JPH07278577A - Fuel oil additive composition and fuel oil composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition high in the deposit-removing ability and cleanliness holding ability in the intake system for fuel, comprising a basic nitrogen atom-bearing compound component, a component such as an alkylene oxide adduct to a hydroxy compound, and a specific antioxidant. CONSTITUTION:This fuel oil additive composition comprises (A) a basic nitrogen atom-bearing compound of formula I (R<1> is a 6-28C alkyl or an alkenyl; (n) is 5-30; AO is a 2-6C oxyalkylene) such as a polyetheramine, (B) an alkylene oxide adduct to a 10-50C alcohol, alkylphenol or alkenylphenol, of e.g. formula II (R<2> is a 6-28C alkyl or an alkenyl; (m) is 5-30; A'O is a 2-6C oxyalkylene), an esterified or etherified product thereof, and polyisobutene or poly-alpha-olefin, and (C) an antioxidant capable of extending the liquid state holding time at 280 deg.C for the mixture of the components A and B by 1.5-30 times.

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. . In other words, the deposits generated in the intake valves and intake ports cause a decrease in engine output, deterioration of drivability, an increase in exhaust gas, etc., but engines that are becoming increasingly sophisticated in recent years are subject to such deposits. I'm sensitive to it.

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 and preventing adhesion in the gasoline intake system such as the carburetor and intake valve, and purifying combustion chamber formation.

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.

However, in recent years, engines that have become more and more sophisticated require a higher level of cleaning of the intake system, especially the intake valve, and in particular, in order to make the detergent act more effectively, carrier oil is used. Are required to have appropriate heat resistance (the intake valve has a high temperature of 200 to 300 ° C.), compatibility with a detergent, and solubility of contaminants in the intake system (engine oil and oxidative deterioration of fuel).

In order to solve such a problem, a fuel for an internal combustion engine using two different compounds as a carrier oil (Japanese Patent Laid-Open No. 173194/1990), the following general formula RO- (AO) _m- ( Fuel oil additive containing a compound represented by C ₃ H ₆ NH) _n H
No. 229797), a fuel oil additive comprising a polyether compound and a compound having an amine nitrogen atom and an oxyalkylene group or polyamine (JP-A-4-11408).
No. 9) are proposed.

However, these fuel oil additives are
None of these were sufficiently satisfactory in terms of cleaning effect.

[0009]

Under such circumstances, the inventors of the present invention have conducted diligent research and, as a result, have mixed a fuel oil additive with a large amount of an antioxidant to some extent under specific heating conditions of the fuel oil additive. The present invention has been completed based on the finding that it is possible to improve the heat resistance and to greatly improve the cleaning effect while maintaining an appropriate thermal decomposability by preventing the oxidization.

That is, the present invention provides the following component (a),
(B) and (c) (a): Compound having basic nitrogen atom (b): Alcohol having 10 to 50 carbon atoms, alkylene oxide adduct of alkylphenol or alkenylphenol, esterified product or etherified product thereof,
Polyisobutene or poly-α-olefin (c): Fuel oil additive composition containing an antioxidant that prolongs the liquid retention time at 280 ° C. of the mixture of component (a) and component (b) by 1.5 to 30 times It relates to things.

The compound having a basic nitrogen atom as the component (a) is not particularly limited as long as it is a compound conventionally used as a detergent for a fuel intake system. For example, the following (a)
To (d), etc., and each can be used alone or in combination of two or more kinds. (A) Succinimide derivative represented by the general formula (4)

[0012]

[Chemical 3]

The compound (4) can be obtained, for example, by reacting a polyolefin such as polybutene with maleic anhydride to obtain a polyalkenyl succinic anhydride, and then reacting this with a polyamine such as polyethylene polyamine.

(B) Polyalkenylamine represented by the general formula (5) R ^5- (NHCH ₂ CH ₂ ) _b -NH-X ² (5) (In the formula, R ⁵ is a polyalkenyl group having a molecular weight of 700 or more. X ² represents a hydrogen atom or a polyalkyl group having a molecular weight of 700 or more, and b represents an integer of 0 to 5) This compound (5) is obtained by, for example, chlorinating a polyolefin and then reacting this with a polyamine. Can be obtained by

(C) Benzylamine derivative represented by the general formula (6)

[0016]

[Chemical 4]

These compounds (6) can be obtained, for example, by reacting an alkylated phenol, formaldehyde and polyamine by the Mannich reaction.

(D) Polyetheramines represented by the general formula (1) RO- (AO) _n -R'-NH ₂ (1) (In the formula, R represents a hydrocarbon group having 6 to 34 carbon atoms. Show, R '
Represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and n AO
May be the same or different and each represents an oxyalkylene group having 2 to 6 carbon atoms, and n represents a number of 5 to 30. )

In the compound (1), the compound represented by the general formula (1)
In the above, the structure of the alkyleneoxy group of AO is not particularly limited, and may be a form in which an alkylene oxide of any structure or a mixture of isomers thereof is added.

Of these, the component (a) is (d)
Polyether amines (1) are preferable, and especially the following general formula (2)

[0021]

[Chemical 5]

Polyetheramines represented by the formula (wherein R ¹ represents an alkyl group or an alkenyl group having 6 to 28 carbon atoms, AO and n have the same meanings as described above) are preferred.

Of the component (b), the alkylene oxide adduct of alcohol, alkylphenol or alkenylphenol having 10 to 50 carbon atoms has 10 to 10 carbon atoms.
Examples of the alcohol of 50 include various saturated or unsaturated natural alcohols, linear monohydric alcohols by the Ziegler method, branched alcohols obtained by oxo reaction and Guerbet reaction, and the like. Specifically, decyl alcohol,
Natural alcohols such as lauryl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, oleyl alcohol, elaidyl alcohol, and erca alcohol, linear monohydric alcohols having 10 to 30 carbon atoms by the Ziegler method, carbons by the oxo method A branched alcohol having several 10 to 24, a branched alcohol having 16 to 24 carbon atoms by the Guerbet method, and the like are used.

The alkylphenol or alkenylphenol having 10 to 50 carbon atoms has 4 to 4 carbon atoms.
Those having 1 or 2 0, particularly 4 to 30 alkyl or alkenyl groups are preferable. Specifically, butylphenol, amylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, cumylphenol, alkylphenol having an alkyl group having 18 to 24 carbon atoms, α-olefin having 6 to 30 carbon atoms and phenol are reacted. The obtained alkylphenol etc. can be used conveniently.

The alkylene oxide added to these alcohols, alkylphenols or alkenylphenols has 2 to 6 carbon atoms, especially 3 or 4 carbon atoms.
Are preferred. The structure is not particularly limited, and any isomer or mixture may be used.
The number of added moles of alkylene oxide is preferably 10 or more. When it is less than 10, the cleaning effect at the intake valve becomes weak, which is not preferable. Further, the upper limit of the number of added moles is not particularly limited, but if it exceeds 50, it is economically unfavorable because production is difficult.

These alkylene oxides can be added to the alcohol or alkylphenol by a conventional method. For example, if necessary, a suitable solvent may be used, and alcohol may be added in the liquid or in the form of gas while reacting with alcohol in the presence of caustic while heating to 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 sequentially added first may be performed.

It is also possible to use an esterified product or an etherified product of an alkylene oxide adduct of the above alcohol, alkylphenol or alkenylphenol. Examples of the esterified product include esters with fatty acids having 1 to 21 carbon atoms, Examples of etherified products include alcohols having 1 to 20 carbon atoms, for example, those having 20 or less carbon atoms among the above alcohols, and ethers with methanol, ethanol, propanol, butanol and the like.

Also, polyisobutene or poly-α-olefin can be used as the component (b).

Of these, as the component (b), the following general formula (3)

[0030]

[Chemical 6]

(In the formula, R ² represents an alkyl group or an alkenyl group having 6 to 28 carbon atoms, m A'O may be the same or different and each represents an oxyalkylene group having 2 to 6 carbon atoms. , M represents a number of 5 to 30).

The blending ratio of the component (a) and the component (b) in the fuel oil additive composition of the present invention is a weight ratio of (a) :( b) = 5: 95 to 99: 1, particularly 30:70.
It is preferably about 98: 2.

As the antioxidant of the component (c), any of antioxidants such as phenol-based, amine-based, organic sulfur-based, phosphite-based, and composite-based thereof may be used so long as they improve the heat resistance of the fuel oil additive. Can be used, but for example, styrenated phenol (Sumitomo Chemical Industries Sumili
zer S), n-octadecyl-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) -propionate (Sumitizer B manufactured by Sumitomo Chemical Co., Ltd.
P-76, Ciba-Geigy IRGANOX107
6), 2,2'-methylene-bis (4-methyl-6-t)
-Butylphenol) (Sumitomo Chemical Industries Sumil
izer MDP-S), 2-t-butyl-6- (3 '
-T-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate (Sumitizer GM manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol) )
(Sumitomo BBM- manufactured by Sumitomo Chemical Co., Ltd.
S), alkylated bisphenol (Sumitomo Chemical Co., Ltd.
Sumilizer NW), 1,3,5-Tris (4
-T-Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate (Sumitomo Chemical Co., Ltd., Sumi
riser BP-179), tetrakis [methylene-
3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Sumitizer BP-101 manufactured by Sumitomo Chemical Co., Ltd., IRGANOX 1010 manufactured by Ciba Geigy), 3,9-bis [ Two
-[3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane (Sumitize made by Sumitomo Chemical Co., Ltd.
rGA-80), hindered phenol compound (IRGANOX L108 manufactured by Ciba-Geigy), medium-polymer hindered phenol (IR manufactured by Ciba-Geigy)
GANOX L109), sulfur-based hindered phenol (IRGANOX L115 manufactured by Ciba-Geigy),
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX 24 manufactured by Ciba-Geigy)
5), 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 25 manufactured by Ciba-Geigy)
9), 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine (Ciba Geigy IRG
ANOX 565), 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane (Adeka Stab Mark AO-3 manufactured by Asahi Denka Co., Ltd.)
0), phenols such as a reaction product of phenyl-β-naphthylamine and acetone (Antigene DA manufactured by Sumitomo Chemical Co., Ltd.); alkylated diphenylamine (Sumilizer 9A manufactured by Sumitomo Chemical Co., Ltd.), N, N′-diaryl-p-phenylene. Diamine (Sumitizer MXA manufactured by Sumitomo Chemical Co., Ltd.), N, N'-di-se
c-Butyl-p-phenylenediamine (Sumitizer BPA manufactured by Sumitomo Chemical Co., Ltd.), N, N'-di-s
Modified product of ec-butyl-p-phenylenediamine (Sumitizer BPA-M1 manufactured by Sumitomo Chemical Co., Ltd.),
N, N'-diphenyl-p-phenylenediamine (Sumitomo Chemical Co., Ltd. Antigene P), N-phenyl-N'-isopropyl-p-phenylenediamine (Sumitomo Chemical Co., Antigene 3C), N-phenyl-N '. -1,3-Dimethylbutyl-p-phenylenediamine (Sumitomo Chemical Co., Ltd. Antigene 6
C), other p-phenylenediamine derivatives (such as Sumilizer 4M manufactured by Sumitomo Chemical Co., Ltd.), a reaction product of diphenylamine and acetone (Nocrac B manufactured by Ouchi Shinko Chemical Co., Ltd.), 4,4′-bis (α, α) -Dimethylbenzyl) diphenylamine (Ouchi Shinko Chemical Industry Co., Ltd.
Amines such as Nocrac CD); 2,2,4-trimethyl-1,2-dihydroquinoline polymer (Antigene RD-G manufactured by Sumitomo Chemical Co., Ltd.), 6-ethoxy-
Reaction products of 2,2,4-trimethyl-1,2-dihydroxyquinoline (Sumitomo Chemical Co., Ltd. Antigene AW) and other (Sumitomo Chemical Co., Ltd. Antigene FR, AS, etc.) amines and ketones; Type antioxidant (Sumitizer A manufactured by Sumitomo Chemical Co., Ltd.
Z, the same MPS, the same 9L); and dl-α-tocopherol and the like.

Of these, Sum is preferred.
ilizer S, BBM-S, BP-101, NW,
BPA, 4M, IRGNOX 1010, L109, L
115, 245, 259, 565, Nocrac B, Nocrac CD, ADEKA STAB MARK AO-30, An
titanium DA, RD-G, AS, dl-α-tocopherol, and more preferably Sum.
ilizer BBM-S, BP-101, NW, IR
GANOX 1010, L109, L115, 245,
259, Nocrac B, Nocrac CD, ADEKA STAB MARK AO-30, Antigen DA, RD
-G, AS, dl-α-tocopherol are mentioned, and particularly preferable ones are ADEKA STAB MARK AO-3.
0, AntigenDA, RD-G, AS, and Nocrac B.

These antioxidants may be conventionally added in a small amount to fuels and gasoline additives for the purpose of preventing oxidation during storage, but in the present invention, the components (a) and (b) are used. The mixture is mixed in an amount such that the liquid holding time at 280 ° C. is extended by 1.5 to 30 times, preferably 2.0 to 10 times. Here, the liquid retention time in the present invention means a mixture of the component (a) and the component (b), or (a)
20 μl of a 50% kerosene solution of the mixture of the component, the component (b) and the component (c) was dropped onto an aluminum disk having a diameter of 5 cm which was heated and maintained at a surface temperature of 280 ° C., and the additive was volatilized to retain a liquid state. It means the time until it disappears (average value of 5 times). Therefore, "extending the liquid retention time by 1.5 to 30 times" means [(a) + (b) + (c) liquid retention time] / [(a) + (b) liquid retention time] = 1.5 ~
It shows that it is 30. Therefore, the blending amount thereof varies depending on the liquid-holding time extension performance of the antioxidant, and those having excellent extension performance can obtain the same effect with a smaller amount than those having poor extension performance. If the extension of the liquid holding time is less than 1.5 times, the heat resistance and cleanability are not sufficiently improved, and if it exceeds 30 times, the cleanability is rather deteriorated and the cost is not 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 and metal deactivators.

[0038]

EFFECT OF THE INVENTION The fuel oil additive composition of the present invention is excellent in the ability to remove deposits in the intake system of fuel and to maintain cleanliness.

[0039]

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 1 was used to measure the deposit amount after the engine was operated. As the fuel used,
In this test, gasoline having an intake valve deposit of 1520 mg / 1 valve was used, and an additive having the composition and concentration shown in Table 1 was added thereto. The results are also shown in Table 1. The test conditions and the compounds used are as shown below.

<Conditions> Test engine: Toyota 1G-EU engine (2000
cc) Test mode: Idle with the following 4 steps as one cycle 30 seconds 1300 rpm 60 seconds 1850 rpm 120 seconds 3000 rpm 60 seconds Test time: 120 hours (1600 cycles)

<Compound used>

[0043]

[Chemical 7]

C-1: Sumilizer NW (manufactured by Sumitomo Chemical Co., Ltd.) c-2: Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.) c-3: ADEKA STAB MARK AO-30 (manufactured by Asahi Denka Co., Ltd.) c-4 : IRGANOX L109 (Ciba-Geigy) c-5: IRGANOX L115 (Ciba-Geigy) c-6: IRGANOX 245 (Ciba-Geigy) c-7: IRGANOX 259 (Ciba-Geigy) c -8: IRGANOX 1010 (manufactured by Ciba Geigy) c-9: Nocrac B (manufactured by Ouchi Shinko Chemical Co., Ltd.) c-10: dl-α-tocopherol (manufactured by Wako Pure Chemical Industries) c-11: Antigen DA (Sumitomo Chemical Co., Ltd.)

[0045]

[Table 1]

As is clear from Table 1, the product of the present invention containing an antioxidant in the range of extending the liquid holding time by 1.5 to 30 times was shown to have an excellent intake valve cleaning effect. .

Claims (7)

[Claims] 1. The following components (a), (b) and (c) (a): a compound having a basic nitrogen atom (b): an alkylene oxide addition of an alcohol, alkylphenol or alkenylphenol having 10 to 50 carbon atoms. Thing, its esterified product or etherified product,
Polyisobutene or poly-α-olefin (c): Fuel oil additive composition containing an antioxidant that prolongs the liquid retention time at 280 ° C. of the mixture of component (a) and component (b) by 1.5 to 30 times object. 2. The mixing ratio of the component (a) and the component (b) is
The fuel oil additive composition according to claim 1, wherein the weight ratio of (a) :( b) = 5: 95 to 99: 1. 3. The component (c) is the component (a) and the component (b).
The liquid holding time at 280 ° C of the mixture of
The fuel oil additive composition according to claim 1 or 2, which is an antioxidant that extends 0 times. 4. The compound having a basic nitrogen atom as the component (a) is represented by the following general formula (1) RO- (AO) _n -R'-NH ₂ (1) (wherein R represents a carbon number of 6 to 34 hydrocarbon group, R '
Represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and n AO
May be the same or different and each represents an oxyalkylene group having 2 to 6 carbon atoms, and n represents a number of 5 to 30. )
The fuel oil additive composition according to any one of claims 1 to 3, which is a polyether amine represented by: 5. A compound having a basic nitrogen atom as the component (a) is represented by the following general formula (2): (In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 28 carbon atoms, n AO may be the same or different,
Each represents an oxyalkylene group having 2 to 6 carbon atoms, n
Indicates a number of 5 to 30. The fuel oil additive composition according to any one of claims 1 to 3, which is a polyether amine represented by the formula (4). 6. The component (b) is represented by the following general formula (3): (In the formula, R ² represents an alkyl group or an alkenyl group having 6 to 28 carbon atoms, m A′O may be the same or different, each represents an oxyalkylene group having 2 to 6 carbon atoms, and m is The fuel oil additive composition according to any one of claims 1 to 5, which is a compound represented by a number of 5 to 30). 7. A fuel oil composition containing 0.1 to 50,000 ppm of the fuel oil additive composition according to any one of claims 1 to 6.