JP2602553B2 - Fuel additive - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a fuel additive and a fuel composition containing the same, and more particularly, to a fuel additive excellent in cleanliness of a fuel system and a combustion chamber of an internal combustion engine. The present invention relates to a fuel additive and a fuel composition using the same.

In the present invention, the fuel refers to fuel used for internal combustion engines such as gasoline, diesel light oil, and heavy oil.

[Problems to be solved by conventional technology and invention]

When deposits such as sludge and deposits are formed in the fuel system and the combustion chamber of the internal combustion engine, the function of the engine is degraded and the exhaust gas is adversely affected.

Fuel detergents, such as gasoline detergents, remove deposits and prevent adhesion of gasoline intake systems such as carburetors and intake valves.
It is added to gasoline for the purpose of purifying the combustion chamber. Deposits generated at the intake valves and the intake ports cause a decrease in engine output, a decrease in drivability, and an increase in exhaust gas. In recent years, engines have become increasingly sophisticated and, as a result, have become more sensitive to such deposits. In particular, this is a major problem in the fuel nozzles of the fuel injection system, which have been increasing recently. That is, since the injection nozzle has a narrow fuel flow path, if a deposit is formed in the fuel nozzle, the injection pattern of the fuel is distorted, and serious adverse effects such as poor startability, poor operability, and reduced output appear. In addition, adverse effects such as deterioration of fuel efficiency and increase of exhaust gas also appear.

Various fuel additives have been proposed to solve such a problem. For example, USP 3,849,083, JP-B-57-
No. 24398 discloses an etheramine, which is used as a cleaner for a vaporizer, but has a small cleaning effect on an intake system other than the vaporizer.

Like fuel injection in gasoline vehicles, fouling of injection nozzles in diesel engines, mainly coking, has a significant effect on performance. When coking is generated, the amount of hydrocarbons generated by the partial combustion of sulfate, fuel and lubricating oil derived from black smoke in exhaust gas or sulfur in fuel (these collectively are called particulates) increase. I do.

In order to solve such a problem, Japanese Patent Application Laid-Open No. Sho 62-68891 proposes an oxyalkylene compound of an alkylamine.

 However, the cleaning function of the injection nozzle is not sufficient.

The present inventors have found that certain amines or amine oxides, such as alkyl ether amines, have a significant effect on cleaning the fuel system and combustion chamber of an internal combustion engine. As the prior art, US Pat. No. 3,478,096 and US Pat. No. 3,637,358 describe use of alkyl ether amine as a fuel additive.However, these inventions have an effect as a fuel stabilizer, and No cleaning action could be expected as an additive.

Under the circumstances described above, an object of the present invention is to provide a fuel additive having excellent cleanliness resistance to a fuel system and a combustion chamber of an internal combustion engine and a fuel composition containing the same. It is.

[Means for solving the problem]

In order to solve such problems of the related art, the present inventors have made intensive studies and, as a result, have reached the present invention.

That is, the present invention relates to (a) an alkyl group having 3 to 18 carbon atoms, an alkyl group having 9 to 37 carbon atoms including the branched portion, and (b) an alkyl group having 2 to 4 carbon atoms. A fuel additive comprising an amine or an amine oxide having at least one oxyalkylene group.

(A) having an alkyl group having 3 to 18 carbon atoms, having an alkyl group having 9 to 37 carbon atoms including the branched portion, and (b) having 2 to 4 carbon atoms. Examples of the amine or amine oxide having one or more oxyalkylene groups include compounds represented by the following general formulas (1), (2) or (3).

[Wherein, R ₁ and R ₂ are hydrocarbon residues having 3 to 18 carbon atoms, and the sum of the carbon numbers of R ₁ and R ₂ is 8 to 36.

n is 0 or an integer of 1-4.

Y ₁ is the formula An amine or amine oxide residue represented by the formula: Y ₂ , Y ₃ is a formula In represented by amine or amine oxide residue represented a (where B is an alkylene group having 2 to 4 carbon atoms, m is an integer of 0, R represents _{-, - CH 2 CONH -,} - CH 2 CH (OH ) −, − CH ₂ CO−
A is-or an alkylene group having 1 to 4 carbon atoms, R ₃ and R ₄ are H or an alkyl group or a hydroxyalkyl group or an aminoalkyl group having 1 to 4 carbon atoms, and _L is 1 or 2
Is). As R ₁ and R _{2 in the} formulas (1) to (3), a linear hydrocarbon group or a branched hydrocarbon group is used. Examples of the linear hydrocarbon group include, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n
-Undecyl group, n-dodecyl group, n-tridecyl group,
Examples thereof include an n-tetradecyl group, an n-pentadecyl group, and an n-hexadecyl group. Examples of the branched hydrocarbon group include an iso-propyl group, an iso-butyl group, an iso-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group,
3-methylbutyl group, (5-methylhexyl group), (1,1,3-trimethylbutyl group), (1,3,3-trimethylbutyl group), CH ₃ CH ₂ CH ₂ CH (CH ₃ ) CH ₂
CH _2- (3-methylhexyl group), (1,2,4-trimethylpentyl group), (1,3-dimethylhexyl group), (3,3,5-trimethylhexyl group), (3,5,5-trimethylhexyl group), (3,4,6-trimethylheptyl group), (3,5,6-trimethylheptyl group), (3,5-dimethyloctyl group), (1,3,4,6-tetramethylheptyl group), (1,1,3,5,5-pentamethylhexyl group), (1,4,7-trimethyloctyl group), (1,3,3,6-tetramethylheptyl group), (3,5,6,8-tetramethylnonyl group), (3,3,5,7-pentamethyloctyl group), (3,6,9-trimethyldecyl group), (1,2,4,6,8-pentamethylnonyl group), (4,5,7,9,11-pentamethylundecyl group) and the like.

The sum of the carbon numbers of R ₁ and R ₂ is 8-36. If the number is less than 8, the cleaning effect is not sufficient, and if it exceeds 36, the solubility of the obtained compound in fuel decreases. In addition, a combustion residue is generated.

Considering such characteristics, as the carbon chain length of a portion of the R _1, R ₂ 3 to 18, R ₁ and the sum of the number of carbon atoms in R ₂ is preferably 8 to 36, more preferably from 10 to 32.

Still referring to compounds of formula (1) ~ (3), Y 1 ~Y 3 represented by amine or amine oxide residues in the - (BO) _m - or - (BO) _{m + 1} - Represents an oxyalkylene or polyoxyalkylene ether structure. The alkylene group B in this case has 2 to 4 carbon atoms, and the alkylene group used in this case includes ethylene, propylene and butylene (1,2-; 2,3; 1,3 and 1,4-) groups. No. M is 0 to 10.

In the method for producing the compounds represented by the above general formulas (1) to (3), for example, R in Y ₁ , Y ₂ , and Y ₃ is-(O and A are directly bonded), and A is carbon. In the case of an alkylene group of the formula 3, the following general formulas (8), (9), and (10) (Wherein R ₁ , R ₂ , n, m, and B have the above-mentioned meanings.) The compound represented by the formula (1) is cyanoethylated with acrylonitrile and then hydrogenated, or further cyanoethylated with acrylonitrile and hydrogenated. And can be obtained repeatedly. The cyanoethylation reaction can be obtained by heating and stirring under a strong alkali catalyst such as caustic alkali. The hydrogenation can be obtained by reacting under a hydrogenation catalyst such as Raney nickel.

Also, to give examples of other synthesis methods, (Wherein, R ₁ , R ₂ , and n are as described above, and X represents a halogen atom, preferably a chlorine atom or a bromine atom), and H—O—Y ₁ , H—COO— Y ₂ or (Wherein Y ₁ , Y ₂ and Y ₃ are as described above) by reacting with an alkoxide which has been reacted with an alkali metal or an alkaline earth metal or an oxide or hydroxide thereof. can get.

Further, when a detailed example of the above synthesis method is given, for example, in the case of the formula (8) in the above synthesis method, a branched alcohol represented by the following general formulas (11) and (12) is used. It is used as it is or as an alkylene oxide adduct of these branched alcohols.

(R ₅ and R _{6 each} have ₃ to ₁₆ carbon atoms and the sum of the carbon numbers of R ₅ and R ₆ is 10
~ 32 hydrocarbon residues, and R ₇ and R ₈ have 3 to 15 carbon atoms and
R ₇ and R ₈ are hydrocarbon residues having a total of 8 to 30 carbon atoms. Such alcohols are called so-called hyperbranched alcohols and can be obtained directly by condensing two molecules of natural or synthetic aliphatic alcohols, for example by the Guerbet reaction, or by the reaction of acetic anhydride with α-olefins. It can also be obtained by reducing the obtained branched fatty acid.

The alcohol that can be used as a raw material of the present invention is, for example, 2-butyldodecyl alcohol, 2-butylhexadecyl alcohol, 2-hexyloctyl alcohol, 2-hexyldecyl alcohol,
2-hexyltetradecyl alcohol, 2-hexyloctadecyl alcohol, 2-heptylnonyl alcohol, 2-heptylundecyl alcohol, 2-octyldodecyl alcohol, 2-octylhexadecyl alcohol, 2-nonylundecyl alcohol, 2-nonyltriyl Decyl alcohol, 2-decyl dodecyl alcohol,
2-decyltetradecyl alcohol, 2-decyloctadecyl alcohol, 2-undecylpentadecyl alcohol, 2-dodecyltetradecyl alcohol, 2-dodecylhexadecyl alcohol, 2-tridecylheptadecyl alcohol, 2-tetradecylhexadecyl alcohol , 2-tetradecyloctadecyl alcohol, 2-
Hexadecyloctadecyl alcohol, 4-hexyldodecyl alcohol, 4-octyltetradecyl alcohol, 4-nonylpentadecyl alcohol, 4-decylhexadecyl alcohol, 4-dodecyloctadecyl alcohol, [2- (1 ', 2', 4'-trimethylpentyl) -5,6,8
-Trimethylnonanol], [2- (1 ', 3', 4'-trimethylpentyl) -5,7,8
-Trimethylnonanol], [2- (1 ', 3'-dimethylhexyl) -5,7-dimethyldecanol], [2- (1 ', 3', 4 ', 6'-tetramethylheptyl)-
5,7,8,10-tetramethylundecanol], [2- (1 ', 3', 4'-trimethylpentyl) -5,6,8
-Trimethylnonanol], [2- (5'-methylhexyl) -3,5,6,8-tetramethylnonanol], [2- (1 ', 1', 3'-trimethylbutyl) -5,5,7-
Trimethyloctanol], [2- (1 ', 3', 3'-trimethylbutyl) -5,7,7-
Trimethyloctanol], [2- (1 ', 3', 3'-trimethylbutyl) -5,5,7-
Trimethyloctanol], [2- (1 ', 1', 3 ', 5', 5'-pentamethylhexyl) -5,5,7,9,9-pentamethyldecanol], [2- (1 ', 4', 7'-trimethyloctyl) -5,8,11
-Trimethyl dodecanol], [2- (1 ', 3', 3 ', 6'-tetramethylheptyl)-
5,7,7,10-tetramethylundecanol], [2- (1'2 ', 4', 6 ', 8'-heptamethylnonyl)
−5,6,8,10,12-heptamethyltridecanol], [2- (3'-methylbutyl) -7-methyloctanol], [2- (1'-methylbutyl) -5-methyloctanol] and the like.

For the chain length of these highly branched alcohols, R ₅ and R ₆
Is 10 to 32, preferably 12 to 30. If it is less than 10, the dispersing power of the alkyl ether amine obtained therefrom to sludge is not preferred. And the sum of the carbon atoms in R ₇ and R ₈ are 8 to 30, preferably from 10 to 28. When the ratio is less than 8, sludge dispersibility is deteriorated. On the other hand, if the sum of the above-mentioned carbon numbers is too large, the solubility of the obtained alkyl ether amine in fuel oil is reduced, and it cannot be used.

In the case of an alkyl ether amine having a straight-chain alcohol having no branch, or a small branched alcohol such as a methyl group, for example, oxo alcohol or the like as a raw material alcohol, not only poor solubility in fuel oil, but also cleanliness,
The properties aimed at by the present invention, such as thermal decomposability, were also much less effective.

Considering such properties, the carbon chain length of the R ₅ and R ₆ portions is 3 to 16, and the carbon chain length of the R ₇ and R ₈ portions is 3 to
Must be 15. In particular, when R ₅ and R ₆ have 6 to 12 carbon atoms and the sum of the carbon numbers of R ₅ and R ₆ is 12 to 22,
Further, when R ₇ and R ₈ have 5 to 11 carbon atoms and the sum of the carbon numbers of R ₇ and R ₈ is 11 to 21, more favorable results can be obtained. If the chain length is too large, the solubility in gasoline is undesirably reduced as described above.

As a starting material satisfying the suitability as described above, a highly branched alcohol obtained by subjecting an alcohol having a single composition or a mixed composition to a Guerbet reaction is most preferred.

Using one or more of the above-mentioned branched alcohols as they are or using an alkylene oxide adduct thereof as a starting material, the above-described cyanoethylation and subsequent reduction are performed, and if necessary, cyanoethylation and reduction are performed again. A compound represented by the following general formula (4) or (5) can be obtained.

(Hydrocarbon residue in the formula, R _5, R ₆ where the sum of carbon numbers of and R ₅ and R ₆ is 3 to 16 carbon atoms 10 to 32, l is 1 or 2) (Wherein, R ₇ and R ₈ are hydrocarbon residues having 3 to 15 carbon atoms and the sum of the carbon numbers of R ₇ and R ₈ is 8 to 30, 1 is 1 or 2) The general formula (4) or The compound represented by (5) will be described in more detail with respect to the large-branched-chain portions R _{5 to} R _{8. As} long as R _{5 to} R ₈ have the above-mentioned specific carbon number, those which form a straight chain and are further branched Any of the carbon chains gives a favorable effect, but those having a straight chain are more excellent in detergency. Particularly, a compound in which R _{5 to} R ₈ are a linear hydrocarbon residue, and R _{5 to} R ₈
By using, as an additive, a mixture with a compound which is a hydrocarbon residue having a further branched chain, a remarkable effect on cleanliness can be obtained. These former and latter are preferably 0.
The most remarkable effect can be obtained by mixing at a weight ratio of 02 to 50, particularly preferably 0.1 to 10.

Although raw material alcohols further having small branched chain portions to a large branched chain moiety R ₅ to R ₈ are as described above, is preferred, particularly with a methyl branched chain as a small branched chain portions. As such a highly branched alcohol, oxo alcohols of propylene dimer to pentamer, butylene, dimer oxo alcohols such as isobutylene, or a mixture thereof are synthesized by using the Guerbet method. Can be easily obtained.

Further, in the formulas (1) to (3), R in Y ₁ , Y ₂ , and Y ₃
There _{-CH 2 CONH -, - CH 2} CH (OH) - or is a group selected from -CH ₂ CO-, for example, the following equation (8), (9)
Or (10) And chloroacetic acid or epichlorohydrin, and then reacting with a corresponding amine compound, or / and adding an alkylene oxide having 2 to 4 carbon atoms.

Further, in formulas (1) to (3), R in Y ₁ , Y ₂ , and Y ₃
Is-(O and A are directly bonded), for example, the following formulas (8) to (10) Can be obtained by halogenating the terminal hydroxyl group with a halide such as phosphorus tribromide and then reacting with a corresponding amine compound, or adding an alkylene oxide.

In the formulas (1) to (3), Y ₁ A group represented by or Y ₂ , Y ₃ In the case of compounds which are a group represented by the, Y ₁ is A group represented by or Y ₂ , Y ₃ It is obtained by reacting an organic peroxide with a compound which is a group represented by

However, the method for synthesizing the compounds represented by the formulas (1) to (3) is not limited to the method described above.

When the fuel additive of the present invention is used in combination with a mineral oil or a synthetic oil which is generally called a carrier oil, the fuel additive exhibits an excellent effect of removing deposits and an effect of maintaining cleanliness. In particular, the effects of synthetic oils are excellent, especially olefin polymers, such as poly-α-olefin and polybutene, or alkylene oxide adducts of alcohol or alkylphenol, alkylene oxide polymers, particularly propylene oxide, alkylene oxides such as butylene oxide. Adducts and their ester or ether compounds are excellent. In addition, the mixing ratio thereof is such that a mineral oil or a synthetic oil is added to 1 part by weight of the amine or amine oxide according to the present invention.
0.05 to 20 parts by weight is preferred.

More preferably, the compound represented by the following general formula (6) or (7) as a synthetic oil is added in an amount of 0.1 to 10 per 1 part by weight of the amine or amine oxide according to the present invention.
It is blended by weight.

R ₉ -O- (DO _d R 'or R ₉ -O- (DO _d OCR' ...
(6) (Wherein, R ₉ and R ₁₀ are each an alkyl group having 1 to 30 carbon atoms, R ′ is hydrogen or an alkyl group having 1 to 20 carbon atoms, D is an alkylene group having 3 to 4 carbon atoms, and d = 1 to 50. The fuel additive according to the present invention has a highly branched structure not found in conventional fuel additives, and has an ether bond and an amino group or a derivative thereof in the molecule. It is easy to handle because it shows sludge dispersibility and deposit removal properties, has little heat residue, and has excellent solubility in fuel oil.

The fuel additive of the present invention is blended in the fuel in an amount of 0.1 to 50,000 ppm. The higher the amount, the better the cleanliness.
A practically excellent result is obtained at 20,00020,000 ppm. The additives of the present invention may be used in combination with other fuel oil additives such as rust inhibitors, demulsifiers, metal deactivators and the like. Thus, by blending the fuel additive of the present invention, a fuel composition having excellent cleanliness can be obtained.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

Synthesis Example 1 400 g of 2-octyldodecyl alcohol was placed in a four-necked flask, and 83.85 g of acrylonitrile was added dropwise over 3 hours while heating and stirring at a temperature of 76 to 80 ° C. in a nitrogen atmosphere using 0.222 g of caesari as a catalyst. After the dropwise addition, the mixture was reacted at 76 to 80 ° C. for 2 hours, then neutralized with acetic acid to remove excess acrylonitrile under reduced pressure to obtain a cyanoethylated product.

300 g of the cyanoethylated product was put into one autoclave, and hydrogenation was carried out using Raney nickel as a catalyst under a hydrogen pressure of 20 kg / cm ² to obtain a compound of the formula C ₁₀ H ₁₇ CH (C ₈ H ₁₇ ) CH ₂ OC ₃ H ₆ NH ₂
2-octyldodecyloxypropylamine represented by was obtained.

SYNTHESIS EXAMPLE 2 Using 2-tetradecyl octadecyl alcohol as a starting alcohol, the process of formula C ₁₆ H ₃₃ CH (C ₁₄
H ₂₉ ) ₂ -tetradecyloctadecyloxypropylamine represented by CH ₂ OC ₃ H ₆ NH ₂ was obtained.

Synthesis Example 3 The 2-tetradecyloctadecyloxypropylamine obtained in Synthesis Example 2 was cyanoethylated in the same manner as in Synthesis Example 1, and then hydrogenated to give a compound of the formula C ₁₆ H ₃₃ CH (C ₁₄ H ₂₉ ) CH. ₂ O
It was obtained (C ₃ H ₆ NH) 2- tetradecyl-octadecyl propyl propylene diamine represented by ₂ H.

Synthesis Example 4 Using 2-decyltetradecyl alcohol as a raw material alcohol, and in the same manner as in Synthesis Example 1, the formula C ₁₂ H ₂₅ CH (C ₁₀ H
₂₁₎ to give 2-decyl tetradecyl oxypropyl amine represented by _{CH 2 OC 3 H 6 NH 2} .

Synthesis Example 5 n-octyl alcohol and n-dodecyl alcohol
The Guerbet reaction was performed at a 1: 1 molar ratio. From the obtained mixed macrobranched alcohol, a macrobranched alkoxypropylamine was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 6 A fine oxocoll 180 manufactured by Nissan Chemical Industries, Ltd. was used in the same manner as in Synthesis Example 1 to obtain a compound represented by the following formula. A highly branched alkoxypropylamine represented by the formula was obtained.

Synthesis Example 7 Using 2-pentadecanylnonadecanol as a raw material alcohol, the method of formula A highly branched alkoxypropylamine represented by the formula was obtained.

Synthesis Example 8 Using 2-heptylundecanol as a raw material alcohol, a method similar to that of Synthesis Example 1 was used. A highly branched alkoxypropylamine represented by the formula was obtained.

Synthesis Example 9 Using 2-hexyldecanol as the raw material alcohol, the method of Formula 1 was repeated in the same manner as in Synthesis Example 1. A highly branched alkoxypropylamine represented by the formula was obtained.

Synthesis Example 10 Nissan Fine Oxocol 140 [Representative structure Or Is used as a starting alcohol, and in the same manner as in Synthesis Example 1, as a representative structure, A highly branched alkoxypropylamine represented by the formula was obtained.

SYNTHESIS EXAMPLE 11 Using 2-methylnonadecyl alcohol as a starting alcohol, the compound of formula C ₁₇ H ₃₅ CH (CH ₃ ) CH ₂ OC was obtained in the same manner as in Synthesis Example 1.
Represented by ₃ H ₆ NH ₂ to give 2-methyl-nonadecyl oxy propylamine.

Synthesis Example 12 n-Docosyloxypropylamine represented by the formula nC ₂₂ H ₄₅ OC ₃ H ₆ NH ₂ was obtained in the same manner as in Synthesis Example 1 using n-docosyl alcohol as a starting alcohol.

Synthesis Example 13 62.5 g of (2-aminoethyl) ethanolamine, 8 g of magnesium powder, and 500 ml of xylene were placed in a three-necked flask and refluxed for 2 hours. To this, 132 g of chlorinated polybutene (MW950) dissolved in 100 ml of xylene was gradually added, and refluxed for 6 hours. The precipitate formed was cooled, filtered off, washed with water and dried under reduced pressure to obtain poly-iBu-OC ₂ H _{4
NHC 2 H 4 NH 2 (poly} -iBu; polyisobutenyl group, MW950) to give a polyisobutenyl oxy ethylene diamine represented by.

 Table 1 shows examples of other compounds of the present invention.

Example 1 A dispersibility test was performed by the following method in order to observe the sludge deposition preventing and removing effects of the additives obtained in Synthesis Examples 1 to 13 and Compound Examples 14 to 26.

The hexane-insoluble, chloroform-soluble portion of the sludge scraped from the crankcase of the engine after traveling a high number of miles was added to a typical base gasoline containing the test additives as a chloroform solution to a sludge amount of 600 ppm. The additive concentrations were 100 ppm, 200 ppm, and 400 ppm, and the amount of sludge 30 minutes after the addition of the sludge solution was examined.

Judgment was made in three stages. When there was no sludge settling, ○,
When there was a little, it was marked as △, and when there was much precipitation, it was marked as x.

Without additives, the sludge is insoluble in gasoline and precipitates.

 The results are shown in Table 2.

As is clear from Table 2, the product of the present invention has excellent sludge dispersing power.

Example 2 To determine whether the additive itself was deposited in the combustion chamber, a thermal decomposition test was performed by the following method.

About 1 g of the additive sample (50% kerosene solution) was precisely weighed, placed in an aluminum cup, heated at 200 ° C. for 15 hours in a thermostat, and the residual weight was measured. Assuming that the additive sample weight is Wi and the remaining weight is Wr, the decomposition rate was calculated by the following equation.

Decomposition rate (%) = (Wi−Wr−Wi / 2) / (Wi / 2) × 100 The appearance of the residue was visually observed.

 Table 3 shows the obtained results.

As is clear from Table 3, the product of the present invention is superior in thermal decomposability as compared with the comparative product.

Example 3 When water is mixed in a gasoline tank, an additive causes emulsification, which may cause a trouble.

Therefore, in order to confirm the effect of the additive on the water-gasoline system, a water separation test was performed by the following method.

Additive sample concentration 200ppm gasoline 80ml and pure water 20ml
Into a graduated cylinder with a stopper and shake by hand for 1 minute. Rate the fuel phase and interface after 5, 10, 15 and 30 minutes. The rating criteria are as follows.

Fuel phase 1 = glossy transparent 2 = slight turbidity 3 = turbidity 4 = strong turbidity 5 = emulsified Boundary surface 1 = colorless and transparent 1B = less than 50% of the boundary surface covered with a small amount of small bubbles 2 = boundary surface 50% or more and less than 100% of small bubbles or small pieces of string-like emulsion 3 = large string-like emulsion exists on the entire boundary surface, but less than 1 ml 4 = less than 3 ml of scum 5 = Table 4 shows the results of the presence of scum of 3 ml or more.

As is clear from Table 4, the product of the present invention is superior in water separation property as compared with the comparative product.

Example 4-1 (Actual vehicle running test 1) Evaluation as gasoline additive The thermal decomposability of various fuel additives (hereinafter referred to as gasoline additive) shown in Table 5 and an actual vehicle running test were performed by the following methods.

 Table 5 shows the results.

(1) Evaluation of thermal decomposability The thermal decomposability was determined by placing 1 g of gasoline additive in an aluminum disk with a diameter of 5 cm, leaving it on a hot plate maintained at 280 ° C, removing the disk after 30 minutes, cooling, and Was evaluated.

Judgment of appearance The standard was used.

(2) Actual vehicle running test One tank (61) of gasoline with 1% by weight of gasoline additive added to gasoline runs on a general road, and the intake system (intake valve, intake port), combustion chamber and carburetor before and after the test Was evaluated by disassembling the engine and visually observing the degree of deposit removal. The test was conducted using a Toyota Carina 1800cc (engine model 1S).

The degree of deposit removal before and after the test was determined based on the following criteria.

As the compound, those mixed at the following ratio were used.

Example 4-2 (Real vehicle running test 2) A real vehicle running test was performed on Compound Examples 14 to 22 and 26 in the same manner as in Example 4-1.

 Table 6 shows the results.

From the results in Tables 5 and 6, the single product of the present invention shows a good deposit removing effect, but the compound shows a more excellent deposit removing effect. The formulation also has good thermal decomposition properties.

Example 5 (Actual vehicle running test 3) Various gasoline additive compositions obtained by mixing the compound of Synthesis Example 6, the compound of Synthesis Example 8, nonylphenol (BO) ₁₅ and an aromatic solvent at a ratio shown in Table 7 were prepared. Manufactured.

An actual vehicle running test was performed on these compositions by the same test method as in Examples 4-1 and 4-2. Table 7 shows the results.

As is clear from the results in Table 7, by mixing the compound of Synthesis Example 6 and the compound of Synthesis Example 8, a more excellent deposit removing effect was obtained.

Example 6 (actual vehicle running test 4) An example in which the product of the present invention is used for diesel light oil will be described.

In practice, 50% of the compounds of Synthesis Examples 1 to 10 and the compounds of Compound Examples 14 to 18 were added to the aromatic solvent as single products.
Diluted and used as Test Examples 1 to 15, and as a compound, Synthesis Example 8
A mixture of the compound of formula (1) with 15 mol of nonylphenol butylene oxide adduct {nonylphenol (BO) ₁₅ } and an aromatic solvent at a ratio shown in Table 8 was used.
~ 18.

 In addition, a sample without the additive was used as Test Example 19.

<Evaluation of Performance> With respect to the additives of the present invention in Test Examples 1 to 18, the cleaning performance of the caulk of the diesel injector nozzle was evaluated by the following method.

That is, the additives of the present invention of Test Examples 1 to 18 were
Using the fuel oil added by weight%, the vehicle traveled 500 km in an urban area. About the injector nozzle before and after actual driving,
The air flow rate when the needle lift amount was 0.2 mm was measured.
By calculating the ratio of the new nozzle to the air flow rate by the following equation, the cleaning ability of the caulk at the nozzle was evaluated.

Table 8 shows the evaluation results of the cleaning ability of the injector nozzle tested by the above method.

The test vehicle is a Toyota Corolla van (displacement 1.83l)
Was used.

As can be seen from the results in Table 8, the additive of the present invention
The caulk at the injector nozzle of the diesel engine was cleaned and the air flow was restored.

When the additive of the present invention is added to diesel light oil, it has a rust-preventing effect, and also has good water separation when water is mixed.

Claims (7)

(57) [Claims] (1) an alkyl group having (a) an alkyl branch having 3 to 18 carbon atoms, an alkyl group having 9 to 37 carbon atoms including the branched portion, and (b) an alkyl group having 2 to 4 carbon atoms. A fuel additive comprising an amine or an amine oxide having at least one oxyalkylene group. 2. A fuel additive comprising a compound represented by the following general formula (1), (2) or (3). [Wherein, R ₁ and R ₂ are hydrocarbon residues having 3 to 18 carbon atoms, and the sum of the carbon numbers of R ₁ and R ₂ is 8 to 36. n is 0 or an integer of 1-4. Y ₁ is the formula The amine or amine oxide residue represented by the formula, Y ₂ and Y ₃ are represented by the formula In represented by amine or amine oxide residue represented a (where B is an alkylene group having 2 to 4 carbon atoms, m is an integer of 0, R represents _{-, - CH 2 CONH -,} - CH 2 CH (OH ) −, − CH ₂ CO−
Group selected from, A is - or alkylene group having 1 to 4 carbon atoms, R _3, R ₄ is H or an alkyl or hydroxyalkyl group or an aminoalkyl group having 1 to 4 carbon atoms, _l is 1 or 2
Is). ] 3. The fuel additive according to claim 1, comprising a compound represented by the following general formula (4) or (5). (Hydrocarbon residue in the formula, R _5, R ₆ where the sum of carbon numbers of and R ₅ and R ₆ is 3 to 16 carbon atoms 10 to 32, _l is 1 or 2) (Wherein, R ₇ and R ₈ are hydrocarbon residues having 3 to 15 carbon atoms and the sum of the carbon numbers of R ₇ and R ₈ is 8 to 30; _l is 1 or 2) 4. A mixture of a compound in which R _{5 to} R ₈ are a linear hydrocarbon residue and a compound in which R _{5 to} R ₈ are a hydrocarbon residue having a methyl branched chain. Fuel additive. 5. A fuel additive composition comprising a mineral oil or a synthetic oil and the fuel additive according to claim 1. 6. A fuel additive according to claim 1, wherein the formula (4) or compound R ₅ to R ₈ is a hydrocarbon residue of a straight chain in the compounds represented by formula (5) and R ₅ ~ R ₈ is is a mixture according to claim 5 fuel additive composition according to the compound is a hydrocarbon residue having a methyl branched chain. 7. The fuel additive composition according to claim 5, wherein the synthetic oil is a compound represented by the following general formula (6) or (7). R ₉ -O- (DO _d R 'or R ₉ -O- (DO _d -OCR' ...
(6) (Wherein, R ₉ and R ₁₀ are each an alkyl group having 1 to 30 carbon atoms, R ′ is hydrogen or an alkyl group having 1 to 20 carbon atoms, D is an alkylene group having 3 to 4 carbon atoms, and d = 1 to 50. Integer.)