JPH05117672A - Gasoline additive composition - Google Patents

Abstract

(57) [Summary] [Structure] The gasoline additive composition of the present invention comprises a polyoxyalkylene glycol monoester having an average molecular weight of 500 to 5,000 and / or an average molecular weight of 500 to 5,000.
A diester of polyoxyalkylene glycol and monosuccinimide and / or bissuccinimide, an amino acid ester compound of polyoxyalkylene glycol, and a lubricating oil fraction having a viscosity of 3 mm ² / s to 35 mm ² / s (100 ° C.). Consists of. [Effect] Use of the gasoline additive composition of the present invention can reduce deposits and improve cleanliness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gasoline additive composition, and more particularly to a gasoline additive composition capable of significantly reducing deposits on intake valves of automobile engines.

[0002]

2. Description of the Related Art Conventionally, polyalkenyl succinimide, hydroxypolyether polyamine, etc. have been known as detergents for carburetors and engines in automobiles, and polyalkenyl succinimide and oxy compounds have xylene as a composition for gasoline addition. Those which are dispersed or dissolved in the above organic solvent are also known.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an improvement in this type of gasoline additive composition, and in particular, it is an object of the invention to provide a gasoline additive composition capable of significantly reducing deposits in intake valves.

[0004]

The gasoline additive composition of the present invention has an average molecular weight of 50 represented by the following general formula (1).
0-5000 polyoxyalkylene glycol monoester and / or polyoxyalkylene glycol diester represented by the following general formula (2) having an average molecular weight of 500-5000, and monosuccinimide represented by the following general formula (3): Or or a bissuccinimide represented by the following general formula (4), an amino acid ester compound of polyoxyalkylene glycol represented by the following general formula (5), and a viscosity of 3 mm ² / s to 35 mm ² / s (100 ° C.) It consists of a lubricating oil fraction.

General formula (1) R ₂ O—R ₁ — (OR ₁ ) ₁ —OCOR ₃ General formula (2) R ₃ COO—R ₁ — (OR ₁ ) ₁ —OCOR ₃ (wherein R ₁ is alkylene The group, R ₂ is a hydrogen, aliphatic, cycloaliphatic, or aromatic hydrocarbon group, and R ₃ is a fatty acid residue.)

[0006]

[Chemical 3]

(In the formula, R ₄ represents an olefin oligomer group having 30 or more carbon atoms, R ₅ represents a C _{2 to} C ₄ alkylene group, and m represents an integer of 1 to 10.)

[0008]

[Chemical 4]

[0009] (wherein, R _6, R ₆ 'is an olefin oligomer group having at least 30 carbon atoms, R ₇ represents an alkylene group of C ₂ ~C _4, n is an integer of 0.) In formula (5) R'-O- (R "O) n -CO- (CH 2) m - NH 2 ( wherein, R 'is hydrogen, or a lower alkyl group, R" is .m showing a lower alkylene group , 2 to 8, and n represents an integer of 5 to 110.) In formulas (1) and (2), R ₁ is an alkylene group, preferably ethylene, propylene, butylene, or a mixed alkylene group thereof. .

R ₂ represents hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbon group, and particularly methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
(T) -butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, tolyl,
Xylyl, phenethyl, p-methoxyphenyl, cyclohexyl and cyclopentyl groups are preferred.

R ₃ represents a fatty acid residue, and acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, n-decanoic acid, n-undecanoic acid, n-dodecanoic acid (laurin Acid), n-pentadecanoic acid, n-heptadecanoic acid, n-hexadecanoic acid (palmitic acid), n-octadecanoic acid (stearic acid), n-
Esterification residue of eicosanoic acid, n-docosanoic acid (behenic acid), n-pentaeicosanoic acid, n-heptaeicosanoic acid, n-hexaeicosanoic acid, n-octaeicosanoic acid, n-triacontanoic acid, etc. Groups. It is also possible to use mixed fatty acids derived from natural products such as fish oil fatty acids, beef tallow fatty acids, coconut oil fatty acids, etc., and preferably hydrogenated fatty acids thereof.

These polyoxyalkylene glycol esters are preferably those having an average molecular weight of 500 to 5,000, preferably 1,000 to 3,000. When the average molecular weight is 500 or less, the effect of preventing deposits from deposits is significantly reduced. On the other hand, if it exceeds 5,000, the fluidity on the surface of the intake valve is lowered, and it itself becomes a substance causing deposits, which is not preferable.

Esters of polyoxyalkylene glycol are preferably added so as to be contained in an amount of 10 ppm to 5000 ppm with respect to the total amount of gasoline.

Next, the succinimides in the gasoline additive composition of the present invention will be described.

Generally, the succinimides are obtained by polymerizing a polyolefin polymer obtained by polymerizing olefins in the presence of a polymerization catalyst, first by reacting it with maleic anhydride to give polyalkenyl succinic anhydride. The acid is prepared by reacting a polyalkylene polyamine in the presence of a diluent. Monosuccinimides are prepared by reacting a polyalkenyl succinic anhydride and a polyalkylene polyamine at a molar ratio of 1: 1.
The bissuccinimides are obtained by reacting at a molar ratio of 2: 1.

The polyolefin polymer constituting the succinimide may have 30 or more carbon atoms, preferably 40 to 400 carbon atoms and an average molecular weight of 500 to 5,000 in consideration of compatibility with gasoline. Examples of the olefin used for its production include ethylene, propylene,
C2-C8 alpha-olefins, such as 1-butene, isobutylene, 1-hexene, 2-methylpentene-1, 1-octene, can be used. The polyolefin polymer is preferably polypropylene or polyisobutylene.

Further, as the polyalkylene polyamine,
The number of repeating units in the above formulas (3) and (4) is 1 to 10
It is good to use the thing corresponding to these, and polyethylene polyamine, polypropylene polyamine, polybutylene polyamine, etc. are mentioned, Especially polyethylene polyamine is preferable.

Further, a mixture of the above monosuccinimide and bissuccinimide can also be preferably used.

The succinimides may be added so as to be contained in the amount of 10 ppm to 5000 ppm with respect to the total amount of gasoline.

The polyoxyalkylene glycol monoamino acid ester compound in the composition of the present invention is a polyoxyalkylene glycol represented by the above general formula (5) or an ester of a monoalkyl ether thereof and an ω-amino fatty acid. is there.

In the formula, R'is hydrogen or a lower alkyl group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or an octyl group, and R "is
Lower alkylene group, preferably ethylene group (-CH ₂ -CH
_2- ), propylene group (-CH (CH ₃ ) -CH _2- ), butylene group (-CH
(C ₂ H ₅ ) -CH ₂ )-) is preferable.

As the amino acid ester of polyoxyalkylene glycol, it is preferable to use one having an average molecular weight of 500 to 5,000, preferably 1,000 to 3,000. When the average molecular weight is 500 or less, the effect of preventing deposits from deposits is remarkably reduced. On the other hand, if it exceeds 5,000, the fluidity on the surface of the intake valve is lowered, and it itself becomes a substance causing deposits, which is not preferable.

The monoamino acid ester compound of polyoxyalkylene glycol is 10 pp with respect to the total amount of gasoline.
It is advisable to add so as to contain m to 5000 ppm.

A lubricating oil fraction is added as a carrier oil to the composition of the present invention.

The lubricating oil fraction has good compatibility with the esters of polyoxyalkylene glycol and the amino acid ester of polyoxyalkylene glycol, and enhances the fluidity of these additives after the gasoline is evaporated on the intake valve surface. , Has the function of increasing the solubility in gasoline.

As such a lubricating oil fraction, 3 mm ² / s
A lubricating oil fraction having a viscosity of ˜35 mm ² / s (100 ° C.), for example, a raffinate obtained by subjecting a vacuum distillation distillate oil to an extraction treatment with a solvent such as phenol, furfural, or N-methylpyrrolidone to produce propane or methyl ethyl ketone. Hydrocarbon distillate obtained after solvent dewaxing with a solvent such as the above, and then subjecting it to further hydrorefining to improve hue and remove unstable substances, if necessary (total aromatic carbon number). Percentages based on carbon number (2% to 20%), or mixtures of this hydrocarbon distillate with solvent extracted, solvent dewaxed and solvent deoxidized residual oils can be used. Further, catalytic dewaxing treatment may be performed instead of solvent dewaxing treatment. Further, highly hydrogenated refined oil (percentage of aromatic carbon atoms based on the total carbon number of 2% or less) can also be used. These refined mineral oils are paraffin-based, naphthene-based, etc., either alone or as a mixed type lubricating oil fraction in terms of composition.

If the viscosity of the lubricating oil fraction is less than 3 mm ² / s, it will evaporate together with gasoline and will not function as a carrier oil. If it exceeds 35 mm ² / s, the fluidity will decrease and the lubricating oil fraction itself Becomes a causative substance of the deposit, which is not preferable.

The lubricating oil fraction is preferably used in an amount of 0.5 to 5 parts by weight per 1 part by weight of the total amount of additives.

The gasoline additive composition of the present invention may be diluted with an organic solvent before use or storage. Organic compounds that are inert as such solvents, such as kerosene, benzene, toluene, xylene, ethylbenzene, propylbenzene, trimethylbenzene, chlorobenzene, methoxybenzene, ethoxybenzene, pentane, hexane, heptane, octane, nonane, decane, undecane. , Dodecane, cyclohexane, cyclopentane, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl ether, propyl ether, isopropyl ether, butyl ether, isoamyl ether, isobutyl ether, methyl n-propyl ether, methyl isobutyl ether, methyl Amyl ether and ethyl n-butyl ether are preferred, and toluene, xylene, ethylbenzene and trimethylbenzene are particularly preferred, alone or It may be used in combination with these.

The gasoline to which the composition of the present invention is added is
It is a normal automobile fuel having a gasoline boiling range obtained from straight-distilled naphtha, polymerized gasoline, natural gasoline, or a feed oil obtained by catalytic cracking or thermal cracking or catalytic reforming.

In addition to the above additives, gasoline also contains
An octane number improver such as methyl tert-butyl ether (MTBE), an antistatic agent, a corrosion inhibitor, an antioxidant, an antifreezing agent and a dye may be added to the composition of the present invention.

[0032]

The composition for gasoline addition of the present invention comprises an additive comprising a polyoxyalkylene glycol ester, a succinimide, and a polyoxyalkylene glycol amino acid ester, and a viscosity of 3 mm ² / s.
Since it is composed of a lubricating oil fraction of 35 mm ² / s (100 ° C), it has excellent thermal stability, and in addition to the effect of the additive to prevent deposit adhesion, the lubricating oil fraction functions as a carrier oil for the additive. It is presumed that the composition can be a gasoline additive composition having an excellent dispersion effect in gasoline, and can effectively prevent deposition of deposits on metal surfaces such as intake valves. .

Hereinafter, the composition for adding gasoline of the present invention will be described with reference to Examples.

[0034]

Example 1 Density 0.752 g / cm ² (15 ° C.), Reid vapor pressure 0.750 Kgf / cm ² (37.8 ° C.), aromatic content 40.
2%, olefin content 19.6%, 10% distillation temperature 46.
5 ° C, 50% distillation temperature 99.0 ° C, 90% distillation temperature 14
Sample oil 1 was prepared by adding the following additives to gasoline having a distillation property of 7.0 ° C. so as to contain the following amount with respect to the total amount of gasoline. Preparation conditions are oil temperature 40-60
C. and stirring time was about 30 minutes.

(1) Acetic acid ester of monobutyl ether of polyoxypropylene glycol (average molecular weight 110
0) 50 ppm by weight, (2) commercially available mono-type succinimide {containing 20% by weight of bis-form, substituted with polyisobutenyl group, m = 4 in polyethylene polyamine, average molecular weight 1500 (measured by GPC method) )} 50% by weight, commercially available bis type succinimide {containing 20% by weight of mono-form, substituted with polyisobutenyl group, n = 3 in polyethylene polyamine, average molecular weight 25
00 (measured by the GPC method)} 50 wt.% Of a succinimide mixture of 50 wt.

[0036]

[Chemical 5]

An ester of polyoxyisobutylene glycol monobutyl ether and 3-aminopropionic acid represented by (average molecular weight 1000, decomposition starting temperature 320
℃) 50 ppm by weight, (4) Viscosity 4.7 mm ² / s (100
(° C) lubricating oil (150 neutral oil, nd-M analysis result, percentage of paraffin carbon number to total carbon number 7
0.0%, the percentage of naphthene carbon number to total carbon number 2
5.0%, percentage of aromatic carbon number to total carbon number 5.
0%) is 250 ppm by weight.

This sample oil 1 and a multi-grade oil as an engine oil (SAE engine oil viscosity number 10W30)
Was used to carry out a deposit accumulation test on an intake valve using an actual machine.

This test is based on the Toyota IG connected to a dynamometer.
-Using an FE type engine (in-line 6-cylinder 4-valve system), operating for 100 hours under predetermined conditions, disassembling the engine and taking out the intake valve, and checking the deposit state based on the CRC evaluation criteria. The evaluation was conducted by visual judgment consisting of 10 steps from an evaluation point 1 of the maximum amount of deposits to an evaluation point 10 of no deposits. The intake valve was weighed at room temperature within 1 hour after removing the intake valve from the engine. The weight of the deposited deposit is
It was determined by subtracting the weight of the clean intake valve measured in advance before the test from the weight of the intake valve after the test. The number of samples (intake valves) was n = 12.

The results are shown in the table below.

[0041]

Example 2 A sample oil 2 was prepared by adding the same amount of polyacetic acid ester of polyoxypropylene glycol (average molecular weight 1100) in place of the polyoxypropylene glycol monoether in Example 1.

Using this sample oil 2, the same test as in Example 1 was carried out, and the results are also shown in the table.

[0043]

Example 3 The monoester used in Example 1 was 25 ppm, and the diester used in Example 2 was 25 p.
Sample oil 3 was prepared in the same manner as in Example 1 so as to contain pm.

Using this sample oil 3, the same test as in Example 1 was carried out, and the results are also shown in the table.

[0045]

[Comparative Example] Comparative oil 1 was prepared using only gasoline without adding an additive in Example 1, and the same test results as in Example 1 are shown in the same table.

[0046]

[Table 1]

From these results, it can be seen that all of the sample oils 1 to 3 have a smaller amount of adhered deposits and improved cleanliness than the comparative oil 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // (C10M 169/04 101: 02 145: 38 149: 12) C10N 20:02 30:04 40 : 25 (72) Inventor Kiyomi Adachi 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute

Claims (1)

[Claims] 1. A monoester of polyoxyalkylene glycol having an average molecular weight of 500 to 5000 represented by the following general formula (1) and / or a polyoxyalkylene glycol having an average molecular weight of 500 to 5000 represented by the following general formula (2). A diester, a monosuccinimide represented by the following general formula (3) and / or a bissuccinimide represented by the following general formula (4), and an amino acid ester compound of polyoxyalkylene glycol represented by the following general formula (5), And viscosity 3mm ² / s ~ 35mm ² / s (100 ℃)
A composition for adding gasoline, which comprises a lubricating oil fraction of Formula _{(1) R 2 OR 1 -} (OR 1) l -OCOR 3 formula _{(2) R 3 COO-R} 1 - (OR 1) l -OCOR 3 ( where, R ₁ is an alkylene radical, R ₂ is hydrogen, aliphatic, cycloaliphatic, or aromatic hydrocarbon group, and R ₃ is a fatty acid residue.) (In the formula, R ₄ represents an olefin oligomer group having 30 or more carbon atoms, R ₅ represents a C _{2 to} C ₄ alkylene group, and m is 1 to
Indicates an integer of 10. ) [Chemical 2] (In the formula, R ₆ and R ₆ ′ represent an olefin oligomer group having 30 or more carbon atoms, R ₇ represents a C _{2 to} C ₄ alkylene group,
n shows the integer of 0-10. Shows - "NH ₂ (wherein, R 'is hydrogen, or a lower alkyl _{group, R O) n -CO- (CH} 2) m" is a lower alkylene group) Formula (5) R'-O- (R . M represents an integer of 2 to 8 and n represents an integer of 5 to 110.)