JPH07331263A - Additive for fuel, additive composition for fuel and fuel composition - Google Patents

Abstract

PURPOSE:To obtain an additive for a fuel useful as an ashless cleaning agent, an abrasion inhibitor for a fuel injection pump following reduction in sulfur of a light oil or a storage stabilizer for a fuel oil containing a particulate substance-reducing agent, comprising a prescribed substituted hydroxylated aromatic ester derivative, etc. CONSTITUTION:This additive for a fuel oil comprises one or more of substituted hydroxylated aromatic ester derivative of formula I [R<1> and R<2> are each >=6C organic group; 1<=a<=3; 1<=b<=3; 0<=c<=3; 1<=d<=3; 1<=e<=3; 3<=(a+b+e)<=6, 1<=(c+d)<=5] and formula II [R<3> to R<5> are each >=6C organic group; 0<=f<=3; 0<=g<=6; 1<=(f+g)<=3; 0<=h<=4; 0<=i<=3; 1<=(h+i)<=6; 0<=j<=3; 1<=k<=3; 1<=m<=3; 3<=(f+g+h+i+m)<=8; 1<=(j+k)<=5], is useful as an ashless cleaning agent, an abrasion inhibitor for a fuel injection pump following reduction in sulfur of a light oil or a storage stabilizer for a fuel oil containing a particulate substance-reducing agent and has excellent high-temperature stability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fuel additive, a fuel additive composition, and a fuel composition. More specifically, the present invention is useful as an ashless detergent, and as an antiwear agent for an injection pump accompanying the low sulfur content of gas oil, and a particulate reducing agent such as a polyoxyethylene compound was added. Additive for fuel useful as storage stabilizer for fuel oil, additive composition for fuel which is excellent in high temperature stability (high temperature detergency) and has fine particle dispersibility and is useful as an excellent detergent and dispersant for fuel oil And a fuel composition containing the additive for fuel and the additive composition, particularly a fuel composition for an internal combustion engine.

[0002]

2. Description of the Related Art In recent years, among internal combustion engines, countermeasures against environmental pollution due to exhaust gas such as particulates and NOx have become an important issue especially in diesel engines. Development of exhaust gas purifying devices such as an oxidation catalyst, a particulate trap, and a NOx removal catalyst is urgently required as a countermeasure against these problems. For this reason, it is required to reduce the sulfur content of gas oil required for introducing these devices. However, there is a concern about the problem of wear of the injection pump due to the decrease of polar substances accompanying the low sulfur of light oil. Further, in Japanese Patent Publication No. 29519/1990 as a measure for reducing particulates, as a fuel composition for a diesel engine, a method in which a specific polyoxyethylene compound is added to a light oil as an essential component is used as an easy and inexpensive method. By doing so, the particulates can be remarkably reduced. However, the fuel composition for diesel engines produces sludge when stored for a long period of time, and has a problem in storage stability (for this reason, it is proposed to use a specific sorbitan ester together). Further, a detergent dispersant is used to prevent deposits from adhering to injectors or to remove deposits, but their stability at high temperatures (high temperature detergency) is not always sufficient. On the other hand, U.S. Pat. No. 4,098,708 proposes an ester of an alkyl-substituted hydroxyaromatic carboxylic acid having at least about 10 carbon atoms and a derivative thereof as a dispersant for lubricating oil and fuel oil. And, as a suitable alcohol component of the ester, monohydric or polyhydric hydrocarbon alcohols are listed,
Cresol etc. are mentioned as the specific example. However, the stability at high temperature (high temperature cleanability) is not fully satisfactory.

[0003]

Under the circumstances, the present invention is useful as an ashless detergent, and as an antiwear agent for injection pumps accompanying the low sulfur content of light oil, and polyoxyethylene. An additive for fuel that is also useful as a storage stabilizer for fuel oil containing a particulate reducing agent such as a compound. It has excellent high-temperature stability (high-temperature detergency) and also has fine particle dispersibility, making it an excellent fuel oil. An object of the present invention is to provide a fuel additive composition useful as a detergent-dispersant, and a fuel composition containing the fuel additive or the additive composition, particularly a fuel composition for an internal combustion engine.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a fuel additive containing a specific substituted hydroxyaromatic ester derivative is a fuel oil. It has been found that it is useful as an ashless detergent of (1), has excellent wear resistance of the injection pump, and has excellent storage stability for fuel oil containing a particulate reducing agent and the like. Further, the additive for fuel (ashless detergent)
It has been found that by blending the above with a conventional dispersant, an additive composition for fuel which is excellent in high-temperature stability (high-temperature detergency) and has a fine particle dispersing action and which is useful as a detergent-dispersant can be obtained. The present invention has been completed based on such findings. That is, the present invention provides (1) the general formula (I)

[0005]

[Chemical 5]

[In the formula, R ¹ and R ² each represent an organic group having 6 or more carbon atoms, and they may be the same or different, and a, b, c, d and e are each 1
≦ a ≦ 3,1 ≦ b ≦ 3,0 ≦ c ≦ 3,1 ≦ d ≦ 3,1 ≦
e ≦ 3, 3 ≦ (a + b + e) ≦ 6 and 1 ≦ (c + d) ≦
An integer that satisfies the relationship of 5 is shown. Further, when R ¹ and R ² are a plurality, the plurality of R ¹ and R ² may be different even in the same in each. ] And general formula (II)

[0007]

[Chemical 6]

[Wherein R³, R^FourAnd R^FiveRespectively
Indicates an organic group having 6 or more carbon atoms, which are identical to each other
May be different, f, g, h, i, j, k and m
Are 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g), respectively.
≦ 3,0 ≦ h ≦ 4,0 ≦ i ≦ 3,1 ≦ (h + i) ≦ 6
0 ≦ j ≦ 3, 1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g +
h + i + m) ≦ 8 and 1 ≦ (j + k) ≦ 5
Indicates an integer. Also, R ³, R^FourAnd R^FiveIf there are multiple
If more than one R³, R^FourAnd R^FiveIn each
It may be the same or different. ] The substitution represented by
A few selected from hydroxy aromatic ester derivatives
At least one fuel additive, (2) (a) general formula
Substituted hydroxyaromatic ester represented by (I) and (II)
At least one selected from tellurium derivatives and (b)
Fuel additive composition containing dispersant, (3) fuel
In contrast, substituted hydrides represented by the general formulas (I) and (II)
At least one selected from Roxy aromatic ester derivatives
A fuel composition containing one kind of (4) fuel
And (a) a substituted hydroxide represented by the general formula (I) or (II)
At least one selected from Roxy aromatic ester derivatives
A fuel composition containing one kind and (b) a dispersant,
Is provided.

The fuel additive of the present invention has the general formulas (I) and (II)

[0010]

[Chemical 7]

[0011]

[Chemical 8]

[0012] It is composed of at least one selected from the substituted hydroxyaromatic ester derivatives represented by, and is useful as an ashless detergent instead of a metal detergent. Further, the fuel additive of the present invention is useful as an ashless detergent, and as an antiwear agent for an injection pump due to the low sulfur of light oil, and a particulate reducing agent such as a polyoxyethylene compound. It is also useful as a storage stabilizer for the added diesel gas oil composition.

In the above general formulas (I) and (II), R
¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an organic group having 6 or more carbon atoms. Examples of the organic group having 6 or more carbon atoms include hydrocarbon groups having preferably 6 to 7,000 carbon atoms, more preferably 8 to 225 carbon atoms, and particularly preferably 9 to 150 carbon atoms. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group and an aralkyl group, which have a non-hydrocarbon substituent and a hetero atom in the chain or ring. Good. Specifically, hydrocarbon groups such as hexyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, triacontyl group, and groups derived from olefin polymers such as polyethylene, polypropylene, and polybutene can be used. Can be mentioned. Further, when a low-viscosity substituted hydroxyaromatic ester derivative is desired, it is preferable that R ¹ , R ² , R ³ , R ⁴ and R ⁵ are substantially linear hydrocarbon groups. R ¹ and R ² may be the same or different from each other, and R ³ , R ⁴ and R ⁵ may be the same or different from each other.

In the above general formula (I), a, b, c,
d and e are 1 ≦ a ≦ 3, 1 ≦ b ≦ 3, 0 ≦ c, respectively.
≦ 3,1 ≦ d ≦ 3,1 ≦ e ≦ 3,3 ≦ (a + b + e) ≦
6 and an integer satisfying the relationship of 1 ≦ (c + d) ≦ 5.
When b is 2 or 3, a plurality of R ¹ may be the same or different, and when d is 2 or 3, a plurality of R ² may be the same or different. Further, in the general formula (II), f, g, h, i, j, k, and m are 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g) ≦ 3, respectively.
0 ≦ h ≦ 4, 0 ≦ i ≦ 3, 1 ≦ (h + i) ≦ 6, 0 ≦ j
≦ 3,1 ≦ k ≦ 3, 1 ≦ m ≦ 3,3 ≦ (f + g + h + i
+ M) ≦ 8 and 1 ≦ (j + k) ≦ 5 are integers. When h is 2, 3 or 4, a plurality of R ³ may be the same or different, and when i is 2 or 3, a plurality of R ⁴ may be the same or different. Also,
When k is 2 or 3, plural R ^{5 s} may be the same or different.

Specific examples of the substituted hydroxyaromatic ester derivative represented by the above general formula (I) include (hexylhydroxybenzoic acid) hexylphenyl ester, (hexylhydroxybenzoic acid) dodecylphenyl ester, and (octylhydroxybenzoic acid). ) Octylphenyl ester, (nonylhydroxybenzoic acid) nonylphenyl ester, (nonylhydroxybenzoic acid) hexadecylphenyl ester, (dodecylhydroxybenzoic acid)
Nonylphenyl ester, (dodecylhydroxybenzoic acid) dodecylphenyl ester, (dodecylhydroxybenzoic acid) hexadecylphenyl ester, (hexadecylhydroxybenzoic acid) hexylphenyl ester,
(Hexadecylhydroxybenzoic acid) dodecylphenyl ester, (hexadecylhydroxybenzoic acid) hexadecylphenyl ester, (eicosylhydroxybenzoic acid) eicosylphenyl ester, (C 11-11
5 mixed alkylhydroxybenzoic acid) 11 to 1 carbon atoms
5, mixed alkyl phenyl ester, (long chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) dodecyl phenyl ester, (long chain Alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms] A group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyl hydroxybenzoic acid) hexyl hydroxy phenyl ester,
(Octyl hydroxybenzoic acid) octyl hydroxyphenyl ester, (dodecyl hydroxybenzoic acid) nonyl hydroxyphenyl ester, (dodecyl hydroxybenzoic acid) dodecyl hydroxyphenyl ester, (hexadecyl hydroxybenzoic acid) dodecyl hydroxyphenyl ester, (hexadecyl hydroxybenzoic acid) acid)
Hexadecyl hydroxyphenyl ester, (eicosyl hydroxybenzoic acid) eicosyl hydroxyphenyl ester, (mixed alkyl hydroxybenzoic acid having 11 to 15 carbon atoms) mixed alkyl hydroxyphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, A group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) dodecyl hydroxyphenyl ester,
(Long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) Long-chain alkyl [eg, derived from polydecene having 30 or more carbon atoms] Group, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (hexyldihydroxybenzoic acid) hexylphenyl ester,
(Nonyldihydroxybenzoic acid) nonylphenyl ester, (nonyldihydroxybenzoic acid) dodecylphenyl ester, (dodecyldihydroxybenzoic acid) nonylphenyl ester, (dodecyldihydroxybenzoic acid) dodecylphenyl ester, (hexadecyldihydroxybenzoic acid) hexadecylphenyl Ester, (eicosyldihydroxybenzoic acid) hexadecylphenyl ester, (eicosyldihydroxybenzoic acid) eicosylphenyl ester, (mixed alkyldihydroxybenzoic acid having 11 to 15 carbon atoms) mixed alkylphenyl ester having 11 to 15 carbon atoms, (Long-chain alkyl [eg, having 3 carbon atoms
Group derived from 0 or more polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) dodecylphenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, Group derived from polybutene having a weight average molecular weight of 400 or more] Dihydroxybenzoic acid) long-chain alkyl [for example, group derived from polydecene having a carbon number of 30 or more, group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester , (Hexyldihydroxybenzoic acid) hexylhydroxyphenyl ester, (nonyldihydroxybenzoic acid) nonylhydroxyphenyl ester, (nonyldihydroxybenzoic acid) dodecylhydroxyphenyl ester, (dodecyldihydroxybenzoic acid) nonylhydroxy Phenyl ester, (dodecyldihydroxybenzoic acid) dodecylhydroxyphenyl ester, (hexadecyldihydroxybenzoic acid) hexadecylhydroxyphenyl ester, (eicosyldihydroxybenzoic acid) hexadecylhydroxyphenyl ester, (eicosyldihydroxybenzoic acid) eicosylhydroxy Phenyl ester, (mixed alkyldihydroxybenzoic acid having 11 to 15 carbon atoms) Mixed alkyl hydroxyphenyl ester having 11 to 15 carbon atoms, (long chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, weight average molecular weight Group derived from polybutene having 400 or more] dihydroxybenzoic acid) dodecylhydroxyphenyl ester, (long-chain alkyl [eg group derived from polydecene having 30 or more carbon atoms] The weight average molecular weight of 400 or more groups derived from polybutene] dihydroxybenzoic acid) long-chain alkyl [e.g., a group derived from a polydecene having 30 or more carbon atoms, the weight average molecular weight of 400
The above-mentioned groups derived from polybutene] hydroxyphenyl ester and the like.

On the other hand, specific examples of the substituted hydroxyaromatic ester derivative represented by the above general formula (II) include (hexylhydroxynaphthoic acid) hexylphenyl ester, (hexylhydroxynaphthoic acid) hexadecylphenyl ester, and (nonyl). (Hydroxynaphthoic acid) nonylphenyl ester, (dodecylhydroxynaphthoic acid) dodecylphenyl ester, (hexadecylhydroxynaphthoic acid) hexadecylphenyl ester, (dodecylhydroxynaphthoic acid) eicosylphenyl ester, (eicosylhydroxynaphthoic acid) eicosyl Phenyl ester, (mixed alkyl hydroxynaphthoic acid having 11 to 15 carbon atoms) Mixed alkyl phenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [eg Group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) dodecylphenyl ester, (long-chain alkyl [eg, a group derived from polydecene having a carbon number of 30 or more, weight average molecular weight of 400 The above-mentioned group derived from polybutene] hydroxynaphthoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms,
Group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (octyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, ( Dodecyl hydroxynaphthoic acid) hexadecyl hydroxyphenyl ester,
(Hexadecyl hydroxynaphthoic acid) hexadecyl hydroxyphenyl ester, (Hexadecyl hydroxynaphthoic acid) eicosyl hydroxyphenyl ester,
(Mixed alkyl hydroxynaphthoic acid having 11 to 15 carbon atoms) Mixed alkyl hydroxyphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, weight average molecular weight 400
Group Derived from Polybutene] Hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (long-chain alkyl [eg, group derived from polydecene having 30 or more carbon atoms, group derived from polybutene having a weight average molecular weight of 400 or more]) Hydroxynaphthoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (hexyldihydroxynaphthoic acid) hexylphenyl ester, ( Hexyldihydroxynaphthoic acid) hexadecylphenyl ester, (nonyldihydroxynaphthoic acid) nonylphenyl ester, (dodecyldihydroxynaphthoic acid)
Dodecyl phenyl ester, (dodecyl dihydroxynaphthoic acid) eicosyl phenyl ester, (hexadecyl dihydroxy naphthoic acid) hexadecyl phenyl ester, (eicosyl dihydroxy naphthoic acid) eicosyl phenyl ester, (mixed alkyl dihydroxy naphthoic acid having 11 to 15 carbon atoms Acid) Mixed alkylphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecyl Phenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) long-chain alkyl [eg, carbon Group derived from a few more than 30 polydecene, and the group] phenyl ester derived from the weight-average molecular weight of 400 or more polybutenes, (hexyl dihydroxy naphthoic acid) dodecyl-hydroxyphenyl ester,
(Octyldihydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl dihydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl dihydroxynaphthoic acid) hexadecyl hydroxyphenyl ester, (hexadecyl dihydroxynaphthoic acid) hexadecyl hydroxyphenyl ester, (hexadecyl) Dihydroxynaphthoic acid) eicosyl hydroxyphenyl ester, (mixed alkyldihydroxynaphthoic acid having 11 to 15 carbon atoms) mixed alkylhydroxyphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, derived from polydecene having 30 or more carbon atoms] Group, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecyl hydroxyphenyl ester, ( Alkyl [e.g., 3 carbon atoms
Group derived from 0 or more polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) long chain alkyl [eg group derived from polydecene having a carbon number of 30 or more, weight average molecular weight 400
The above-mentioned groups derived from polybutene] hydroxyphenyl ester and the like. Among these substituted hydroxyaromatic ester derivatives, the general formula (III)

[0017]

[Chemical 9]

[Wherein R ¹ , R ² , b, d and e are the same as above, and the sum of b and e is 2-5. ]
And the general formula (III ′)

[0019]

[Chemical 10]

[Wherein R ³ , R ⁴ , R ⁵ , h, k and m
Is the same as above, n is 0, 1 or 2, the sum of h and n is 1 to 6, and the sum of h, n and m is 2 to 7. ] The compound represented by these is suitable. The fuel additive of the present invention may be composed of one kind of the compound represented by the general formula (I) or may be composed of two or more kinds. The compound represented by the general formula (II) may be composed of one kind or two or more kinds. Further, it may be composed of one or more compounds represented by the general formula (I) and one or more compounds represented by the general formula (II). There is no particular limitation on the method for producing the substituted hydroxyaromatic ester derivative represented by the general formula (I), but, for example, the general formula (IV)

[0021]

[Chemical 11]

[In the formula, R ¹ , a, b and e are the same as above. ] At least one of the organic group-substituted hydroxybenzenecarboxylic acids represented by the general formula (V)

[0023]

[Chemical 12]

[In the formula, R ² , c and d are the same as above. ] The substituted hydroxy aromatic ester derivative represented by the general formula (I) can be obtained by reacting with at least one of the organic group-substituted phenols represented by On the other hand, the method for producing the substituted hydroxyaromatic ester derivative represented by the general formula (II) is not particularly limited, but for example, the general formula (VI)

[0025]

[Chemical 13]

[In the formula, R ³ , R ⁴ , f, g, h, i and m are the same as above. ] At least one organic group-substituted hydroxynaphthalenecarboxylic acid represented by the general formula (VII)

[0027]

[Chemical 14]

[In the formula, R ⁵ , j and k are the same as above. ] The substituted hydroxy aromatic ester derivative represented by the general formula (II) can be obtained by reacting with at least one of the organic group-substituted phenols represented by In these reactions, the organic group-substituted hydroxyaromatic carboxylic acid and the organic group-substituted phenol are used in a molar ratio of 1: 0.01 to 1: 4, preferably 1 :.
The range of 0.2 to 1: 2.5 is preferable. The reaction temperature is
It is usually selected in the range of 100 to 300 ° C, preferably 150 to 250 ° C. This reaction may be carried out without catalyst,
It may be carried out in the presence of an acid or alkali catalyst. In carrying out this reaction, a solvent such as a hydrocarbon oil can be used. The above-mentioned organic group-substituted hydroxyaromatic carboxylic acid can be produced by various methods, and as an example, it can be obtained by a known Kolbe-Schmidt reaction from an organic group-substituted phenol or an alkali metal salt of naphthol and carbon dioxide. It can be produced by hydrolyzing the product.

In the present invention, the substituted hydroxyaromatic ester derivative represented by the above general formula (I) or (II) is, if necessary, reacted and / or reacted with at least one of them and at least one of the boron-containing compounds. By mixing, it may be used as a boron-containing substituted hydroxyaromatic ester derivative. Examples of the boron-containing compound used at this time include boric acid such as orthoboric acid, metaboric acid, and tetraboric acid, diboron trioxide, halogenated boric acid, boric acid amide, and the like.
Examples thereof include boric acid esters. These boron-containing compounds may be used alone or in combination of two or more. The molar ratio of the ester derivative to the boron-containing compound is 1: 0.05 to 1: 2, preferably 1: 0.1 to 1: 1. Further, when the reaction is carried out, the reaction temperature is usually selected in the range of 80 to 250 ° C, preferably 100 to 200 ° C. In carrying out this reaction, a solvent such as a hydrocarbon oil can be used. This boron-containing substituted hydroxyaromatic carboxylic acid ester derivative is, as in the above-mentioned method, a method of adding a boron-containing compound after obtaining an ester derivative from a substituted hydroxyaromatic carboxylic acid as a raw material and a hydroxy compound. It can also be produced by a method of reacting and / or mixing a starting material, a substituted hydroxyaromatic carboxylic acid, a hydroxy compound, and a boron-containing compound. At this time, the type and mixing ratio of each component,
Furthermore, reaction conditions and the like may be selected according to the method described above.

Next, the fuel additive composition of the present invention is
As the component (a), a fuel additive comprising at least one selected from the substituted hydroxyaromatic ester derivatives represented by the above general formulas (I) and (II) is contained, and dispersed as the component (b). Containing an agent,
It is used as an ashless detergent dispersant that has excellent high-temperature stability (high-temperature detergency) and has a fine-particle dispersing effect. The (b)
The dispersant of the component is not particularly limited, and conventionally known ones, for example, carboxylic acid imide type, carboxylic acid ester type, hydroxybenzylamine type, polyolefin amine type, polyoxyalkylene amine type, etc. may be used alone or in combination. Can be used. The preferred acid site of the carboxylic acid imide type and the carboxylic acid ester type is succinic acid, and a hydrocarbon group having a molecular weight of 200 or more in the molecular structure,
Or what has an oxyalkylene group is suitable. The hydrocarbon group is an alkyl group or an alkenyl group, and may have a non-hydrocarbon substituent and a hetero atom in the chain or ring. The oxyalkylene group is an oxyethylene group, an oxypropylene group, an oxybutylene group or the like, and the group may be composed of one kind or two or more kinds.

The above-mentioned carboxylic acid imide type and carboxylic acid ester type include (1) at least 1
Organic nitrogen compounds having one —NH— group, for example, reaction products with amines, ureas, hydrazines, etc., and (2) reaction products with hydroxy compounds such as phenols and alcohols. In addition, the reaction product of the carboxylic acid derivative and the reactive metal or the reactive metal compound may be contained in the range not affecting. In addition, these post-treatment products are also useful. Examples of post-treatment agents include sulfur and sulfur compounds, urea, thiourea, guanidine, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, polyoxyalkylene-substituted succinic anhydrides, nitriles, epoxides, boron compounds. , Phosphorus compounds and the like (the details of these carboxylic acid imide-based compounds and carboxylic acid ester-based compounds are described in Japanese Patent Publication No. 3-60876). On the other hand, the hydroxybenzylamine-based compounds are, for example, sulfur-crosslinked phenols. And a hydrocarbon-substituted phenol such as methylene-bridged phenol, formaldehyde, and a nitrogen compound having at least two —NH— groups, for example, a reaction product of polyamine.

Polyolefin amines are chlorinated poly-
It is a reaction product of an α-olefin with a nitrogen compound having at least one —NH— group, for example, ammonia or polyamine. The polyoxyalkylene amine-based compound is a reaction product of a polyoxyalkylene compound such as polyalkylene glycol or alkylphenyl polyalkylene glycol and (1) dichloromethane and polyamine, specifically, aminoalkyleneaminoalkanol, 2) a reaction product of phosgene and polyamine, (3) a reaction product of ammonia and hydrogen, and further a reaction product of N-alkyl-2-morpholinone.

In the fuel additive composition of the present invention,
The component (a), a fuel additive comprising at least one selected from the substituted hydroxyaromatic ester derivatives represented by the general formulas (I) and (II), and the component (b), the dispersant. The blending ratio with is 10: 90-9 by weight.
It is desirable to be in the range of 9: 1, preferably 15:85 to 75:25. In addition, the fuel composition of the present invention contains (a) at least one selected from the substituted hydroxyaromatic ester derivatives represented by the above general formulas (I) and (II), and in some cases ( b) It contains the above-mentioned dispersant. The components (a) and (b) are each 0.005 to the fuel based on the total amount of the fuel composition.
It is desirable to add 10% by weight, preferably 0.02 to 5% by weight. Examples of the fuel include gasoline,
Examples include kerosene, light oil, and heavy oil. The fuel composition of the present invention has a good cleaning action such as preventing deposits from adhering to a carburetor or an injector of an internal combustion engine and removing deposits. In the fuel composition of the present invention, in addition to the above-mentioned fuel additive composition, other detergents, cetane number improvers, antioxidants, metal deactivators within a range not impairing the object of the present invention. , Known additives for fuels such as fluidity improvers, corrosion inhibitors, organometallic complex fuel additives, demulsifiers, oxygen-containing fuel additives can be blended in appropriate amounts.

[0034]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Reference Example 1 In a 2 liter autoclave, polybutene (Mw: 9
87) 1,100 g, cetyl bromide 6.4 g (0.021 mol)
And 115 g (1.2 mol) of maleic anhydride were added, the atmosphere was replaced with nitrogen, and the mixture was reacted at 240 ° C. for 5 hours. The temperature was lowered to 215 ° C, unreacted maleic anhydride and cetyl bromide were distilled off under reduced pressure, the temperature was lowered to 140 ° C, and the mixture was filtered. The yield of the obtained polybutenyl succinic anhydride was 1,099 g. In a 2 liter separable flask, 500 g of the obtained polybutenyl succinic anhydride and tetraethylene pentamine (TEP
A: manufactured by Tosoh Corporation) 64 g (0.34 mol) and mineral oil 3
00 g was added and the mixture was reacted at 150 ° C. for 2 hours under a nitrogen stream. The temperature was raised to 200 ° C., unreacted TEPA and generated water were distilled off under reduced pressure, the temperature was lowered to 140 ° C., and filtration was performed. The yield of the obtained polybutenyl succinimide was 784 g. 5
In a 00 ml separable flask, 240 g of the above polybutenyl succinimide and 28 g of boric acid were placed and reacted at 150 ° C. for 4 hours under a nitrogen stream. The produced water was distilled off under reduced pressure at 150 ° C, the temperature was lowered to 140 ° C, and the mixture was filtered. The yield of the obtained reaction product was 231 g.

Example 1 A hexadecylphenol (1-
319 g (1 mol) of a reaction product of hexadecene and phenol and 200 g of xylene were added and stirred to be uniform. Heated to 70 ° C, 48 wt% NaOH aqueous solution 80
g was added and xylene was refluxed for 2 hours under a nitrogen stream to distill off water. Transfer the reaction solution to a 1 liter autoclave,
It was pressurized to 10 kg / cm ² G with carbon dioxide and reacted at 155 ° C. for 1 hour. The temperature was lowered to 80 ° C., the mixture was transferred to a 2 liter flask, 120 g of xylene was added, and the mixture was stirred so as to be uniform. Further, 250 g of 20 wt% sulfuric acid was added over 30 minutes and the reaction was carried out for 1 hour. The reaction solution was washed with water, phase-separated, and then filtered to remove xylene. The yield of the obtained reaction product was 312 g. In a 500 ml flask, 300 g of the obtained reaction product and 100 g of hexadecylphenol were placed, and the temperature was 250 ° C. under a nitrogen stream.
The reaction was carried out for 5 hours at 250 ° C., and the produced water and hexadecylphenol were distilled off under reduced pressure at 250 ° C. The yield of the obtained reaction product was 195 g. This product was a mixture of compounds represented by the following formulas (VIII) and (IX).

[0036]

[Chemical 15]

Example 2 The procedure of Example 1 was repeated, except that dodecylphenol (a reaction product of 1-dodecene and phenol) was used instead of hexadecylphenol. This product was a mixture of compounds represented by the following formulas (X) and (XI).

[0038]

[Chemical 16]

Example 3 The procedure of Example 1 was repeated, except that a mixture of dodecylphenol and dinonylphenol (a reaction product of a propylene oligomer and phenol) was used instead of hexadecylphenol. . This product was a mixture of compounds represented by the following formulas (XII) and (XIII).

[0040]

[Chemical 17]

Example 4 The procedure of Example 1 was repeated, except that nonylphenol (a reaction product of a propylene oligomer and phenol) was used instead of hexadecylphenol. This product was a mixture of compounds represented by the following formulas (XIV) and (XV).

[0042]

[Chemical 18]

Example 5 The procedure of Example 1 was repeated except that 5-octylsalicylic acid and p-octylphenol were used. This product was a compound represented by the following formula (XVI).

[0044]

[Chemical 19]

Example 6 Example 6 was repeated except that a mixed alkylphenol having 11, 12, 13, 14, and 15 carbon atoms (a reaction product of a propylene oligomer and phenol) was used in place of hexadecylphenol. It carried out similarly to 1. This product was a mixture of compounds represented by the following formulas (XVII) and (XVIII).

[0046]

[Chemical 20]

Example 7 262 g of p-dodecylphenol (reaction product of propylene oligomer and phenol) was placed in a 1-liter flask.
(1.0 mol) and xylene (262 g) were added and stirred to be uniform. The mixture was heated to 70 ° C., 80 g of a 48 wt% sodium hydroxide aqueous solution was added, and xylene was refluxed for 2 hours under a nitrogen stream to distill off water. The reaction solution was transferred to a 1 liter autoclave, pressurized with carbon dioxide to 10 kg / cm ² G and reacted at 155 ° C. for 1 hour. Cool down to 80 ℃,
Transferred to a 1 liter flask and stirred. Further, 250 g of a 20 wt% sulfuric acid aqueous solution was added dropwise over 30 minutes, and the reaction was carried out for 1 hour. The reaction solution was washed with water, phase-separated, and then filtered to remove xylene. The yield was 257g. Furthermore, it refine | purified and obtained 5-dodecyl salicylic acid. In a 500 ml flask, 110 g of 5-dodecylsalicylic acid and 100 g of dodecylcatechol (a reaction product of propylene oligomer and catechol) were added, and the mixture was reacted at 250 ° C for 5 hours under a nitrogen stream, and the produced water and unreacted product were depressurized at 250 ° C. Distilled off. This product has the formula (X
IX) was the main component.

[0048]

[Chemical 21]

Example 8 Example 8 was carried out in the same manner as in Example 7 except that dodecylcatechol was used instead of p-dodecylphenol. This product was mainly composed of a compound represented by the following formula (XX).

[0050]

[Chemical formula 22]

Example 9 The procedure of Example 7 was repeated, except that p-dodecylphenol was replaced with 4-dodecyl-1-naphthol and dodecylcatechol was replaced with p-dodecylphenol. did. This product was mainly composed of a compound represented by the following formula (XXI).

[0052]

[Chemical formula 23]

Example 10 In a 300 ml flask, 166 g (0.25 mol) of the mixture obtained in Example 1 and 7.7 g (0.125 mol) of boric acid.
Mol) was added and the mixture was reacted under a nitrogen stream at 150 ° C. for 4 hours, then the produced water was distilled off under reduced pressure and pressure filtration was performed. The yield of the obtained boron-containing reaction product was 128 g, and the boron content was 0.7.
It was 5% by weight.

Examples 11 to 20 Preparation of fuel additive composition (ashless detergent dispersant) 75% by weight of the dispersant (boric acid-treated polybutenyl succinimide) obtained in Reference Example 1 and Example 1 25% by weight of the substituted hydroxyaromatic ester derivative obtained in 10 to 10 was blended to prepare a fuel additive composition.

Examples 21 to 30 Preparation of Samples for Evaluation of Fuel Additive Compositions 10% by weight of fuel additive compositions of Examples 11 to 20 based on the total amount of the composition in mineral oil of 500 neutral fraction.
(Substituted hydroxy aromatic ester derivative 2.5% by weight, dispersant 7.5% by weight) was blended to prepare a sample for evaluation of a fuel additive composition. The performance of this fuel additive composition was evaluated by the following hot tube test. The results are shown in Table 1. (Hot tube test conditions) An evaluation sample of 0.3 ml / hr and air of 10 ml / min were continuously flowed in a glass tube having an inner diameter of 2 mm for 16 hours while keeping the temperature of the glass tube at 310 ° C. The lacquer attached to the glass tube and the color sample were compared, and a rating of 10 points for transparent and a score of 0 for black were given, and the weight of the lacquer attached to the glass tube was measured. The higher the score, the more
The smaller the lacquer weight, the higher the performance.

Comparative Example 1 The procedure of Example 1 was repeated except that dodecylphenol (a reaction product of a propylene oligomer and phenol) was used in place of hexadecylphenol, and further purified to give 5-dodecyl. Salicylic acid was obtained. This 5-dodecylsalicylic acid and p-cresol were reacted in the same manner as in Example 1. This product has the formula (X
It was a compound represented by XII).

[0057]

[Chemical formula 24]

Next, in mineral oil of 500 neutral fraction,
Based on the total amount of the composition, 2.5% by weight of the substituted hydroxyaromatic ester derivative and 7.5% by weight of the dispersant of Reference Example 1 were blended to prepare a sample for evaluating an additive composition for fuel, The performance was evaluated by the tube test. The results are shown in Table 1.

Comparative Example 2 Comparative Example 1 except that salicylic acid was used in place of 5-dodecylsalicylic acid and hexadecylphenol (a reaction product of 1-hexadecene and phenol) was used in place of p-cresol in Comparative Example 1. It carried out similarly to.
This product was a compound represented by the following formula (XXIII).

[0060]

[Chemical 25]

Then, a sample for evaluating an additive composition for fuel was prepared in the same manner as in Comparative Example 1 using the above compound, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 3 Comparative Example 1 except that 5-t-butylsalicylic acid was used in place of 5-dodecylsalicylic acid and pt-butylphenol was used in place of p-cresol in Comparative Example 1.
It carried out similarly to. This product has the following formula (XXIV)
Was a compound represented by.

[0063]

[Chemical formula 26]

Then, a sample for evaluating an additive composition for fuel was prepared in the same manner as in Comparative Example 1 using the above compound, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 4 A sample for evaluation of a fuel additive composition was prepared in the same manner as in Comparative Example 1 using the compound represented by the following formula (XXV), and its performance was evaluated by a hot tube test. did. The results are shown in Table 1.

[0066]

[Chemical 27]

Comparative Example 5 A sample for evaluation of a fuel additive composition was prepared in the same manner as in Comparative Example 1 using the compound represented by the following formula (XXVI), and its performance was evaluated by a hot tube test. did. The results are shown in Table 1.

[0068]

[Chemical 28]

Comparative Example 6 A compound for evaluation of a fuel additive composition was prepared in the same manner as in Comparative Example 1 using a compound represented by the following formula (XXVII),
The performance was evaluated by a hot tube test. The results are shown in Table 1.

[0070]

[Chemical 29]

[0071]

[Table 1]

As can be seen from Table 1, the fuel additive compositions of Examples 21 to 30 using the fuel additive of the present invention are the substituted or unsubstituted hydroxy aromatic ester derivatives of Comparative Examples 1 to 4. , A hydroxy group-free aromatic ester derivative of Comparative Example 5, octadecyl-3- of Comparative Example 6
(3,5-di-t-butyl-4-hydroxyphenyl)
Compared with the one using propionate, it showed good results in the hot tube test and showed excellent high temperature stability (high temperature detergency).

Examples 31 and 32 Preparation of Fuel Composition JIS K-2204 No. 2 gas oil was blended with 2% by weight of the substituted hydroxyaromatic ester derivative obtained in Examples 1 and 2, based on the total amount of the fuel composition. , A fuel composition was prepared. The performance of this fuel composition was evaluated by the following shell four-ball test. The results are shown in Table 2.

(Shell four-ball test) ASTM D-278
The amount of wear (mm) was determined in accordance with No. 3, under the conditions of a load of 2 kg, an oil temperature of 50 ° C., and a time of 30 minutes.

Comparative Example 7 The performance of JIS K-2204 No. 2 gas oil was evaluated by a shell four-ball test. The results are shown in Table 2.

[0076]

[Table 2]

From Table 2, it can be seen that the fuel additive of the present invention has excellent wear characteristics.

Examples 33 and 34 Preparation of Fuel Composition A polyoxyethylene compound represented by C ₁₆ H ₃₃ NH (CH ₂ CH ₂ O) ₆ H based on JIS K-2204 No. 2 diesel fuel, based on the total amount of the fuel composition. 1% by weight and 0.2% by weight of the substituted hydroxyaromatic ester derivative obtained in Examples 1 and 2 were blended to prepare a fuel composition. The performance of this fuel composition was evaluated by the following storage stability test. The results are shown in Table 3.

(Storage stability test) Fuel composition 1
The amount of sludge produced was measured after collecting 00 ml, corking a cork and leaving it in the dark for 2 months.

Comparative Example 8 A fuel composition was prepared by blending JIS K-2204 No. 2 gas oil with 1% by weight of the polyoxyethylene compound used in Examples 33 and 34 based on the total amount of the fuel composition.
The performance of this fuel composition was evaluated by a storage stability test. The results are shown in Table 3.

[0081]

[Table 3]

From Table 3, it can be seen that the fuel composition of the present invention has excellent storage stability.

[0083]

The fuel additive comprising the specific substituted hydroxyaromatic ester derivative of the present invention can be blended with fuel oil for internal combustion engines. In addition, this fuel additive is useful as an ashless detergent, and as an antiwear agent for injection pumps accompanying the low sulfur content of light oil, and a particulate reducing agent such as a polyoxyethylene compound was added. It is also useful as a storage stabilizer for fuel oil. Further, a fuel additive composition containing a dispersant is excellent in high-temperature stability (high-temperature detergency), has fine particle dispersibility, and is useful as an excellent detergent-dispersant for fuel oil. Prevents deposits from attaching to vaporizers and injectors,
The deposit can be removed. Therefore, this fuel additive composition can be blended with gasoline, kerosene, light oil, heavy oil, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Katsumata Satokeura City, Chiba Prefecture 1280 Kamizumi Idemitsu Kosan Co., Ltd.

Claims (8)

[Claims] 1. A compound represented by the general formula (I):[In the formula, R¹And R²Are organics each having 6 or more carbon atoms
Represents a group, which may be the same or different
, A, b, c, d and e are 1 ≦ a ≦ 3, 1 respectively.
≦ b ≦ 3,0 ≦ c ≦ 3,1 ≦ d ≦ 3,1 ≦ e ≦ 3,3 ≦
The relationship of (a + b + e) ≦ 6 and 1 ≦ (c + d) ≦ 5 is satisfied.
Indicates the integer to add. Also, R¹And R²If there are multiple
Are multiple R¹And R²Are the same in each
Or they may be different. ] And general formula (II)[In the formula, R³, R^FourAnd R^Five Each has 6 or more carbon atoms
, Which are the same or different
, F, g, h, i, j, k and m are respectively
0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g) ≦ 3, 0 ≦ h
≦ 4,0 ≦ i ≦ 3,1 ≦ (h + i) ≦ 6,0 ≦ j ≦ 3
1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g + h + i + m)
Indicates an integer that satisfies the relations ≦ 8 and 1 ≦ (j + k) ≦ 5.
You Also, R ³, R^FourAnd R^Five If there are multiple
R³, R^FourAnd R^Five Are the same in each
Or they may be different. ] A substituted hydroxy represented by
At least one selected from aromatic ester derivatives
Fuel additive consisting of. 2. A substituted hydroxyaromatic ester derivative has the general formula (III): [In the formula, R ¹ and R ² each represent an organic group having 6 or more carbon atoms, and they may be the same or different, and b, d and e are 1 ≦ b ≦ 3, 1 ≦, respectively. d ≦
3, an integer that satisfies the relationship of 1 ≦ e ≦ 3 and 2 ≦ (b + e) ≦ 5. Further, when R ¹ and R ² are a plurality, the plurality of R ¹ and R ² may be different even in the same in each. ] Or general formula (III ') [In the formula, R ³ , R ⁴ and R ⁵ each represent an organic group having 6 or more carbon atoms, and they may be the same or different, and h, n, k and m are each 0 ≦ h. ≦ 4
0 ≦ n ≦ 2, 1 ≦ (h + n) ≦ 6, 1 ≦ k ≦ 3, 1 ≦ m
An integer that satisfies the relationship of ≦ 3 and 2 ≦ (h + n + m) ≦ 7 is shown. Further, if R ^3, R ⁴ and R ⁵ have more than one plurality of R ^3, R ⁴ and R ⁵ may be different even in the same in each. ] The fuel additive according to claim 1, which is represented by the formula 3. A fuel additive containing (a) at least one member selected from the substituted hydroxyaromatic ester derivatives represented by the general formulas (I) and (II) and (b) a dispersant. Composition. 4. The fuel additive composition according to claim 3, wherein the substituted hydroxyaromatic ester derivative is represented by the general formula (III) or (III ′). 5. General formulas (I) and (II) for fuels
A fuel composition containing at least one selected from the substituted hydroxyaromatic ester derivatives represented by: 6. A fuel containing (a) at least one selected from the substituted hydroxyaromatic ester derivatives represented by the general formulas (I) and (II) and (b) a dispersant. A fuel composition. 7. The fuel composition according to claim 5, wherein the substituted hydroxyaromatic ester derivative is represented by the general formula (III) or (III ′). 8. The fuel composition according to claim 5, which is a fuel composition for an internal combustion engine.