JPH07179869A - Fuel oil additive composition and fuel oil composition - Google Patents

Abstract

PURPOSE:To obtain an additive composition excellent in the ability to remove deposit from a fuel intake system and retentivity of the ability to clean. CONSTITUTION:This additive composition is prepared by mixing a polyisobuteneamine (a) represented by the formula {wherein PIB is polyisobutenyl; R<1> is hydrogen, methyl or vinyl; and R<2> is a 1-20C alkyl or a group represented by the formula: (CHR<3>)m[X<1>(CH2)p]-qX<2>R<4> (wherein R<3> is hydrogen or a group represented by NR<5> (wherein R<5> is hydrogen or a 1-10C alkyl or (CH2)rX<3>R<6> (wherein R<6> is hydrogen or a 1-10C alkyl; X<3> is O or NH; and (r) is an integer of 2-4)]; R<4> is hydrogen or a 1-10C alkyl; (m) is an integer of 1-4; (p) is an integer of 2-4; (q) is an integer of 0-10; and q x X<1>(CH2)p groups may be the same or different from each other]} with a polyetheramine (b) represented by the formula: R<7>-O-(AO)nCH2CH2CH2NH2 (wherein R<7> is a 10-50C hydrocarbon residue; A is a 2-6C alkylene; and (n) is 10-50) in an (a) to (b) ratio of 80/2- to 30/70.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel oil additive composition having an excellent cleaning effect on a fuel intake system and a fuel oil composition containing the same.

[0002]

2. Description of the Related Art It is known that when sludge, deposits, and other deposits are generated in the fuel system and combustion chamber of an internal combustion engine, the function of the engine is degraded and exhaust gas is adversely affected. . That is, the deposits generated in the intake valve, combustion chamber, intake port, etc.
Although it causes a decrease in engine output, deterioration of drivability, an increase in exhaust gas, etc., an engine that is becoming more and more sophisticated in recent years is sensitive to such a deposit.

Above all, the deposit in the intake valve has become a serious problem particularly in the electronically controlled fuel injection device whose mounting rate in passenger cars has been increasing recently. That is, the electronically controlled fuel injection device controls the gasoline mixture precisely and is effective not only for improving engine performance but also for saving fuel and improving exhaust gas. There was a problem that the injected gasoline hits the deposit, and the control of the gasoline mixture was lost, resulting in an impact on drivability.

Various fuel oil additives have been added to gasoline and the like for the purpose of removing deposits, preventing adhesion, and cleaning the combustion chamber in a gasoline intake system such as a carburetor and an intake valve.

As the fuel oil additive conventionally used, an oil-soluble activator having a basic nitrogen such as an amino group or an amide group in a molecule called a detergent is used in combination with a mineral oil or a synthetic oil as a carrier oil. What you have done is known.
The cleaning agent acts on the dirt substance that is trying to accumulate in the intake system of the engine, and keeps the intake system clean.
Carrier oil is also used in order to exert the action of this detergent. As the carrier oil, a viscous and thermally stable liquid with a high boiling point is generally used, and it acts as a dispersion medium to exert the function of a detergent, and acts to protect the metal surface of the intake system with a liquid film. Have. Synthetic oils used as carrier oils include polyolefins and poly (oxyalkylene) s (Japanese Patent Publication No.
6-48556), esters and the like are known.

As the detergent, conventionally, polyisobutene amine-based agents have been widely and generally used, and Japanese Patent Publication No. 56-48556, Japanese Patent Publication No. 55-3927, Japanese Patent Publication No. 55-25489, and Japanese Patent Publication No. 55-25489. Kosho 61-33
No. 016, etc. disclose polyether amine-based detergents. However, although the polyisobutene amine-based detergent is inexpensive, the cleaning effect is inferior, and the cleaning effect of the above polyether amine-based detergent is not satisfactory.

Therefore, as a fuel oil additive having a more excellent cleaning effect, a fuel oil additive containing a compound represented by the following general formula RO- (AO) _m- (C ₃ H ₆ NH) _n H Kaihei 3-
229797), a polyether amine compound,
Fuel oil additive comprising a compound having an amine nitrogen atom and an oxyalkylene group or a polyamine (JP-A-4-11)
No. 4089) has been proposed.

However, these are generally expensive, and a higher level of cleaning is required for engines that are becoming more and more sophisticated in recent years.

Therefore, an object of the present invention is to provide a fuel oil additive which is cheaper and has an excellent cleaning effect.

[0010]

Under such circumstances, as a result of intensive studies, the present inventors have found that when polyisobutene amines and specific polyether amines are used in combination at a specific ratio, the synergistic effects of both are extremely clean. The present invention has been completed by finding that a fuel oil additive composition having excellent effects can be obtained at low cost.

That is, according to the present invention, the following components (a) and (b) are mixed in a weight ratio of (a) :( b) = 80: 20-3.
The present invention relates to a fuel oil additive composition containing 0:70, and a fuel oil composition containing the additive composition. (A) Polyisobutene amines represented by the general formula (1)

[0012]

[Chemical 2]

[In the formula, PIB represents a polyisobutenyl group, R ¹ represents a hydrogen atom, a methyl group or a vinyl group, and R ²
Alkyl group or 1 to 20 carbon atoms is _{^{- (CHR 3) m [X}} 1 (CH 2) p]
_q X ² R ⁴ {R ³ is a hydrogen atom or a methyl group, and X ¹ and X ² are-.
O- or -NR ⁵ - [R ⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or ^{_{(CH 2) r X 3 R}} 6 (R 6 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X ³ is -O- or -NH-
And r represents an integer of 2 to 4. ) Represents a group represented by. ], R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 4, p is an integer of 2 to 4, and q is
Represents an integer of 0 to 10. The q X ¹ (CH ₂ ) _p may be the same or different. } Shows group represented by. ] (B) Polyetheramines represented by the general formula (2) R ⁷ -O- (AO) _n -CH ₂ CH ₂ CH ₂ NH ₂ (2) (In the formula, R ⁷ has 10 to 50 carbon atoms. Is a hydrocarbon residue, A is an alkylene group having 2 to 6 carbon atoms, and n is 10
Indicates a number from -50. )

The polyisobutene amine represented by the general formula (1) which is the component (a) used in the present invention is a carbonyl-functionalized polyisobutene as described in a conventionally known method such as JP-A-2-261806. [PIB]-
It can be produced by reacting COR ¹ with amines H ₂ NR ² and then hydrogenating the reaction product.

The carbonyl-functionalized polyisobutene can be produced, for example, by passing a molecular oxygen-containing gas through the polyisobutene at 140 to 200 ° C. under normal pressure or pressure. It can also be produced by other methods such as ozonation of polyisobutene. The carbonyl functionalized polyisobutene preferably has an average molecular weight of about 600-10,000 and an oxygen content of 1-10% w / w.

A solvent may or may not be used in the reaction of the carbonyl-functionalized polyisobutene and the amines, and the carbonyl-functionalized polyisobutene itself may be used as the solvent. The reaction is 50 to 250 ° C., especially 12
It is preferably carried out at 0 to 180 ° C. under reduced pressure to increased pressure.
As the amines, monoamines, that is, those in which R ² is an alkyl group having 1 to 20 carbon atoms can be used, but in order to introduce an appropriate amount of nitrogen atom into the product, an aliphatic polyamine is used. Preference is given to using. Examples of the aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine and dipropylenediamine. The amount of aliphatic polyamine used is from about 0.2 to 2. per mole of carbonyl-functionalized polyisobutene.
It is preferably 5 mol.

As the amines, alcohol amines such as N- (2-aminoethyl) ethanolamine and N, N-bis (2-hydroxyethyl) ethylenediamine, and ether amines can also be used.

The hydrogenation of the imines, which are intermediates formed by the reaction of carbonyl-functionalized polyisobutenes with amines, can be carried out using a hydrogenation catalyst, but the imines can be heated (preferably under normal pressure). It is preferable to carry out by reacting formic acid (50 to 130 ° C.). The amount of formic acid with respect to imines is a formic acid: imines = 0.5: molar ratio.
1-5: 1, especially 0.5: 1-2: 1 are preferred.

The above-mentioned reaction is carried out by reacting carbonyl-functionalized polyisobutenes with amines in the presence of hydrogen and a hydrogenation catalyst or in the presence of formic acid without isolation of intermediate imines. It can also be performed in one step. The general formula (2) which is the component (b) used in the present invention
The polyether amines represented by, for example, have 10 carbon atoms.
~ 50 alcohols or alkylene oxide adducts of alkylphenols can be obtained by cyanoethylation with acrylonitrile followed by hydrogenation. The cyanoethylation reaction is carried out by heating and stirring in the presence of a strong alkali catalyst such as alkali hydroxide. Also, the hydrogenation can be carried out in the presence of a hydrogenation catalyst such as Raney nickel.

Here, the alcohol used as the raw material is
For example, various saturated or unsaturated natural alcohols, linear monohydric alcohols by the Ziegler method, branched alcohols obtained by oxo reaction or Guerbet reaction, and the like can be used.

Particularly preferably, natural alcohols such as decyl alcohol, lauryl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, oleyl alcohol, elaidyl alcohol, and erucic alcohol, and those having 10 to 30 carbon atoms by the Ziegler method are used. A chain monohydric 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 a total carbon number of 10 to 50 can be used, and an alkyl group having a carbon number of 4 to 30 is particularly preferable.

For example, specifically, butylphenol, amylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, cumylphenol, or an alkylphenol having an alkyl group having 18 to 24 carbon atoms and an α-olefin having 6 to 30 carbon atoms. Alkylphenol and the like, which are obtained by reacting a phenol with phenol, can be preferably used.

The alkylene oxide to be added to the above alcohol or alkylphenol has 2 to 6 carbon atoms, and particularly preferably 3 or 4 carbon atoms,
The structure is not particularly limited, and any isomer or mixture may be used. The number of added moles of alkylene oxide must be 10 or more. If it is less than 10, the cleaning effect on the intake valve will be weakened, and the purpose of the present invention will not be met. If it exceeds 50, manufacturing problems will be involved, which is economically undesirable.

The alkylene oxide adduct can be prepared by various methods. For example, an alcohol or an alkylphenol is added in the form of a liquid or a gas of an alkylene oxide having 2 to 6 carbon atoms in the presence of a catalyst such as an alkali hydroxide while heating, using a suitable solvent, if necessary, to react them.

Random addition polymerization in which two or more kinds of alkylene oxides are mixed and reacted, or block addition polymerization in which several kinds of alkylene oxides are sequentially added may be carried out.

The blending ratio of the components (a) and (b) in the fuel oil additive composition of the present invention is such that the weight ratio is (a) :( b).
= 80: 20 to 30:70, but 70:30 to 4
0:60 is preferable.

The fuel oil additive composition of the present invention also comprises
Further, when (c) a mineral oil or a synthetic oil is blended, a more excellent deposit removing effect and a detergency maintaining effect are exhibited. In particular, the effect of synthetic oil is excellent, especially olefin polymers such as poly-α-olefins and polybutenes, alkylene oxide adducts of alcohols or alkylphenols, alkylene oxide polymers, particularly alkylene oxides such as propylene oxide and butylene oxide. The adduct and its ester or ether compound are excellent. The mixing ratio of these is {(a) +
(B)} :( c) = 95: 5 to 30:70, especially 80:
20-50: 50 is preferable.

The fuel oil additive composition of the present invention is used in a fuel oil such as gasoline or light oil in an amount of 0.1 to 50,000 pp.
It is preferable to add m, especially 1 to 20,000 ppm.

The fuel oil additive composition of the present invention can be used in combination with other fuel oil additives such as rust preventives, demulsifiers, antioxidants and metal deactivators.

[0031]

Industrial Applicability The fuel oil additive composition of the present invention is excellent in deposit removing ability and cleanliness retaining ability of the fuel intake system and is inexpensive.

[0032]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 The fuel oil additive composition having the composition shown in Table 2 was used to measure the deposit amount after the engine was operated in the test mode shown in Table 1. As the fuel, Showa Shell Regular Gasoline with 5% of C10 diene added was used.
Additives having the compositions and concentrations shown in Table 2 were added thereto. The results are shown in Table 2. The evaluation criteria and the compounds used are as shown below.

[0034]

[Table 1]

<Evaluation Criteria> ⊚: Large deposit removal effect ○: Deposit removal effect Δ: Some deposit removal effect x: Increased deposit amount

[0036]

[Chemical 3]

[0037]

[Table 2]

As is apparent from Table 2, the product of the present invention in which the component (a) and the component (b) are blended in a specific ratio is used when each is used alone and when both components are blended outside the specific ratio. Compared with the above, not only the deposits in the fuel intake system and the combustion chamber can be removed very well, but also high cleanliness can be maintained.

Claims (3)

[Claims] 1. A fuel oil additive composition comprising the following components (a) and (b) in a weight ratio of (a) :( b) = 80: 20 to 30:70. object. (A) Polyisobutene amines represented by the general formula (1): [In the formula, PIB represents a polyisobutenyl group, R ¹ represents a hydrogen atom, a methyl group or a vinyl group, and R ² represents 1 carbon atom.
20 alkyl group or a _{^{- (CHR 3) m [X}} 1 (CH 2) p] q X 2 R 4 {R 3
Is a hydrogen atom or a methyl group, X ¹ and X ² are —O— or —
NR ⁵ - [R ⁵ is an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, or ^{_{(CH 2), r X 3}} R 6 (R 6 is a hydrogen atom or a carbon atoms 1 to 1
0 is an alkyl group, X ³ is —O— or —NH—, and r is 2
Indicates an integer of ˜4. ) Represents a group represented by. ], R ⁴
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is 1
~ 4, p is an integer of 2 to 4, q is an integer of 0 to 10. The q X ¹ (CH ₂ ) _p may be the same or different. } Shows group represented by. ] (B) Polyetheramines represented by the general formula (2) R ⁷ -O- (AO) _n -CH ₂ CH ₂ CH ₂ NH ₂ (2) (In the formula, R ⁷ has 10 to 50 carbon atoms. Is a hydrocarbon residue, A is an alkylene group having 2 to 6 carbon atoms, and n is 10
Indicates a number from -50. ) 2. The fuel oil additive composition according to claim 1, further comprising (c) a mineral oil or a synthetic oil. 3. A fuel oil composition containing 0.1 to 50,000 ppm of the fuel oil additive composition according to claim 1 or 2.