selected, but is usually preferably selected in the range of 60 to 200 ° C, and is preferably selected in the range of 100 to 160 ° C. More preferred. 1. The nitrogen-containing compound of the present invention represented by the general formula (1) is a very useful compound as an additive for fuel oil.

The term "fuel oil" as used herein means liquid hydrocarbons mainly intended for combustion, and usually has a boiling point of 30 to 700 ° C (preferably 40 to 600 ° C). Various types of liquid hydrocarbon fuel oils can be used and are not particularly limited, for example, petroleum, waste, oil sierre, oil sand, coal, biomass. Any liquid hydrocarbon fuel oil derived from the above can be used, but under the current environment, it is preferable to use a crude oil or a petroleum fraction as a main component.

As the crude oil that can be used as the liquid hydrocarbon fuel oil of the present invention, any crude oil such as barrafin base crude oil, naphthene base crude oil, mixed base crude oil, special crude oil, or a mixture thereof can be used.

The petroleum fraction that can be used as the fuel oil of the present invention is a fraction or residue obtained by appropriately performing distillation, cracking, reforming, or other refining treatment of the above crude oil or a mixture thereof. More specifically, for example, gasoline fractions represented by gasoline for automobile engines, gasoline for internal combustion engines for agriculture, gasoline for internal combustion engines for forestry, etc .; naphtha represented by naphtha for fuel, etc. Distillates (light naphtha, heavy naphtha, whole range naphtha, etc.); jet fuel fractions represented by jet fuel, aviation gasoline, etc .; kerosene for cooling and heating, kerosene for kitchens, kerosene for petroleum engines, industrial fuel Kerosene fraction typified by kerosene, etc .; Light oil fraction typified by light oil for automobile diesel engines, light oil for heating fuel, etc .; Heavy oil for boilers, for building heating Oil, fuel oil for marine diesel engines, heavy oil fractions typified ceramics for oil (A heavy oil, B heavy oil, C heavy oil); and the like and mixtures thereof. Examples of liquid hydrocarbon fuel oil derived from waste include, for example, urban Wastes, industrial wastes, waste oils, etc. are derived by decomposition, refining and other treatment. As the fuel oil in the present invention, any of the above-mentioned various liquid hydrocarbon fuel oils and mixtures thereof can be used, but the nitrogen-containing compound of the present invention was added to the gasoline for special engine engine. In this case, the gasoline engine exhibits extremely excellent cleanliness in the intake system and combustion chamber. More specifically, examples of the gasoline for internal combustion engines include gasoline No. 1 and gasoline No. 2 specified in JISK 222 “Automobile gasoline”.

Although the amount of the nitrogen-containing compound of the present invention to be added to the fuel oil is not particularly limited, the content of the nitrogen-containing compound is usually 0 based on the total amount of the fuel oil composition in consideration of the effect and economics of the addition. 0.05 to 10% by mass, preferably 0.01 to 5% by mass. In particular, when added to gasoline for internal combustion engines, the content of nitrogen-containing compounds is reduced on the basis of the total amount of the fuel oil composition, since it has an excellent effect on the cleanliness of the gasoline engine's intake system and combustion chamber. It is desirable to add so that the amount is 0.05 to 5% by mass, preferably 0.01 to 4% by mass, and more preferably 0.02 to 3% by mass.

The fuel oil composition to which the nitrogen-containing compound of the present invention is added has an extremely excellent effect on the cleanliness of the intake system and the combustion chamber of a gasoline engine, especially when gasoline for an internal combustion engine is used as the fuel oil. However, known fuel oil additives can be added alone or in combination of several types in order to further enhance the performance.Specifically, these additives include, for example, alcohols such as methanol and ethanol, and the like. Octane number improvers represented by ethers such as isopropyl ether, methyl tertiary butyl ether, and methyl tertiary amyl ether; octane improvers represented by aromatic amines; terephthalate represented by nitrate esters and organic peroxides Surface igniters; prevention of surface ignition represented by organic phosphates, halogenated organophosphates, etc. Antioxidants represented by phenols such as 2,6-di-tert-butyl-p-cresol, aromatic amines such as phenyl-phenyl-naphthylamine; and represented by salicylidene derivatives Metal deactivator; metal sulfone Detergents such as carboxylate, metal phosphate, metal salicylate, etc .; Ashless detergents and dispersants, such as alkenyl succinic acid imide, alkyl polyamine, polyether polyamine, etc .; Anti-freezing agents; microbial germicides represented by glycol ethers, boron compounds, etc .; burners represented by metal naphthenates, metal sulfonates, allyl sulfate, etc .; ethylene-vinyl acetate copolymers, Low-temperature fluidity improver represented by alkenyl succinic acid amide; corrosion inhibitor such as aliphatic amine and alkenyl succinic ester; antistatic agent such as anionic, cationic and amphoteric surfactant; Coloring agents such as azo dyes; and the like.

Optionally also the addition amount of the time of addition of these additives, typically, 0 individual added pressure of the additive of the total amount of the composition. 5 wt% or less, preferably is 0. 2% by weight or less _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 according to the present invention will be described 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 and 10 g (0.1 mol) of methylisobutyl ketone were added.

1 mol) and 100 ml of toluene, and the inside of the reaction vessel was replaced with nitrogen.

The mixture was heated at 120 ° C. for 5 hours to cause dehydration and ketimination reaction. After the ketimine reaction, the reaction mixture was cooled to room temperature, 5.6 g of potassium hydroxide was added thereto as an addition catalyst, and the atmosphere was replaced with nitrogen gas.After that, the mixture was heated to 120 ° C and heated to 87.0 g (1 5 mol), 9-3.2 g (0.5 mol) of 2-ethylhexylglycidyl ether was added,

The reaction was performed for 5 hours. Further, 7.9 g (0.1 mol) of 2-chloropropane was added and reacted for 2 hours, and then the reaction product solution was 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 100 g of the target nitrogen-containing compound. This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 190, and was yellow. As a result of ¹³ C—NMR analysis, this nitrogen-containing compound is represented by the formula (48). It was a random copolymer having an average structure. CH ₃

CH ₃ CH + OCHCH "^ OCHCH ₂ OCH ₂ CH ₂ NH ₂ ^ 48)

C ₄ H ₉ CHCH ₂ OCH ₂ CH ₃

C ₂ H ₅ ― —One-Synthesis example 2

In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet, 6.1 mol (0.1 mol) of monoethanolamine, 10 g (0.1 mol) of methyl isobutyl ketone and 10 mol of toluene 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 ketimine reaction. After the ketimine reaction, the reaction mixture was cooled to room temperature, 5.6 g of potassium hydroxide was added thereto as an addition catalyst, and the atmosphere was replaced with nitrogen gas.Then, the mixture was heated to 120 ° C and heated to 40.6 g of propylene oxide. (0.7 mol) and 130.4 g (0.7 mol) of 2-ethylhexylglycidyl ether were added and reacted for 5 hours. After completion of the reaction, the reaction product solution was neutralized with hydrochloric 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, 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 185 and was yellow. As a result of ¹³ C-NMR analysis, this nitrogen-containing compound was a random copolymer having an average structure represented by the formula (49).

_/ CH ₂ CH ₂ OH

H— OCHCH ₂ —— OCHCH ₂ —— OCH ₂ CH ₂ N (49) C4H9CHCH2OCH2 CH ₃ CH ₂ CH ₂ OH

C ₂ H ₅ Synthesis Example 3

N-? In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet —Hydroxitytyl morpholine 13.1 g (0.1 mol), toluene 100 ml, potassium hydroxide 5.6 g were added, and after purging with nitrogen gas, heated to 120 ° C, tert-butyl glycidyl ether 156. 1 g (1.2 mol) was added and reacted for 5 hours. Was added and reacted for 5 hours. After completion of the reaction, the reaction product solution was neutralized with hydrochloric acid and filtered to remove the additional catalyst. The toluene was further removed to obtain 150 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 1700, 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 (50).

(50)

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 diethylamine, 28.4 g (0.2 mol) of diisobutyl 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 ketimine 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 replaced with nitrogen gas.Then, the mixture was heated to 120 ° C and heated to 40.6 g (0.7 And tert-butylglycidyl ether (130.2 g, 1.0 mol) were added and reacted for 5 hours. After addition of 9.3 g (0.1 mol) of 1-methyl-2-methylpropane and reaction for 2 hours, the reaction product solution was filtered to remove the additional catalyst ₍ addition of 5 g of water. The mixture was subjected to a hydrolysis reaction for 3 hours at 90 ° C. Subsequently, excess water, toluene and ketone were removed to obtain 165 g of the target nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 1850, and was yellow. As a result of ¹³ C-NMR analysis, this nitrogen-containing compound was a random copolymer having an average structure represented by the following formula (51).

Synthesis example 5

In a pressure-resistant reaction vessel equipped with a thermometer, stirrer, reflux condenser and nitrogen inlet, 10.4 g (0.1 mol) of 2- (2-aminoethylamino) ethanol and 14.2 g (0.1 mol) of diisobutyl ketone 1 mol) and toluene 100 ml, and the inside of the reaction vessel was purged with nitrogen, and then heated at 120 ° C for 5 hours to cause dehydration and ketimination reaction. After the ketimination reaction, the reaction mixture was cooled to room temperature, added with 5.6 g of aqueous hydroxide as an additional catalyst, replaced with nitrogen gas, heated to 120 ° C, and heated to 87.0 g of propylene oxide (1. 5 mol) and 93.2 g (0.5 mol) of 2-ethylhexylglycidyl ether were added and reacted for 5 hours. Further, 9.3 g (0.1 mol) of 1-methyl-1-methylpropane was added and reacted for 2 hours. Then, the reaction product solution was 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, 4.4 g (0.1 mol) of ethylene oxide was added to obtain 175 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2,000, and was yellow. As a result of ¹³ C-NMR analysis, this nitrogen-containing compound was a random copolymer having an average structure represented by the formula (52).

Examples 1 to 5 and Comparative Examples 1 to 3

A base gasoline (gasoline for internal combustion engines) 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-Two---One Reid vapor pressure 0.66 kgf / cm ²

Specific gravity 0.724

Boiling range 30 to 1 90 ° C

Octane number 98.0

The base gasoline was blended with the nitrogen-containing compound of the present invention obtained in Synthesis Examples 1 to 5 to prepare fuel oil compositions having the compositions shown in Examples 1 to 5 in Table 1.

Each of these fuel oil compositions was subjected to the following engine evaluation tests. The results are shown in Table 1.

[Engine evaluation test]

① Intake system deposit cleanliness evaluation test

Using a passenger car equipped with an unused engine with a total displacement of 2,000 ml and a fuel injector, the following one-cycle, one-hour running mode was repeated for 200 hours using only base gasoline, and then the engine was disassembled. The amount of deposit adhering to the intake valve was measured.

Driving mode

Idling: 1 minute

Engine speed 1 50 Orpm, intake negative pressure-20 OmmHg: 30 minutes

Engine speed 270 Orpm, intake negative pressure-30 OmmHg: 20 minutes

Engine stop: 9 minutes

Next, the engine was assembled without removing the deposit, the fuel was changed to the fuel oil compositions of Examples 1 to 5, and the above-mentioned running mode was repeated for 30 hours.

After the test was completed, the engine was disassembled again and the amount of deposit adhering to the intake valve was measured, and the difference from the amount of deposit before use of the fuel oil composition of the example was determined. The cleanliness was evaluated.

② Combustion chamber deposit cleanliness evaluation test

Using a passenger car equipped with a fuel injection type unused engine with a total displacement of 200 ml, using the fuel oil composition of the example as fuel, engine speed 150 rpm, suction negative pressure 1 It was operated for 96 hours under the operating conditions of 15 O mmHg and a cooling water temperature of 50 ° C. After that, the engine was disassembled and the amount of deposits in the combustion chamber was measured to determine the difference from the amount of deposits in the combustion chamber when only base gasoline was used.

For comparison, in the case of base gasoline alone without a nitrogen-containing compound added (Comparative Example 1), the case of using a polybutenylamine-based detergent instead of the nitrogen-containing compound of the present invention (Comparative Example 2 and The same engine evaluation test was performed for Comparative Example 3). The results are also shown in Table 1.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition Base gasoline [99.96] [99.96] [99.96] [99.96] [99.96] [100.00] [99.96] [99.96] Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5

Nitrogen-containing compounds--

[0.04] [0.04] [0.04] [0.04] [0.04]

Quantity

Polybutenyl Polybutenyl

% Other Amine 1 ¹ ) Amine 2 ² )

[0.04] [0.04] Expiratory deposit

Gene -75.1 -38.4 -55.4 -62J -82.4 +24.8 -29.4 -46.3 Change in amount (mg)

, >>

Test Combustion chamber deposit

¾ 'b ^ Tasu15.3 -0.8 Tasu8.9! - Tasu18.0 Tasu21.3 +331 .6 Tasu786.2 amount ³⁾ (mg)

1) Polybutenylamine detergent 1

Positive component: imid of polybutenyl succinic acid and tetraethylene pentamine (number average molecule it about 300)

2) Polybutenylamine detergent 2

Active ingredient: polybutenyltetraethylenepentamine (number average molecular weight about 350)

3) Difference from combustion chamber deposit amount when base gasoline is used

As is evident from the results of the engine evaluation test in Table 1, the fuel oil compositions of Examples 1 to 5 to which the nitrogen-containing compound according to the present invention was added generated a deposit in the combustion chamber as compared with the case where none was added. It has a very good effect on the cleanliness of the deposits in the intake system with almost no increase in air pollution. On the other hand, when the fuel oil of Comparative Example 1 containing no detergent was used, the cleanliness of the deposit in the intake system was poor, and the fuel oil of Comparative Examples 2 and 3 using a commercially available polybutenylamine-based detergent was poor. Although the fuel oil composition has a certain degree of T-gas and air-based deposit cleanliness, the amount of combustion chamber deposit increases significantly compared to the case where no detergent is added. Synthesis Example 6

A 1 L three-necked flask equipped with a thermometer, stirrer, and reflux condenser was charged with 61 g (1.0 mol) of monoethanolamine and 500 g (5.0 mol) of methyl isobutyl ketone. After heating at 15 ° C. for 5 hours to cause dehydration and ketimination reaction, excess ketone was removed to obtain 135 g of an aminoamine-protected ethanolamine.

4.45 g (0.06 mol) of tert-butyl alcohol and 3.37 g (0.06 mol) of lithium hydroxide were placed in a 1-liter autoclave, and the system was nitrogenated. After replacing with elemental gas, heat to 90 ° C. Then, 67.07 g (0.36 mol) of 2-ethylhexylglycidyl ether, 62.73 g (1.08 mol) of provenoxide and 100 ml of toluene were added thereto. The reaction was conducted 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 toluene was extracted and the solvent toluene was distilled off to obtain 120 g of a polyoxyalkylene compound.

Next, 8.0 g (0.081 mol) of liquid phosgene was added to a mixed solution of 100 g of this polyoxyalkylene compound (equivalent to 0.04 mol: calculated from the weight average molecular weight) 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 101 g of a chlorine-containing compound.

Then, 100 ml of toluene and 100 ml of pyridine were added to the amino group. After cooling a mixed solution of 57.2 g (0.4 mol) of evening noluamine to 5 ° C, 100 g of the above-mentioned chlorine-containing compound (equivalent to 0.04 mol: calculated from the weight average molecular weight) was added dropwise.

The reaction was carried out for 3 hours while maintaining the system at 5 ° C. After completion of the reaction, unreacted ethanolamine, pyridine, and the generated hydrochloride of pyridine are removed, and 5 g of water is further added.

The hydrolysis reaction was performed at 0 ° C for 3 hours. Subsequently, excess water, toluene and -kedon were removed and purified to obtain 95 g of the desired nitrogen-containing compound.

This amine 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 (53). -O-CH ₂ CH ₂ NH ₂ (53)

Synthesis Example 7

4.45 g (0.06 mol) of tert-butanol and 3.37 g (0.06 mol) of potassium hydroxide were placed in a 1-liter auto crepe, and the system was replaced with nitrogen gas. Then, heat to 90 ° C. Then, 67.07 g (0.36 mol) of 2-ethylhexylglycidyl ether, 62.73 g (1.08 mol) of propylene oxide and 100 ml of toluene were added thereto, and the reaction temperature was 120 ° C. The reaction was performed for 5 hours. After completion of the reaction, the mixture was cooled on ice, and while maintaining the reaction system at 0 ° C., 13.0 g (0.12 mol) of methyl monomethyl acetate was added, and the reaction was carried out at room temperature for 5 hours with stirring. After the completion of the reaction, the excess methyl acetate, the generated inorganic salt and the solvent, toluene, were removed to obtain 125 g of an ester compound.

Next, 100 g of the above ester compound was added to a mixed solution of 10 g of dehydrated P-toluenesulfonic acid, 100 ml of toluene, and 57.2 g (0.4 mol) of the amino group-protected ethanolamine synthesized in Synthesis Example 1. (Equivalent to .04 mol: calculated from the weight average molecular weight), and heat the reaction system to 110 ° C to remove the generated methanol. The transesterification was carried out for 10 hours. After completion of the reaction, unreacted ethanolamine and p-toluenesulfonic acid as a catalyst were removed, and 5 g of water was further added, followed by a hydrolysis reaction at 90 ° C for 3 hours. Subsequently, excess water, toluene and ketone were removed, and 1.76 g (0.04 mol) of ethylene oxide was added to obtain 98 g of the target nitrogen-containing compound.

This amine compound was an oily liquid having a number average molecular weight of about 2400, 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 (54).

CH3 (54)

Synthesis Example 8

Iso-propanol 3.60 g (0.06 mol) and potassium hydroxide 3.37 g (0.06 mol) were placed in a 1 liter autoclave, and the system was purged with nitrogen gas. Heat to C. Thereafter, 48.56 g (0.48 mol) of tert-butyl glycidyl ether, 41.82 g (0.72 mol) of propylene oxide and 100 ml of toluene were added thereto, and the mixture was reacted at a reaction temperature of 120 ° C. for 5 hours. I responded. After completion of the reaction, the reaction product solution was neutralized with hydrochloric acid, and then toluene was extracted and the solvent toluene was distilled off to obtain 85 g of a polyoxyalkylene compound.

Next, 8.0 g (0.081 mol) of liquid phosgene was added to a mixed solution of 8 ° g (equivalent to 0.04 mol: 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 the completion of the reaction, excess phosgene was removed, and toluene as a solvent was distilled off to obtain 81 g of a chlorine-containing compound. Next, a mixed solution of 100 ml of toluene, 100 ml of pyridine and 52.4 g (0.4 mol) of N-3-hydroxyethyl morpholine was cooled to 5 ° C, and then 80 g of the above chlorine-containing compound (0.04 mol Equivalent: calculated from the weight average molecular weight), and reacted for 3 hours while maintaining the system at 5 ° C. After completion of the reaction, unreacted N-?-Hydroxyethylmorpholine, pyridine, the hydrochloride salt of pyridine and the solvent -luene_ are removed and purified to obtain 80 g of the desired nitrogen-containing compound. Was.

This amine compound was an oily liquid having a number average molecular weight of about 1,950, 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 (55).

,, /, 严 \

CH3CH-0- ^ -CH ₂ CHO ^ CH2CHO C-0-CH ₂ CH ₂ NO

12 (55)

II CH ₃ CH ₂ CH ₃ o zu ₂ cu ₂ ^//

O

CH ₃ — C-CH ₃

CH ₃ synthesis example 9

The same equipment as in Synthesis Example 3 except that 35.6 g (0.4 mol) of 2-dimethylaminoethanol was used in place of 52.4 g (0.4 mol) of N_3-hydroxyethylmorpholine By the method, 75 g of the desired amine compound was obtained.

This amine compound was an oily liquid having a number average molecular weight of about 1900, and had a dark orange color. As a result of ¹³ C-NMR analysis, this amine compound was a random copolymer having an average structure represented by the formula (56).

CH ₃ CH— 0- CHCHO- CH ₂ CHO- -CO- -CH CH CH N

12 (56) II CH ₃ CH ₂ CH, o

O

CH ₃ — C-CH ₃

CH ₃ Synthesis example 1 o

In a 1 L three-necked flask equipped with a thermometer, stirrer, and reflux condenser, 2- (2-aminoethylamino) ethanol 1004.2 g (1.0 mol), methyl isobutyl ketone 500 g (5 2.0 mol), heated at 115 for 5 hours, dehydrated and subjected to ketimination reaction, and by removing excess ketone, the amino group was protected 2-(2-aminoethylamino). ) 180 g of ethanol were obtained.

Nonylphenol 13.3 g (0.06 mol) and potassium hydroxide 3.37 g (0.06 mol) were placed in a 1-liter autoclave, and the system was replaced with nitrogen gas. Heat to 90 ° C. Thereafter, 101.4 g (0.78 mol) of t tert-butyl glycidyl ether and 100 ml of toluene were added thereto, and the mixture was reacted at a reaction temperature of 120 ° C. for 5 hours. After completion of the reaction, the mixture was cooled on ice, and while maintaining the reaction system at 0 ° C., 13.0 g (0.12 mol) of methyl acetate was added thereto, and the reaction was carried out at room temperature for 5 hours with stirring. . After the completion of the reaction, the excess methyl acetate, the generated inorganic salt, and the solvent, toluene, were removed to obtain 125 g of an ester compound.

Next, a mixed solution of 10 g of dehydrated P-toluenesulfonic acid, 100 ml of toluene and 93.0 g (0.5 mol) of 2- (2-aminoethylamino) ethanol protected with an amino group To the above was added 100 g of the above ester compound (equivalent to 0.05 mol: calculated from the weight-average molecular weight), and the reaction system was heated to 110 ° C. while removing generated methanol to obtain 100 g. Transesterification was performed for hours. After completion of the reaction, unreacted 2- (2-aminoethylamino) ethanol and p-toluenesulfonic acid as a catalyst were removed, and 5 g of water was added, followed by hydrolysis at 90 ° C for 3 hours. . Subsequently, excess water, toluene and ketone were removed, and purification was performed to obtain 95 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number-average molecular weight of about 250 and exhibited a deep 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 (57).

Synthesis example 1 1

100 g of a nitrogen-containing compound having an average structure represented by the formula (57) synthesized by the same method as in Synthesis Example 10 (equivalent to 0.05 mol: calculated from the weight average molecular weight) was added to 4.40 g of ethylene oxide (0 10 mol) to give 98 g of the desired nitrogen-containing compound.

This nitrogen-containing compound was an oily liquid having a number average molecular weight of about 2150, 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 (58).

Examples 1 to 6 and Comparative Examples 1 to 3

Base gasoline properties

Reed vapor pressure 0.65kgf / cm ²

Specific gravity 0.726

Boiling range 30 ~: L 90 ° C

Octane number 98.0 Using this base gasoline and the nitrogen-containing compound of the present invention obtained in Synthesis Examples 6 to 11, the fuel oil according to the present invention was prepared by blending as shown in each example (Examples 6 to 11) in Table 2. A composition was prepared.

The same engine evaluation test as in Examples 1 to 5 was performed on each of these fuel oil compositions. Table 2 shows the results. For comparison, in the case of base gasoline alone without the addition of nitrogen-containing compounds (Comparative Example 4), the case of using a polybutenylamine-based detergent instead of the nitrogen-containing compound of the present invention (Comparative Example 5 and The same engine evaluation test was performed for Comparative Example 6). The results are shown in Table 2.

Table 2

1) Polybutenylamine detergent 1

Active ingredient: imid of polybuteric succinic acid and tetraethylene pentamine (number Ψ-average molecular Jit about 300)

2) Polybutenylamine detergent 2

Active ingredient: polybutenyltetraethylenepentamine (number-average molecular weight about 350)

3) Difference from the amount of deposit in the combustion chamber when using gasoline

As is clear from the results of the engine evaluation test in Table 2, the fuel oil compositions of Examples 6 to 11 according to the present invention almost all increase the generation of combustion chamber deposits as compared with the case where no fuel oil was added. It has no significant effect on the cleanliness of the deposits in the intake system. In contrast, Comparative Example 4, which did not contain a nitrogen-containing compound, had poor air-based deposit cleanability, and contained a commercially available polybutenylamine-based detergent. However, the amount of combustion chamber deposit increases significantly compared to the case without the addition. In summary, according to the present invention, a fuel oil additive exhibiting an excellent cleaning effect even under severe conditions such as when the engine is cold, and a fuel oil composition containing the additive are obtained. Can be

Claims

Claims A fuel oil additive comprising a nitrogen-containing compound represented by the following general formula (1) (-X (1)

[In the general formula (1), 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 or a hydrocarbon group having 1 to 10 carbon atoms. A group represented by the following general formula (2) (wherein at least one of R ² , R ³ , R ⁴ and R ⁵ is a group represented by the general formula (2)) R ⁶ represents an alkylene group having 1 to ⁶ carbon atoms, Z represents a group represented by one of the following general formulas (3) to (5), and X represents one of the following groups A A represents an integer from 1 to 100, b represents an integer from 0 to: L00, and a + b = 1 to 200, c represents 0 or 1, and d represents 1 to 100. An integer of 3 and e is an integer of 0 to 2 and d + e = 3. However, when Z is the general formula (4) or (5), when e = l, X is not A3, and when e = 2, one of X is A3 and the other is It cannot be A2 or A3. ]

[In the general formula (2), 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 2 carbon atoms. Or an alkylene group having a total number of carbon atoms of 4 to 10 having an alkoxyalkyl group as a substituent; R ^1Q represents hydrogen or a hydrocarbon group of 1 to 30 carbon atoms; : Represents an integer of 0 to 50. ] π

■ 0-C-R (3)

II

0 12

-O-C-O-R (4)

II

o

13 14

-O-R R (5)

[In the general formulas (3) to (5), II ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent an alkynylene group having 1 to 6 carbon atoms in Sl. ]

Group A o A 1: hydrogen

A2: Hydrocarbon group having 1 to 30 carbon atoms

A3: Alkinol group represented by the following general formula (6)

R— 0H (6)

[In the general formula (6), R ¹⁵ represents an alkylene group having ¹⁶ carbon atoms. ]

A: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), R ¹⁶ represents an alkylene group having 2 to 6 carbon atoms, R ¹⁷ represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a group represented by the general formula (6); R ¹⁸ represents hydrogen, a hydrocarbon group having 1 to 30 carbon atoms or a group represented by the above general formula (6), and g represents an integer of 1 to 5. ]

A 5: a group represented by the following general formula (8)

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 6 carbon atoms, and R ^2tl , R ²¹ , R ²² and R ²³ independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group. Y is a methylene group, a hydrocarbon group having 1 to 10 carbon atoms. Represents a methylene group, an imino group, a hydrocarbon group having 1 to 10 carbon atoms or an imino group or an oxygen substituted with a hydroxyl group, and h is 1 when e = 1, and e = In the case of 2, it is 0 or 1 (however, in the case of h20, N (nitrogen) in the general formula (8) corresponds to N (nitrogen) in the general formula (1).].

2 The fuel oil additive according to claim 1, wherein the nitrogen-containing compound is represented by the following general formula (1) _:

[In the general formula (1), R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group or an alkyl aryl group having 6 to 18 carbon atoms, and R ² , RR ⁴ and R ^{5 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (2) (provided that R ² , R ³ , R ⁴ and R ⁵ , at least one is a group represented by the general formula (2)), R ⁶ is an alkylene group having 1 to 4 carbon atoms, and Z is 1 of the following general formulas (3) to (5). X represents a group selected from the following group A, a is an integer of 1 to 100, b is 0 to: an integer of L00, and a + b = 1 to 200, c is 0 or 1, d is an integer of 1 to 3, e is an integer of 0 to 2, and d + e = 3. However, when Z is the general formula (4) or (5), when e = l, X is not A3, and when e = 2, one of X is A3, The other is never A2 or A3. ^] R7

—C-0- R ⁹ _0 R ^1Q ( ² )

R ^{8 f}

In the general formula (2), R ⁷ and R ^{8 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms, and R ⁹ represents 2 to 6 carbon atoms. And R ¹¹¹ represents hydrogen or an alkyl group having 1 to 12 carbon atoms, and f represents an integer of 0 to 30. ]

-O-R — C-O-R-(5)

II

o

[In the general formula (3) ~ (5), R ", R 12, and R ^'4 represents it it individually an alkylene group having 1 to 4 carbon atoms.]

Group A

A 1: hydrogen

A 2: alkyl group having 1 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms or arylalkyl group hydrocarbon group

A: Alkinol group represented by the following general formula (6)

— R ¹ — OH (6)

[In the general formula (6), R ¹⁵ represents an alkylene group having 1 to 4 carbon atoms. ]

A 4: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), R ¹⁶ represents an alkylene group having 2 to 4 carbon atoms, R ¹⁷ represents an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents hydrogen, an alkyl group having 1 to 12 carbon atoms or It represents an aryl group or an arylalkyl group having 6 to 12 carbon atoms, and g represents an integer of 1 to 4. ] A 5: a group represented by the following general formula (8)

[In the general formula (12), 1 ^ is a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group or an alkyl aryl group having 6 to 18 carbon atoms, and R ² , ΕΛ R ⁴ and R ^{5 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (2) (provided that R ² , R ³ , R ⁴ and At least one of R ⁵ is a group represented by the general formula (2)), R ⁶ is an alkylene group having 1 to 4 carbon atoms, and X is a group selected from the following group A. , A is an integer from 1 to 100, b is an integer from 0 to: 100, and a + b = l to 200, c is 0 or 1, d is an integer from 1 to 3, e is 0 It is an integer of ~ 2 and d + e = 3. ]

[In the general formula (2), R ⁷ and R ⁸ it it independently hydrogen, shows the alkoxyalkyl group of the alkyl group or the number of carbon atoms from 2 to 6 1 to 6 carbon atoms, R ⁹ is 2 to 6 carbon atoms R ^1Q represents hydrogen or an alkyl group having 1 to 12 carbon atoms; and f represents an integer of 0 to 30. ]

Group A

A 1: hydrogen

A 2: an alkyl group having 1 to 12 carbon atoms, an aryl group or an arylalkyl group hydrocarbon group having 6 to 12 carbon atoms

A _: an alkanol group represented by the following general formula (6)

— R ¹ — OH (6)

A 4: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), R ¹⁶ represents an alkylene group having 2 to 4 carbon atoms, R ¹⁷ represents an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents hydrogen, and an alkyl group having 1 to 12 carbon atoms. Or an aryl group or an arylalkyl group having 6 to 12 carbon atoms, and g represents an integer of 1 to 4. ]

A 5: a group represented by the following general formula (8)

(8)

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 4 carbon atoms, and R ^2Q , R ²¹ , R ²² and R ²³ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms. Or a hydroxyl group, Y represents a methylene group, an alkyl group having 1 to 6 carbon atoms, an imino group substituted with a hydroxyl group, or oxygen, h represents 1 when e = 1, and 0 or 0 when e = 2 1 (however, when h = 0, N (nitrogen) in the general formula (8) corresponds to N (nitrogen) in the general formula (1).]

4. The fuel oil additive according to claim 1, wherein the nitrogen-containing compound is represented by the following general formula (13).

[In the general formula (13), R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aryl group or an alkyl aryl group having 6 to 18 carbon atoms; ⁴ and R ^{5 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (2) (provided that R ² , R \ R ⁴ and R ⁵ Wherein at least one is a group represented by the general formula (2)), R ⁶ represents an alkylene group having 1 to 4 carbon atoms, R ¹¹ represents an alkylene group having 1 to 4 carbon atoms, and X represents A represents an integer of 1 to 100, b represents an integer of 0 to 100, and a + b = 1 to 200, and c represents 0 or 1. , D is an integer of 1 to 3, e is an integer of 0 to 2, and d + e = 3. ]

[In the general formula (2), R ⁷ and R ^{8 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms, and R ⁹ represents 2 to 6 carbon atoms. R ^1fl represents hydrogen or an alkyl group having 1 to 12 carbon atoms; and f represents an integer of 0 to 30. ]

Group A

A 1: hydrogen

A 2: alkyl group having 1 to 12 carbon atoms, aryl group or aryl group having 6 to 12 carbon atoms Alkyl group hydrocarbon group

A3: alkanol group represented by the following general formula (6)

Fifteen

— R 0H (6)

[In the general formula (6), R ¹⁵ represents an alkylene group having ¹⁴ carbon atoms. ]

A 4: Nitrogen-containing group represented by the following general formula (7)

[In the general formula (7), R ¹⁶ represents an alkylene group having 2 to 4 carbon atoms,

R ¹⁷ represents an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an aryl group or an aryl alkyl group having 6 to 12 carbon atoms, g Represents an integer of 1 to 4. ]

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 4 carbon atoms, and R ² °, R ²¹ , R ²² and R ²³ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group. Y represents a methylene group, an alkyl group having 1 to 6 carbon atoms, an imino group substituted with a hydroxyl group, or oxygen, and h represents 1 when e = 1 and 0 or 1 when e = 2. (However, when h = 0, N (nitrogen) in the general formula (8) corresponds to N (nitrogen) in the general formula (1).) The nitrogen-containing compound is represented by the following general formula ( The fuel oil additive according to claim 1, which is represented by (14) or (15).

[In the general formulas (14) and (15), 1 ^ is a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or an aryl or alkylaryl group having 6 to 18 carbon atoms. R ² , R ³ , R ⁴ and R ^{5 each} independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by the following general formula (2) (provided that R ² At least one of R ³ , R ⁴ and R ⁵ is a group represented by the general formula (2)), R ⁶ is an alkylene group having 1 to 4 carbon atoms, and R ¹² , R ¹³ and R ¹⁴ individually represents an alkylene group having 1 to 4 carbon atoms, X represents a group selected from the following group A, a is an integer of 1 to 100, b is an integer of 0 to 100, And a + b = 1-200, c is 0 or 1, d is an integer of 1-3, e is an integer of 0-2, and d + e = 3. However, when e = l, X is not A3, and when e = 2, one of X is not A3 and the other is not A2 or A3. ]

[In the general formula (2), R ⁷ and R ⁸ it it independently hydrogen, shows the alkoxyalkyl group of the alkyl group or the number of carbon atoms from 2 to 6 1 to 6 carbon atoms, R ⁹ is 2 to 6 carbon atoms Represents an alkylene group or an ethylene group substituted with an alkoxyalkyl group having 2 to 8 carbon atoms, wherein ^1Q represents hydrogen or an alkyl group having 1 to 12 carbon atoms, and f represents an integer of 0 to 30. ]

Group A

A 1: hydrogen

A3: Alkinol group represented by the following general formula (6)

■ R— OH (6) [In the general formula (6), R ¹⁵ represents an alkylene group having 1 to 4 carbon atoms. ]

A: Nitrogen-containing group represented by the following general formula (7)

A 5: a group represented by the following general formula (8)

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 4 carbon atoms, and R ²⁰ , R ²¹ , R ²² and R ²³ independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group. And Y represents a methylene group, an alkyl group having 1 to 6 carbon atoms, an imino group substituted with a hydroxyl group, or oxygen, and h is 1 when e = 1, and is 0 or 1 when e = 2. (However, when h = 0, N (nitrogen) in the general formula (8) corresponds to N (nitrogen) in the general formula (1).) A fuel oil composition comprising a nitrogen-containing compound represented by the formula (1) (

[In the general formula (1), 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, 1 to 1 carbon atoms 0 hydrocarbons A group represented by the following general formula (2), provided that at least one of R ² , R ³ , R ⁴ and R ⁵ is a group represented by the general formula (2) R ⁶ represents an alkylene group having 1 to ⁶ carbon atoms, Z represents a group represented by one of the following general formulas (3) to (5), and X represents one of the following groups A Represents a selected group, a is an integer of 1 to 100, b is an integer of 0 to 100, and a + b = l to 200, c 0 or 1, and d is an integer of 1 to 3 , E is an integer from 0 to 2 and d + e = 3. However, when Z is the general formula (4) or (5), when e = l, X is not A3, and when e = 2, one of X is A3 and the other is It cannot be A2 or A3. ]

[In the general formula (2), 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 having 2 to 10 carbon atoms. 6 represents an alkylene group, or represents an alkylene group having a total of 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, R ^{1 ()} represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, f represents an integer of 0 to 50. ]

-0-CR ¹¹ - ⁽³⁾

II

0

12

■ 0-C-0-R (4)

II

o

0-R ¹³ — C-0-R ^14- (5)

II

0

[In the general formula (3) ~ (5), R ", R 12, R 13 and R ¹⁴ show it it individually an alkylene group having 1 to 6 carbon atoms.]

Group A

A 1: hydrogen A 2: Hydrocarbon group having 1 to 30 carbon atoms

A: Alkinol group represented by the following general formula (6)

― R— 0H (6)

[In the general formula (6), R ¹⁵ represents an alkylene group having 1 to 6 carbon atoms. ]--:

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

R ¹⁷ g

A 5: a group represented by the following general formula (8)

R ²⁰ R ²¹

C = C

, 19 | 'ヽ

-R ¹ NY

ノ h ヽ '( ⁸ )

n C = C

R ²² R ²³

[In the general formula (8), R ¹⁹ represents an alkylene group having 2 to 6 carbon atoms, and R ²⁰ , R ²¹ , R ²² and R ²³ each independently represent hydrogen, a hydrocarbon group having 1 to 10 carbon atoms or Y is a methylene group, a hydrocarbon group having 1 to 10 carbon atoms, a methylene group substituted with a hydroxyl group, an imino group, an imino group substituted with a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group, or oxygen. Where h is 1 when e = 1, 0 or 1 when e = 2 (however, when h = 0, N (nitrogen) in the general formula (8) is a general formula It corresponds to N (nitrogen) in (1).]

7. The fuel oil composition according to claim 5, comprising 0.0005 to 10% by mass of the nitrogen-containing compound based on the total amount of the composition.