JPH0532982A - Fuel additive - Google Patents

Abstract

PURPOSE:To obtain a fuel additive, containing an alkylene oxide adduct of a specific amine compound and an aliphatic amine, etc., and excellent in cleaning effects on inlet systems, especially inlet valves of fuels. CONSTITUTION:The objective additive containing (A) a compound expressed by the formula RO-(A<1>O)m-(C3H6NH)nH (R is 10-50C hydrocarbon; A<1> is 2-6C alkylene; m is an integer of 10-50; n is 1, 2 or 3) and (B) one or more of aliphatic amines, aliphatic ether amines and their alkylene oxide adduct compounds having <=600 molecular weight. Furthermore, the component (A) is obtained by cyanoethylating, e.g. an alkylene oxide adduct of a 10-50C alcohol or alkylphenol with acrylonitrile, then hydrogenating or further repeating the cyanoethylation of the resultant compound with acrylonitrile and hydrogenation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fuel additive, particularly a gasoline additive and a fuel additive composition containing the same,
More specifically, the present invention relates to a fuel additive excellent in the cleanliness of a fuel intake system, particularly an intake valve, and a fuel additive composition using the same.

[0002]

2. Description of the Related Art If deposits such as sludge and deposits are generated in the fuel system and combustion chamber of an internal combustion engine, the function of the engine is deteriorated and the exhaust gas is adversely affected. A fuel detergent, especially a gasoline detergent, is added to gasoline for the purpose of removing deposits and preventing adhesion of a gasoline intake system such as a carburetor and an intake valve, and cleaning the inside of a combustion chamber. Deposits generated in intake valves and intake ports cause a decrease in engine output, deterioration of 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. Of these, intake valve deposits have recently become a major problem. Particularly recently, in Japan, the mounting rate of electronically controlled injection devices for passenger cars has been increasing. The electronically controlled fuel injection device precisely controls the gasoline mixture, and is effective not only for improving engine performance, but also for saving fuel and improving exhaust gas. However, if the deposit adheres to the intake valve, the gasoline injected from the injector hits the deposit, and the control of the gasoline mixture is disturbed. As a result, drivability is adversely affected.

In recent passenger cars, crankcases
It is equipped with a ventilation system (PCV system). These are for returning the blow-by gas leaking into the crankcase from the combustion chamber through the gap between the piston ring and the cylinder wall to the intake system, and burning the unburned gas in the blow-by in the combustion chamber. In the blow-by gas, unburned gas (intake air-fuel mixture or partially oxidized hydrocarbon), engine oil, NOx and SOx exist. The NOx and SOx are dissolved in water generated during combustion and converted into nitric acid and sulfuric acid. When this blow-by gas enters the intake system, it becomes a cause of contamination. In particular, the acid in blow-by has an adverse effect on the detergent and reduces the detergency.

Various fuel additives have been proposed to solve these problems. For example, Japanese Patent Publication No. 56-4855
6, JP-B-55-39278, JP-A-55-254.
Polyetheramines are disclosed in Japanese Patent Publication No. 89 and Japanese Patent Publication No. 61-33016. However, these polyether amines are not yet sufficient in cleaning the intake valve. There is a demand for a fuel additive that exhibits an excellent cleaning effect even under severe driving conditions. Under the circumstances as described above, the present invention provides a fuel additive having excellent cleanliness of the entire intake system and good thermal decomposition property, which is easy to synthesize, and a fuel additive composition containing the same. The purpose is to do.

[0005]

In order to solve such problems of the prior art, the inventors of the present invention have arrived at the present invention as a result of intensive research. That is, the present invention is, (1) (A) compound represented by the general formula (1) R-O- (A 1 O) m - (C 3 H 6 NH) n H (1) ( wherein, R Is a hydrocarbon residue having 10 to 50 carbon atoms, A ¹ is an alkylene group having 2 to 6 carbon atoms, m is an integer of 10 to 50,
n represents an integer of 1 to 3. ), And (B) a fuel additive containing at least one of an aliphatic amine having a molecular weight of 600 or less, an aliphatic ether amine and an alkylene oxide compound thereof, and (2) the fuel addition according to (1) above. Formula (2)
Or (3) R ^1- (A ² O) γ-R ² or R ^1- (A ² O) γOCR ² (2)

[Chemical 5] (In the formula, each R ¹ is an alkyl group having 1 to 30 carbon atoms,
R ² represents hydrogen or an alkyl group having 1 to 20 carbon atoms, A ² represents an alkylene group having 3 to 4 carbon atoms, and γ represents an integer of 1 to 50. The present invention provides a fuel additive composition containing the compound represented by the formula (1).

The compound represented by the above-mentioned general formula (1) is, for example, an alkylene oxide adduct of an alcohol or an alkylphenol having 10 to 50 carbon atoms which is cyanoethylated with acrylonitrile and then hydrogenated, or cyanoethyl with acrylonitrile. It can be obtained by repeating hydrogenation and hydrogenation. The cyanoethylation reaction can be obtained by heating and stirring under a strong alkaline catalyst such as caustic. Further, hydrogenation can be obtained by reacting in the presence of a hydrogenation catalyst such as Raney nickel. However, the method for synthesizing the compound represented by the general formula (1) is not limited to such a method.

In the case of synthesizing by the above production method, the alcohol ROH (where R is the same as R in the general formula (1)) as a raw material needs to have 10 to 50 carbon atoms. Various saturated or unsaturated natural alcohols, linear monohydric alcohols by the Ziegler method, and branched alcohols obtained by oxo reaction or Guerbet reaction can be used. Particularly preferred are natural alcohols such as decyl alcohol, lauryl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, oleyl alcohol, elaidyl alcohol, and erka alcohol, and straight-chain one having 10 to 30 carbon atoms by the Ziegler method. A polyhydric alcohol, a branched alcohol having 10 to 24 carbon atoms by the oxo method, a branched alcohol having 16 to 24 carbon atoms by the Guerbet method, and the like are used.

The alkylphenol used as a raw material has one or two alkyl groups having 4 to 40 carbon atoms,
An alkylphenol having 10 to 50 carbon atoms can be used, and particularly preferably, the alkyl group has 4 to 30 carbon atoms.
The ones are good. For example, specifically butylphenol,
Amylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, cumylphenol, alkylphenol having an alkyl group having 18 to 24 carbon atoms, alkylphenol obtained by reacting an α-olefin having 6 to 30 carbon atoms with phenol, and the like It can be preferably used.

The alkylene oxide to be added to the above alcohol, alkylphenol, etc. must be an alkylene oxide having 2 to 6 carbon atoms, and particularly propylene oxide and butylene oxide (1,2-; 2,
3-; 1,3-; and 1,4-; or mixtures thereof)
Is preferred. The addition mole number of alkylene oxide is 10
Must be above. If it is less than 10, the cleaning effect at the intake valve is weakened, and the object of the present invention is not met. The upper limit of the number of moles added is not particularly limited, but if it exceeds 50, it is economically unfavorable because production is difficult.

The alkylene oxide adduct can be prepared by various methods. For example, an alkylene oxide having 2 to 6 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, etc.) in a liquid or gas state is heated while heating an alcohol in the presence of a catalyst such as caustic, if necessary, using a suitable solvent. Add and react. Random addition polymerization in which two or more kinds of alkylene oxides are mixed and reacted, or block addition polymerization in which one kind of alkylene oxide is first sequentially added may be performed. Further, n in the general formula (1) is 1 to
It is an integer of 3, and if n is 4 or more, emulsification occurs when water is mixed in the fuel, which is not preferable.

An aliphatic amine used in the present invention,
The aliphatic ether amine and its alkylene oxide compound (hereinafter abbreviated as amines) have a molecular weight of 6
It is preferably not more than 00, and further represented by the general formula (4)
Any of the compounds represented by (6) is particularly preferred. If the molecular weight exceeds 600, the effect of suppressing the influence of acid in blow-by becomes low, which is not preferable.

The compound represented by the general formula (4) is as follows.

[Chemical 6] (In the formula, R ³ is an aliphatic hydrocarbon group having 6 to 30 carbon atoms,
X and Y each represent hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an amino group. ) Specifically, primary amines such as heptylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, eicosylamine, behenylamine, dioctylamine, dilaurylamine, distearylamine, ditallowamine and the like 2 Tertiary amines such as primary amines, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethyloleylamine, dilaurylmonomethylamine, trioctylamine or stearylpropylenediamine, beef tallow Diamines such as propylenediamine are exemplified. More preferably, it is a primary amine.

The compound represented by the general formula (5) is as follows.

[Chemical 7] (In the formula, R ⁴ is an aliphatic hydrocarbon group having 3 to 30 carbon atoms, R ⁴ is
⁵ represents hydrogen or an aliphatic hydrocarbon group having 1 to 16 carbon atoms. However, the carbon number of R ⁴ + R ⁵ is 10 to 32. n
Is an integer of from 1 to 5, L is - (CH ₂₎ z - represents a. However, z represents the integer of 1-5. ) The compound of the general formula (5) has the formula (7)

[Chemical 8] (In the formula, R ⁴ and R ⁵ have the same meanings as described above) and are derived from the alcohol according to a conventional method.

For example, the alcohol represented by the general formula (7) can be cyanoethylated with acrylonitrile and then hydrogenated, or can be further obtained by repeating cyanoethylation with acrylonitrile and hydrogenation. The cyanoethylation reaction can be obtained by heating and stirring under a strong alkaline catalyst such as caustic.
Further, the hydrogenation can be obtained by reacting under a hydrogenation catalyst such as Raney nickel. However, the method for synthesizing the compound represented by the general formula (5) is not limited to such a method.

Examples of such alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, and linear alcohols having 11 to 30 carbon atoms such as higher alcohols by the Ziegler method. ,
One having a branched alkyl group having 7 to 30 carbon atoms such as a branched alcohol having 7 to 18 carbon atoms obtained by an oxo reaction, a Guerbet alcohol having 16 to 24 carbon atoms obtained by a Guerbet reaction, or an oleyl alcohol; Examples thereof include polyhydric alcohol. Examples of the compound represented by the general formula (5) include those disclosed in JP-A-3-7797.

The compound represented by the general formula (6) is as follows.

[Chemical 9] (In the formula, R ⁶ is an aliphatic hydrocarbon group having 6 to 24 carbon atoms, A 6
³ represents an alkylene group having 2 to 4 carbon atoms, and x and y represent an integer of 1 or more. However, x + y is 2 to 10. ) In the general formula (6), the number of carbon atoms represented by R ⁶ is 6 to 24.
As the aliphatic hydrocarbon group of, a linear or branched alkyl group, for example, a hexyl group, a heptyl group, an octyl group,
Examples thereof include nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and docosyl group; alkenyl groups such as myristoyl group, palmitolyl group, oleyl group and linoleyl group. Of these, preferred are aliphatic hydrocarbon groups having 8 to 20 carbon atoms, and particularly preferred are decyl, dodecyl and oleyl groups. Examples of the alkylene group having 2 to 4 carbon atoms represented by A ³ include an ethylene group, a propylene group, a butylene group, and a combination of two or more kinds thereof, for example, a combination of an ethylene group and a propylene group. Of these, the ethylene group is preferred. x and y are each an integer of 1 or more, and x + y is 2 to 10, preferably 2 to 6. Examples of the compound represented by the general formula (6) include those disclosed in JP-A-62-68891 and JP-B-63-32837.

The compounding ratio of the compound represented by the general formula (1) and amines is 1: 0.1 to 1, preferably 1: 1, by weight.
It is in the range of 0.1 to 0.5 and is prepared by a conventional method.
For example, it is performed by stirring both at room temperature or under slight heating. At least one amine is used in the present invention, and two or more amines may be used in combination.

The fuel additive of the present invention, when used in combination with mineral oil or synthetic oil generally called carrier oil,
Exhibits excellent effect of deposit removal and cleanliness retention effect. In particular, general formula (2) or (3) R ^1- (A ² O) γ-R ² or R ^1- (A ² O) γOCR ² (2)

[Chemical 10] (In the formula, each R ¹ is an alkyl group having 1 to 30 carbon atoms,
R ² represents hydrogen or an alkyl group having 1 to 20 carbon atoms, A ² represents an alkylene group having 3 to 4 carbon atoms, and γ represents an integer of 1 to 50. The combination composition with a synthetic oil represented by the formula (1) is more excellent. Examples of these synthetic oils include alkylene oxide adducts of alcohols or alkylphenols, particularly alkylene oxide adducts such as propylene oxide and butylene oxide, and ester or ether compounds thereof. Here, such an ester compound can be obtained, for example, by reacting an alkylene oxide adduct of alcohol or alkylphenol with a corresponding carboxylic acid at a high temperature using a slight amount of an acid catalyst or another metal catalyst. Further, the ether compound can be obtained, for example, by using an alcohol or an alkylene oxide adduct of alkylphenol and an alkali to synthesize an alcoholate and further reacting it with a corresponding alkyl halide. However, the synthetic method of these compounds is not limited to such a method. The mixing ratio of these is
0.05 to 1 part by weight of the fuel additive according to the present invention
20 parts by weight is preferred. It is more preferably 0.5 to 5 parts by weight.

The fuel additive composition of the present invention is blended in fuel oil in an amount of 0.1 to 50,000 ppm. The higher the blending amount, the better the cleanliness, but 1 to 20,000ppm
The result is sufficiently excellent in practical use. The fuel additive or fuel additive composition of the present invention may be used in combination with other fuel additives such as rust preventives, demulsifiers, antioxidants and metal deactivators. By thus blending the fuel additive of the present invention, a fuel composition having excellent cleanliness can be obtained.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples, Comparative Examples and Experimental Examples, but the present invention is not limited thereto. Synthesis Example 1 Nonylphenol (BO) ₁₇ (
2-butylene oxide (17 mol adduct) 0.40 mol was placed in a 1-liter four-necked flask, and 0.48 mol of acrylonitrile while heating and stirring at a temperature of 76 to 80 ° C with 8 mmol of caustic potash as a catalyst under a nitrogen atmosphere. Was added dropwise over 3 hours, and after the reaction, the mixture was reacted at 76 to 80 ° C. for 2 hours, then caustic potash was neutralized with acetic acid, and excess acrylonitrile was removed under reduced pressure to obtain a cyanoethylated product. 300 g of this cyanoethylated product was put into a 1 liter autoclave, and 20 k was obtained using Raney nickel as a catalyst.
Hydrogenation was performed by applying a hydrogen pressure of g / cm ² to obtain the compound of A-1 in Table 1 which is a compound represented by the general formula (1).

Synthesis Examples 2 to 4 In the same manner as in Synthesis Example 1, octadecylphenol 20 mol adduct of propylene oxide, 2-heptylundecanol 20 mol of 1,2-butylene oxide and adduct 10 mol of propylene oxide, Compounds of A-2, A-3 and A-4 in Table 1 were obtained from 20 mol of 1,2-butylene oxide adduct of oleyl alcohol.

Synthesis Examples 5 to 7 Nonylphenol (BO) ₁₅ H (15-mol 1,2-butylene oxide adduct of nonylphenol) 0.40
Mole was placed in a 1 liter, 4-necked flask and further 1.
An alcoholate was prepared by adding 1 equivalent of potassium hydroxide and dehydrating under reduced pressure for 2 hours while heating and stirring at 110 ° C. To the obtained alcoholate, 0.48 mol of octyl bromide was dropped under a nitrogen atmosphere at 100 ° C. while controlling the reaction temperature to synthesize ether. After the reaction, the reaction product was washed with water and dried to obtain the target ether compound (C-2 compound in Table 3). Further, by adding 15 mol of 1,2-butylene oxide to nonylphenol, the compound of C-1 in Table 3 was added, and by adding 20 mol of propylene oxide to octadecylphenol, the compound of C-3 in Table 3 was added. Obtained.

EXAMPLES Compounds represented by the general formula (1) (A-1 to A-4 in Table 1), amines shown in Table 2 and synthetic oils shown in Table 3 obtained in the above-mentioned synthesis examples. Was used to prepare the fuel additive or the fuel additive composition of the present invention. The preparation was carried out by diluting to 50% with an aromatic solvent. The obtained products of the present invention are called Additives 1-14. Comparative Examples Additives 1 to 8 according to comparative products having the compositions shown in Table 4 were prepared in the same manner as in Examples.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

Experimental Example 1 (Sludge Dispersibility Test) For the additives shown in Table 4, a dispersibility test was conducted by the following method for the purpose of investigating how the effect of preventing sludge deposition was affected by the presence or absence of an acid. I did. The hexane-insoluble, chloroform-soluble part of the sludge scraped from the crankcase of the engine after running a high mileage was added to a commercially available regular gasoline containing a test additive as a chloroform solution so that the sludge amount was 600 ppm. Additive concentration 100ppm, then 50
The dispersion state of the sludge was examined 30 minutes after the addition of the sludge solution in units of ppm. Without the additive, the sludge is insoluble in gasoline and will precipitate. The minimum additive concentration at which there was no sludge precipitation was determined. In addition, sludge dispersibility test in the presence of acid using nitric acid ethanol solution,
The same sludge dispersibility test was carried out with a nitric acid concentration of 30 ppm coexisting in the test sample. The results are summarized in Table 5. As can be seen from the results in Table 5, the composition containing the compound represented by the general formula (1) according to the present invention and the amines, or the composition containing the synthetic oil further contains an acid such as nitric acid. Even if it is present, the sludge dispersibility is not significantly reduced.

[0029]

[Table 5]

Experimental Example 2 (Engine Evaluation Test) For the purpose of investigating the cleaning performance of the composition of the present invention, an engine evaluation test was conducted under the following test conditions. (Test conditions) Engine: Nissan CA18S (1800 cc) Gasoline: Commercially available regular gasoline Additive: 300 ppm (against gasoline) Operating conditions: Step speed (rpm) Time (min) 1 800 5 2 1500 1500 20 3 1900 30 4 4000 5 The above operation mode was set as one cycle, the engine was operated for 200 cycles (200 hours), and the additives were evaluated.

The condition of the intake system (intake valve, intake port, manifold, carburetor) before and after the test was evaluated by disassembling the engine and visually observing the degree of deposit adhesion. However, the intake valve was weighed before and after the test to determine the deposit adhesion amount. Regarding the engine, a new intake system was used. The degree of cleanliness retention before and after the test was determined according to the following criteria. The criteria for determining the effect were based on the results without addition of the fuel additive. The results are shown in Table 6.
From Table 6, any of the additive containing the compound represented by the general formula (1) according to the present invention and amines or the composition further containing synthetic oil has detergency, and particularly contains synthetic oil. The composition is superior. (Judgment criteria) x: Increase in deposit amount −: Same as result of no addition Δ: Slightly more cleaning effect than result of no addition ○: Almost no deposit ◎: No deposit adhesion

[0032]

[Table 6]

[0033]

Industrial Applicability The fuel additive of the present invention has a function as a detergent for fuel oil, and has a detergent effect on all of the carburetor, manifold, intake port and intake valve.
Further, the fuel additive or the fuel additive composition of the present invention has a small effect of acid in blow-by and exhibits excellent detergency. Therefore, it is excellent in cleaning the entire intake system under harsh conditions, especially when running under high load.

Claims (3)

[Claims] 1. A compound represented by the general formula (1): R—O— (A ¹ O) m — (C ₃ H ₆ NH) n H (1) (wherein R represents 10 carbon atoms). To a hydrocarbon residue, A ¹ is an alkylene group having 2 to 6 carbon atoms, m is an integer of 10 to 50,
n represents an integer of 1 to 3. ), And (B) at least one kind of an aliphatic amine having a molecular weight of 600 or less, an aliphatic ether amine, and an alkylene oxide compound thereof. 2. The fuel additive according to claim 1, further comprising the general formula (2) or (3) R ^1- (A ² O) γ-R ² or R ^1- (A ² O) γOCR ² (2 ) [Chemical 1] (In the formula, each R ¹ is an alkyl group having 1 to 30 carbon atoms,
R ² represents hydrogen or an alkyl group having 1 to 20 carbon atoms, A ² represents an alkylene group having 3 to 4 carbon atoms, and γ represents an integer of 1 to 50. ) A fuel additive composition containing a compound represented by: 3. The fuel additive according to claim 1, wherein the compound described in (B) in claim 1 is a compound represented by any one of formulas (4) to (6). [Chemical 2] (In the formula, R ³ is an aliphatic hydrocarbon group having 6 to 30 carbon atoms,
X and Y each represent hydrogen or an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an amino group. ) [Chemical 3] (In the formula, R ⁴ is an aliphatic hydrocarbon group having 3 to 30 carbon atoms, R ⁴ is
⁵ represents hydrogen or an aliphatic hydrocarbon group having 1 to 16 carbon atoms. However, the carbon number of R ⁴ + R ⁵ is 10 to 32. n
Is an integer of from 1 to 5, L is - (CH ₂₎ z - represents a. However, z represents the integer of 1-5. ) [Chemical 4] (In the formula, R ⁶ is an aliphatic hydrocarbon group having 6 to 24 carbon atoms, A 6
³ represents an alkylene group having 2 to 4 carbon atoms, and x and y represent an integer of 1 or more. However, x + y is 2 to 10. )